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BACKGROUND OF THE INVENTION
The present invention relates to a method of and an arrangement for continuously thickening of suspensions in a filter thickener with candle-shaped filter elements mounted on individually removable collecting pipes.
Filter thickeners of the above-mentioned general type are known in the art. One of such filter thickeners is described, for example, in the German Offenlegungsschrift No. 2,741,639 and has a filter container in which collecting pipes with filter elements suspended therefrom one behind the other are mounted. The collecting pipes lie near one another on supporting members and can be removed from the filter container in rows. A device for backwashing of filter candles arranged in rows in standing position is disclosed in the Austrian Pat. No. 211,329. Line conduits on which the filter elements are mounted extend horizontally at both sides through the wall of the container. This extension at both sides is very expensive to manufacture and thereby cost consuming. In addition to the great number of the reservoir openings, each line conduit is provided with two check valves which require a great number of valves and fittings. In all methods of this art for thickening of suspensions with a filter thickener, after filtration cycle in the event of depositing (alluvium) with filter aid means, the filter aid means must be supplied via a supply conduit.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a method of and an arrangement for thickening of suspensions, which avoid the disadvantages of the prior art.
More particularly, it is an object of the present invention to provide a method of and an arrangement for thickening of suspensions, which make possible a continuous thickening of suspensions with the aid of a filter thickener.
Still another feature of the present invention is to provide a method of and an arrangement for thickening of suspensions, which allows thickening without or with minimum addition of filter aid means.
In keeping with these objects and with others which will become apparent hereinafter, one feature of the present invention resides, briefly stated, in a method of continuous thickening of suspensions, in which a gaseous backwash medium which is used for backwashing filter elements forms over the filter elements a gas chamber which is separated from the suspension fluid and has an adjustable pressure.
Still another feature of the present invention is an arrangement for continuous thickening of suspensions, in which means are provided for forming over the filter element a gas chamber for the gaseous backwash medium so that the gas chamber is separated from a suspension fluid and has an adjustable pressure.
When the method is performed and the arrangement is designed in accordance with the present invention, they eliminate the above-mentioned disadvantages of the prior art and attain the above-mentioned objects.
The novel features which are considered as characteristic for the present invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view schematically showing a filter thickener in accordance with the present invention;
FIG. 2 is a view substantially corresponding to the view of FIG. 1 but showing a filter thickener in accordance with another embodiment of the present invention with a riser pipe;
FIG. 3 is a view showing a lower part of a filter thickener in accordance with a further embodiment of the present invention with a cleaning device; and
FIG. 4 is a view substantially corresponding to the view of FIG. 3, but showing still a further embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
A thickening filter shown in FIG. 1 has a filter container with a cylindrical part 1 having a conical bottom 2, and a cover 3. The cover 3 is connected by a pair of flanges 4 with a cylindrical intermediate part 5. The latter is connected by a pair of flanges 6 with the cylindrical part 1.
The cylindrical part 1 has in its cylindrical portion a supply conduit 7 for a pulp and a withdrawal conduit 8 for a return flow. A valve 9 serves as a mud discharge. A gas conduit 10 with a control valve 11 is provided in the dome-shaped convex cover 3. A conduit 10' leads to a high-pressure valve 40 which is fed by a not-shown pressure gas source. A level regulating element 12 is further provided in the upper part of the arrangement.
Collecting pipes with their conduits 14 and 14' are mounted on a circular ring 13. Only two conduits are shown in the drawings for the sake of simplification. The number of the collecting pipes can be selected in correspondence with the dimensions of the arrangement and the required filtering surface. Filter elements 15 and 15' are mounted on the collecting pipes.
Each of the conduits 14 and 14' has a gas backwash conduit 31 and 31' having valves 32 and 32', respectively. Valves 33 and 33' serve for locking the filtrate conduits 14 and 14'. A tank 34 serves for receiving the pulp and is connected via a conduit 35 with a pump 36 leading to the conduit 7.
In the arrangement shown in FIG. 2 a riser pipe 41 is additionally provided. It starts substantially in the center of the conical bottom 2 and is mounted between the filter elements 15 and 15'. A pressure conduit 42 leads to the riser pipe 41, and a nozzle 43 can be provided at its end. The pressure conduit 42 has a valve 44 which is connected via a supply conduit 45 with a not-shown pressure gas or pressure liquid source.
In the arrangement shown in FIG. 3 the conical bottom 2 has an extension formed by a tube 46 connected with the bottom by flange 47. A pressure conduit 42 extends through the tube 46 downwardly. Shutters 48 and 49 are provided in the tube 46. A sluice 50 is formed between the shutters 48 and 49. The shutter 48 is actuated by an electric motor 51, whereas the shutter 49 is actuated by an electric motor 52.
In the arrangement of FIG. 4, a further tube 46' is provided between the sluice 50 and the tube 46. The tubes 46 and 46' can be closed by shutters 54, 54' and 48. The shutters 54 and 54' are actuated by electric motors 55 and 56. Washing conduits 42 and 42' and venting conduits 53 and 53' lead to the tubes 46 and 46', respectively.
The inventive method is performed and the inventive arrangement operates in the following manner: A pulp is supplied via the supply conduit 7 into the cylindrical part 1. The solid matter deposits on filtering fabric of the perforated filter elements 15 and forms there a solid matter cake. The liquid released from the solid matter flows via the collecting pipes and their conduits 14 as a filtrate out of the container. The upper part of the container contains an air reserve of approximately 1/6-1/4 of the total volume of the filter container 1. The fluid level in the container is maintained constant with the aid of the level regulating element 12. When the fluid level in the container lowers, for example during backwashing with air, a venting valve 11 opens so that the desired level is again attained. When the fluid level rises in the container, a pressure air valve 30 which is controlled via the level regulating elements 12 opens. When the gas pressure in the cover 3 increases, for example, over 2 bar, the valve 11 also opens and releases gas to the desired nominal value.
During the process of filtration proper, a pulp is supplied from the tank 34 by the pump 36 via the supply conduit 7 into the container. It is filtered at constant pressure. The valves 33 and 33' are open, whereas the valves 32 and 32' are closed. In the chamber above the filter elements 15 a gas pressure of 2 bar takes place. For cleaning, for example, of a segment connected with the conduit 14, the valve 33 is automatically closed and the valve 32 connected with a pressure source of for example 3 bar is opened, without interrupting the filtration in other segments. Pressure air or another pressure gas passes through the conduit 14 and releases the filter element of the entire segment. The level regulating element 12 opens to release the inflowing air. Via a pressure transmitter 37 and the valve 30 the pressure is again adjusted to the filtration pressure of 2 bar.
After termination of cleaning, the valve 32 is closed and the valve 33 is open. In an analogous manner the next row of the filter elements is cleaned. If necessary, the individual segments are cleaned after one another. In the event of danger of a pulp flow, the filtrate can be returned back to the tank 34 in short time, by opening of the valve 38 arranged in a return conduit 39. The depositing with filter aid means can be performed via the supply conduit 7.
In accordance with the advantageous embodiment of FIG. 2, the thickened residue is applied on the filter element 15 with the aid of an air-lift pump ccmposed of the riser pipe 41, and gas supplied via the pressure conduit 42. A compressed gas, for example air or a fluid, for example suspension in question can be used as a pressure medium.
In the embodiment of FIG. 3 the thickened residue can be treated again in the tube 46 by pressure gas or cleaning liquid supplied via the conduit 42. The residue is thereby subjected to whirling and therefore cleaned. After opening of the shutter 48, it is settled on the shutter 49. By closing of the shutter 48 and opening of the shutter 49, the cleaned residue accumulated in the sluice 50 is discharged.
In the construction of FIG. 4, the solid matter from the filter elements deposits in the tube 46 in condition of the open shutter 54 and the closed shutter 54'. For washing off the deposit, the washing fluid is supplied via the washing conduit and whirles the solid matter. After settling, the shutter 54 is closed and the contents is supplied from the tube 46 by opening of the shutter 54' into the tube 46' with open venting through the conduit 53. Here a further washing takes place via the conduit 42', and the washing liquid displaces upwardly in the tube 46. By opening of the shutter 48, the solid matter advances in the sluice and is discharged from the latter as described hereinabove. This cycle can now be repeated, whereas the supplied washing liquid can again displace upwardly and leave the system through the filter elements.
The entire operation is controlled with the aid of a control device, and several possibilities can be provided: It can be controlled upon the time in accordance with the experience. The control can be performed upon the filtration speed, i.e. in the event of a smaller flow the backwashing is automatically actuated. The control can be performed upon the return flow with the aid of pulp measurements. The control can be performed upon the discharge of the concentrate by the discharge valve 9 and a timer or mud concentration measurement. The control can be performed upon an excess pressure valve 40 which serves for maintaining a minimum pressure in the head part of the container. The shutters 48 and 49 above and below the sluice 50 can be controlled in a predetermined cycle.
During a fast cycle of cleaning and putting again the filter elements into operation no filter aid means is required in many cases. Thus the inventive method and arrangement is proven to be especially suitable for purification of salt water before and after the electrolysis. It can also be utilized for releasing red pulp from caustic soda, filtration of viscous from spinning baths, separation of condensate, filtration of PVC waste water and filtration of thin juice in sugar industry with excellent results.
It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of constructions differing from the types described above.
While the invention has been illustrated and described as embodied in a method of and an arrangement for thickening of suspensions, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of the present invention.
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A method of and an arrangement for thickening of suspensions includes filtering of a suspension through candlelike filter elements in a filter container, backwashing the filter elements individually without interrupting the filtration process by applying pressure impulses of gaseous backwash medium to the pressure elements in a direction opposite to the filtration direction, wherein the gaseous backwash medium forms a gas chamber over the filter elements separated from the suspension fluid and having an adjustable pressure.
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BACKGROUND
Currently, in the United States, many more cruciate ligament repair surgeries are performed on dogs than on people. Unfortunately, there is broad recognition that the available surgical procedures are sadly wanting in the degree to which the stifle (front knee joint of a dog) is repaired, and the durability of the repair. An improved technique and assembly for performing the technique is needed.
SUMMARY
The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tools and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
In a first separate aspect, the present invention may take the form of a repaired front stifle having a first stifle bone and a second stifle bone in opposed engagement to the first stifle bone, and having a first bone screw, having a head, and a shank fastened into the first stifle bone. A second bone screw having a head and a shank and having a through-hole in the shank, adjacent to the head, is fastened into the second stifle bone. Finally, a suture loop, is slidingly retained between the shaft of the first bone screw and the first stifle bone, and extends through the through-hole of the second bone screw and around the shank of the second bone screw.
In a second separate aspect, the present invention may take the form of a suture assembly that includes a suture loop, having a suture length comprised of woven material that is circular in cross-section, thereby defining a lumen. A tail of the suture length extends through the woven material to enter the lumen and is engaged within the lumen, thereby forming a loop. Further, a tension member is engaged to the suture loop.
In a third separate aspect, the present invention may take the form of a method of repairing a stifle, including a first stifle bone and a second stifle bone in engaged opposition to the first stifle bone. The method begins with screwing a first bone screw into the first stifle bone and screwing a second bone screw, having an aperture in its shank, into the second stifle bone. Next, a tension member is used to pull a suture loop, to engage a portion of the suture loop about the shank of the first bone screw. Then, the tension member is used to pull the suture loop through the aperture of the second bone screw and then into engagement about the shank of the second bone screw.
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following detailed descriptions.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments are illustrated in referenced drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive.
FIG. 1 is a side view of a length of suture material, formed into a U, and to be used in a further part of the production of a suture assembly according to the present invention.
FIG. 2 is a side view of the material of FIG. 10 , in a further step in the process of forming the length of suture material of FIG. 10 into a portion of the suture assembly of the present invention.
FIG. 3 is an isometric view of a length of suture material and a lacing tool that is being used to form the suture material into a suture loop, which forms a portion of a suture assembly according to the present invention.
FIGS. 4-9 are isometric views of the elements of FIG. 3 , in a series of further steps in the process of forming the suture assembly.
FIG. 10 is an isometric view of a final step in the production of one variant of a suture loop, which forms a part of a suture assembly according to the present invention.
FIG. 11 is an illustration of a stitching pattern used in part of suture assembly used in one embodiment of the present invention.
FIG. 12 is a side view of a length of suture material, formed into a U, and to be used in a further part of the production of a suture assembly according to the present invention.
FIG. 13 is a side view of the material of FIG. 12 , in a further step in the process of forming the length of suture material of FIG. 12 into a portion of the suture assembly of the present invention.
FIG. 14 is an isometric view showing a lancing tool arranging the suture of FIG. 12 , so that it interlocks with the suture loop of FIG. 11 .
FIG. 15 is an isometric view of a partially finished suture assembly, according to the present invention.
FIG. 16 is a side view of a finished suture assembly, according to the present invention.
FIG. 17 is a side view of two bone screws that are used in a method of repairing a cranial cruciate ligament, according to the present invention.
FIGS. 18A-18D are successive steps in a cranial cruciate ligament repair surgery that utilizes the suture assembly of FIG. 15 , and the screws of FIG. 17 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Definitions
Bone screw: a screw having a head and an attached shank, and wherein the shank comes to a point at its end, to enable its introduction into bone.
Embodiments of the present invention are described below with reference to the above described figures. It is, however, expressly noted that the present invention is not limited to the embodiments depicted in the figures, but rather the intention is that modifications that are apparent to the person skilled in the art and equivalents thereof are also included.
FIG. 1 shows an open fiber 1 having two tails: a save tail 3 and a cut tail 2 . According to preferred embodiments, the fiber 1 is a biocompatible fiber, such as an ultra-high molecular weight polyethylene (UHMWPE) fiber, although suitable non-preferred materials can be used as well including polyester and POLYBLEND®, for example. Additionally, the fiber 1 is braided as opposed to being monofilamentous. Braided fibers are particularly advantageous in the teachings herein as they are stronger and define a lumen therein, which allows for the tails 3 and 2 to be threaded into the lumen as will be discussed in more detail below.
Referring to FIG. 2 , an entry point 5 and an exit point 6 points can be designated along length of fiber 1 to define a middle section 9 . Save tail 3 includes all of fiber 1 , from exit point 6 , to the nearest end point, as shown. Table I can be utilized as an approximate guide to determine suitable lengths of the starting fiber 1 , save tail 3 , and middle section 9 based on the final loop size desired. For example if a 20 mm final loop size is desired, it would be advantageous to begin with a thread having a length of about 6 inches (152.4 mm), and to configure the thread such that the middle section is 35 mm in length and the save tail section is 40 mm in length. Loop size is measured from the largest inner diameter of the loop formed from fiber 1 , as described below.
TABLE I
Loop
Fiber
Save Tail
Middle Section
Pre-Stretch
Size
Length
Length
Length
Length
(mm)
(in)
(mm)
(mm)
(mm)
15
6
40
30
~13
20
6
40
35
~18
25
7
40
45
~23
30
8
45
60
~28
35
8
50
65
~33
40
10
55
75
~38
As shown in FIG. 2 , the fiber 1 is preferably fluffed at the entry 5 and exit 6 points to make it easier for a lacing tool 7 ( FIGS. 3-5 ) to be inserted through the middle section 9 . One end of the lacing tool 7 ( FIGS. 3-5 ) can include a handle to allow a user to position, guide, push, and pull the tool. The lacing tool 7 ( FIGS. 3-5 ) also includes a main body that is preferably substantially linear and having a diameter, or cross-section, small enough to thread through the fiber 1 . The end of the lacing tool 7 ( FIGS. 3-5 ) opposite of the handle can include a hinged barb 10 to allow for coupling to the fiber 1 . The hinge allows the barb 10 to have a lower profile when traversing through the inside of fiber 1 while minimizing the chance of snags. Other means for coupling to the fiber are readily contemplated and can non-exclusively include one or more barbs (hinged or unhinged) hooks, clamps (such that can be opened and closed by the handle) and the like, for example. Said means for coupling 10 preferably should not prevent or hinder the lacing tool 7 ( FIGS. 3-5 ) from being pushed into or pulled out of the inside of the fiber 1 .
As depicted in FIGS. 3-5 , once the middle section 9 is defined, the barb 10 of the lacing tool 7 is pushed into the lumen of the fiber 1 at the fluffed entry point 5 . The barb 10 is pushed through the inside of the middle section 9 and guided outward through the fluffed exit point 6 . With reference to FIGS. 4 and 5 , the cut tail 2 is then coupled to the barb 10 and configured to allow the lacing tool 7 and cut tail 2 to be pulled back into the middle section 9 at the exit point 6 . The barb 10 and coupled cut tail 2 are pulled out of the middle section 9 at the entry point 5 . As shown in FIG. 6 , this step results in general loop shape with the cut tail section 2 being exposed out of the fiber 1 at the entry point 5 . The exposed cut tail 2 can be cut as close to the entry point 5 as possible, utilizing one or more of the following: scissors, knife, cutting instrument, thermal knife, and/or razor blade, and the like while avoiding cutting the external fiber near the entry point 5 . The remaining cut tail 2 can be retracted within the lumen of the fiber through the entry point 5 , as shown in FIG. 7 by any suitable method, such as by manually or mechanically stretching the loop. One preferred method is to utilize needle holders to cinch the loop. For example, the closed jaws of needle holders or a scissor-like tool can be inserted into the loop then opened to stretch the loop. A preferred machine could be a force gauge.
Next, second entry 15 and exit 16 points ( FIG. 8 ) are defined along the fiber 1 . The second exit point 16 can preferably be positioned within close proximity to the end of the retracted cut tail 2 to minimize the amount of external fiber outside the loop lumen while still allowing for an internal overlap, or proximity, between the save tail and cut tail 2 and 3 within the lumen. These second entry 15 and exit 16 points can also be fluffed to allow for the lacing tool 7 to readily enter and exit the fiber 1 . After the second entry 15 and exit 16 points are defined, the barb 10 of the lacing tool 7 is pushed into the lumen of the fiber 1 at the fluffed second entry point 15 . The barb 10 is pushed through the inside of the fiber 1 and guided outward through the fluffed second exit point 16 . In one preferred embodiment, the assembly is essentially finished at this point, with the save tail being cut close to entry point 5 , to avoid having an unnecessary loose end. The reinforcing regions 20 and 21 , noted below and in FIG. 10 , may then be applied, but simply to entry point 5 or to the location of cut end 2 .
The save tail 3 is then coupled to the barb 10 and configured to allow the lacing tool 7 and save tail 3 to be pulled back into fiber 1 at the second exit point 16 . The barb 10 and coupled save tail 3 can be pulled out of fiber's lumen at the second entry point 15 . As shown in FIG. 9 , this step results with the save tail section 3 being exposed out of the fiber 1 . The exposed save tail 3 is preferably cut near the second entry point 15 , such that a small section of the save tail 3 is still exposed. Cutting can be done utilizing one or more of the following: scissors, knife, cutting instrument, thermal knife, and/or razor blade, and the like while avoiding cutting the external fiber near the second entry point 15 .
After the save tail 3 is initially cut, it is preferred to manually or mechanically expand the loop, thereby causing fiber 1 to contract in transverse dimension, so that it is in closer engagement with tails 2 and 3 . One preferred method is to utilize needle holders to cinch the loop. For example, the closed jaws of needle holders or a scissor-like tool can be inserted into the loop then opened to stretch the loop. A preferred machine could be a force gauge. The inner diameter of the loop can be measured to determine how close it is to the final desired size. If needed, the loop can be stretched using tools or machines prior to the stitching/securing steps described below. As a preferred example, the fiber loop can be manually or mechanically stretched to approximately 100 lbs. One type of suitable machine that can be used for this step is a force gauge.
In one preferred embodiment the stitching steps shown in FIGS. 10 and 11 are not performed, with the natural engagement of the interior surface of fiber 1 with tails 2 and 3 , holding tails 2 and 3 in place. As shown in FIG. 10 , a first stitching section 21 is defined by a section on the fiber 1 that encompasses the first exit point 6 where the cut tail 2 has entered into the lumen. As shown in FIG. 10 , a second stitching section 20 is defined by a section on the fiber 1 that encompasses the ends of the cut tail 2 and the save tail 3 . It is important to note that the location of the first and second entry and exit points 5 , 6 , 15 , and 16 on the fiber 1 in FIGS. 8-10 are non-limiting, as they can be positioned closer to each other or at different locations depending on the final size of the assembly. A needle 25 and thread 23 , such as UHMWPE thread, can be used to readily secure the first exit point 6 at the first stitching section 21 and the cut tail 2 and save tail 3 together at stitching section 20 . Additionally, other means for securing or reinforcing sections 20 , 21 , besides stitching, can also readily be used. Non-exclusive examples, of securing or reinforcing means can include one or more adhesives, such as glue, heat setting, crimping. These means can be used by themselves or in conjunction with each other, or in conjunction with stitching.
After the first section 21 , having the first exit point 6 is stitched, or otherwise secured or reinforced, it is preferred to stitch or otherwise secure the second stitching section 20 where the cut tail 2 and save tail 3 overlap, or are otherwise in close proximity. According to one method, stitching using a needle 25 and thread 23 , such as an UHMWPE thread, can begin below the second entry point 15 , such that the stitching moves in an upwards direction towards the second entry point 15 . Alternatively, and as shown in FIG. 10 , the stitching or reinforcing method can be started above the final section 20 . FIG. 11 illustrates a preferred directional path of stitching along the fiber 1 .
If the stitching reaches a position adjacent and below or above the second entry point 15 , it is preferred to cut off the remaining exposed save tail 3 as close to the second entry point 15 as possible using any suitable cutting instrument, such as a razor blade, while not cutting, and thereby comprising the fiber 1 . Alternatively, this could be the first cut of the exposed save tail 3 as opposed to the second cut. The remaining save tail 3 can be retracted within the lumen of the fiber 1 through the second entry point 15 as shown in FIG. 10 . The save tail 3 can be retracted into the fiber using any suitable method, such as by utilizing needle holders, as described above, or by other manual or mechanical methods of stretching the fiber loop. It is preferred that the save tail 3 is retracted within the lumen in close approximation, or on the same side of the loop, as the retracted cut tail 2 . More specifically, and as shown in FIG. 10 , the save tail 3 and cut tail 2 are preferably aligned adjacent to each other to create an overlap of about ⅙-¼ of an inch depending on the final loop size desired (e.g., 15-60 mm). Additionally, the ends of the cut tail 2 and save tail 3 can be adjacent to each other, or alternatively there could be a small gap between the cut tail 2 and save tail 3 .
Once the save tail 3 is fully retracted within the lumen, and positioned overlapping or near the cut tail 2 , it is preferred to finalize the stitching in the second section 20 . Stitching, or otherwise securing, the cut tail 2 and save tail 3 together helps prevent fraying of the fiber 1 . As with the first section 21 , the second section 20 can be secured or reinforced utilizing other means besides thread and needles stitching. Non-exclusive examples, of securing means can include one or more adhesives, such as glue, heat setting or crimping. These means can be used by themselves or in conjunction with each other, or in conjunction with stitching. According to other embodiments, the save tail 3 can first be retracted within the lumen, and then stitching or securing of the second section 20 can begin. Stitching or securing of the second section 20 advantageously secures the cut tail 2 and save tail 3 together within the braid 1 and to the braided fiber 1 .
According to certain embodiments, the loop 22 can have only one stitched or reinforced section 20 or 21 , and no more. This single reinforced section can be the section shown in 21 that covers the first exit point 6 , where the cut tail 2 enters into the lumen of the fiber 1 . Under this embodiment, the ends of the cut tail 2 and save tail 3 would not be connected within the lumen of the fiber 1 . Alternatively, the single stitched or reinforced section can be the second section 20 that encompasses the cut tail 2 and save tail 3 junction within the lumen, without reinforcing the first exit point 6 . Additional embodiments include having one or more of the reinforced sections 20 and 21 to be doubly stitched. As noted previously, in a preferred embodiment, loop 22 has no reinforced section 20 or 21 , with the natural engagement of tails 2 and 3 within the lumen of suture material 1 , retaining tails 2 and 3 .
Alternative means of inserting the cut tail 2 and the save tail 3 into the lumen of the fiber 1 to achieve a similar final assembly are also readily contemplated herein. For example, a needle or other tool can be used to guide and insert the cut tail 2 and/or save tail 3 directly into the lumen of the fiber 1 without have the tool first being inserted into the lumen. According to alternative embodiments, the cut tail 2 and save tail 3 could be inserted within the lumen and left within, without having the ends first pulled out, cut, and retracted as described above. This could be done with the step of cinching/stretching out the loop, as described above. It is preferred that the cut tail 2 and save tail 3 are inserted substantially within the lumen, and not just their ends. More specifically, it is preferred that the entire circumference of the lumen, or substantially so, is occupied with either the cut tail 2 or save tail 3 , or both with respects to overlapping between the two. In a first preferred embodiment the suture loop 22 is made of USP-2 suture material and in a second preferred embodiment the suture loop is made of USP-5 material.
It is preferred that the assembly 22 is re-measured and re-stretched (e.g., at approximately 100 lbs.) if needed to achieve the final desired loop size.
Referring to FIGS. 12-15 , after loop 22 is complete, construction of assembly 50 continues with a length of suture material 30 , in which an entry point 32 and an exit point 34 are defined and fluffed to facilitate entry and exit of lacing tool 7 . Next ( FIG. 14 ) suture 30 is extended through loop 22 , and lacing tool 7 is introduced into length 30 at entry point 32 , and out at exit point 34 , and captures a free end 36 of length 30 . Referring to FIG. 15 , lacing tool is used to pull free end 36 through exit point 34 and entry point 32 to form a loop 38 , with a first portion 40 of length 30 , passing through a second portion 42 of length 30 . Assembly 50 is now essentially complete, with a further step in which stitching is used to fix portion 40 inside portion 42 , being performed in a preferred embodiment, and a loose end 44 being cut off. Referring to FIG. 16 , at this point, assembly 50 , including loop 22 and eyelet-tail element 48 is complete. In an alternative preferred embodiment, eyelet-tail element 48 is replaced by another form of tension. In one embodiment wire is folded over a portion of loop 22 and used in the same manner as element 48 , in the method described below. In one embodiment this wire is made of nitinol.
Referring to FIGS. 17 and 18A-18D , a veterinary surgery to implant loop 22 , so that it can absorb some of the stress normally born by the cranial (anterior) cruciate ligament is possible, using assembly 50 . A first bone screw 52 is introduced into the femur 54 , and a second bone screw 56 , having an aperture 57 in its shank, as shown is introduced into the tibia 58 . Eyelet-tail element 48 is used to pull loop 22 over the head of screw 52 , so that it is interposed between the head of screw 52 and femur 54 . Next, eyelet-tail element 48 is used to pull loop 22 through aperture 57 , then twist loop 22 , and extend a portion of it over the head of screw 56 , where it is interposed between this head and the tibia. Then screw 56 may be tightened to squeeze the interposed portion of loop 22 tightly between screw head and bone. Screw 52 may be tightened, but should be left loose enough so that loop 22 can slide about it.
While a number of exemplary aspects and embodiments have been discussed above, those possessed of skill in the art will recognize certain modifications, permutations, additions and sub-combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are within their true spirit and scope.
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A method of repairing a stifle, including a first stifle bone and a second stifle bone in engaged opposition to the first stifle bone. The method begins with screwing a first bone screw into the first stifle bone and screwing a second bone screw, having an aperture in its shank, into the second stifle bone. Next, a tension member is used to pull a suture loop, to engage a portion of the suture loop about the shank of the first bone screw. Then, the tension member is used to pull the suture loop through the aperture of the second bone screw and then into engagement about the shank of the second bone screw.
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BACKGROUND OF THE INVENTION
The present invention relates to image data processors for use in playing a battle game or a congeniality divination game, using data on the images of objects such as a plurality of human beings, animals or buildings.
Various game devices using electronic units have been developed and available commercially. For example, a battle type television game device is known which uses a television display screen. In this device, game program data stored in a dedicated cassette provided to the device body is read out in accordance with an keying-in operation, and a person displayed on the display screen is moved in accordance with the game program data to decide victory or defeat of the game.
With this television game device, however, the data on the basis of which victory or defeat of the game is decided is set beforehand as the program in the dedicated cassette. Thus, the result of victory or defeat of the game is fixed and as a result the game is not so interesting.
A competing type game device to which the users themselves input data which is the base of decision of victory or defeat is known as a bar code battle device, as disclosed in published unexamined Japanese patent application Hei 3-193074. In this device, when two kinds of bar code cards are inserted into the device body, a bar code data reader provided in the device body reads the bar code data printed on the two cards, and the device converts the read data items to numerical values. The device compares the numerical values to decide victory or defeat depending on which value is larger, and displays the result of the decision in numerical values and symbols.
With this bar code battle device, the data on the basis of which victory or defeat is decided is input by the users themselves, and the data obtained on the basis of the input bar code data is numerical data. Thus, the game itself is not interesting.
Apart from the battle type game device, a congeniality diagnosis device is known. In this device, the blood types and asterism names of the two persons who are subjected to congeniality divination are input to the device, and the congeniality of the two persons is decided in accordance with a combination of the input data items on the respective blood type and asterism names.
Also, with this congeniality divination device, the input data is limited to the blood types and asterism names of the two persons, so that even when the person who is subjected to the divination has been exchanged with another, the same result of congeniality divination can appear. Thus, the game is not interesting.
The present invention has been made in view of those problems. It is therefore an object of the present invention to provide an image data processor useful for various game devices such as battle games and congeniality divination games.
In order to achieve the above object, the inventive image data processor includes setting means for setting a plurality of object image data items each including a combination of part image data items corresponding to the respective parts of an object, determining means for determining superiority or inferiority between the plurality of image data items set by the setting means on the basis of the part image data items constituting the respective object image data items, and display means for displaying the result of the determination by the determining means. The display means is, for example, liquid crystal display means or printing means for displaying visually the data on the result of the determination.
According to the present invention, the setting means sets a plurality of object image data items each including a combination of part image data items corresponding to the respective parts of an object. The determining means determines superiority or inferiority between the plurality of object image data items set by the setting means on the basis of the part image data items composing the respective object image data items. The display displays the result of the determination by the determining means. Thus, the result of determination about superiority or inferiority between the plurality of object image data items is displayed on a display or in print.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the composition of an internal surface of a montage game device as a first embodiment of the present invention and taken when unfolded;
FIG. 2 is a block diagram of an electronic circuit of the montage game device as the first embodiment;
FIG. 3A shows a stored state of basic part patterns of face montages in a basic part pattern ROM;
FIG. 3B shows a stored state of basic part patterns of whole body montages in the basic part pattern ROM;
FIG. 4A shows a stored state of battle scores for face montages in a battle score ROM;
FIG. 4B shows a stored state of battle scores for whole body montages in the battle score ROM;
FIG. 5A shows a stored state of congeniality scores for face montages in a congeniality score ROM;
FIG. 5B shows a stored state of congeniality scores for whole body montages in the congeniality score ROM;
FIGS. 6A-6C each show a stored state of face expression patterns in an expression part pattern ROM;
FIGS. 7A and 7B each show a stored state of face expression patterns in the expression part pattern ROM;
FIGS. 8A and 8B each show a stored state of main portions of the whole body expression patterns in the expression part pattern ROM;
FIG. 9 shows a stored state of battle victory/defeat messages in a battle message ROM;
FIG. 10 shows a stored state of congeniality message in a congeniality message ROM;
FIGS. 11A and 11B each show a stored state of the numbers of the part patterns, etc., which constitute battle montage data entered in a battle montage RAM;
FIGS. 12A and 12B each show a stored state of the part pattern numbers which constitute congeniality divination montage data entered in a congeniality divination montage RAM;
FIG. 13 is a flowchart indicative of a montage creation process in the first embodiment;
FIG. 14 a flowchart indicative of synthesization and display of a montage involved in the montage creation process;
FIG. 15 is a flowchart indicative of a process for the former half of a battle game;
FIG. 16 is a flowchart indicative of a process for the latter half of the battle game;
FIGS. 17A-17C each show a displayed state of X and Y montages involved in the process for the battle game;
FIG. 18 is a flowchart indicative of a process for the former half of a congeniality divination game;
FIG. 19 is a flowchart indicative of a process for the latter half of the congeniality divination game;
FIGS. 20A-20C each show a displayed state of X and Y montages involved in the process for the congeniality divination game;
FIG. 21 shows data stored in a face type congeniality corresponding ROM used in a second embodiment of the present invention;
FIG. 22 is a flowchart indicative of a process for playing a congeniality divination game according to the second embodiment;
FIG. 23 shows the composition of an internal surface of an infrared optical communication type montage game system as a third embodiment of the present invention and taken when unfolded;
FIG. 24 is a block diagram of an electronic circuit of a large display device of the infrared optical communication type montage game system as the third embodiment;
FIG. 25 is a block diagram of an electronic circuit of a game device body of the infrared optical communication type montage game system as the third embodiment;
FIG. 26 shows the composition of an internal surface of a montage game system having an infrared optical communication function and a ROM exchange function as a fourth embodiment of the present invention and taken when unfolded;
FIG. 27 is a block diagram of an electronic circuit of the montage game system as the fourth embodiment;
FIG. 28 is a block diagram of an electronic circuit of a montage game system as a fifth embodiment of the present invention;
FIG. 29 shows a stored state of luck scores in a score ROM used in the fifth embodiment;
FIG. 30 shows a stored state of luck messages in a message ROM used in the fifth embodiment;
FIG. 31 is a flowchart indicative of a face creating process and a divination process in the fifth embodiment;
FIG. 32 shows a displayed state of a montage involved in the divination process in the fifth embodiment;
FIG. 33 is a block diagram of an electronic circuit of a montage game system as a sixth embodiment of the present invention;
FIG. 34A shows a stored state of part patterns in a basic part pattern ROM of a ROM assembly;
FIG. 34B shows a stored state of part and congenial pattern numbers in a self-congeniality correspondence ROM of a ROM assembly;
FIG. 35A shows a stored state of part pattern number groups in an entry montage RAM of a RAM assembly;
FIG. 35B shows a stored state of congenial part pattern numbers in a self-congeniality montage RAM of the RAM assembly;
FIG. 36 is a flowchart indicative of an optimal congeniality montage display process in the sixth embodiment; and
FIG. 37A-37C each show a displayed state of a montage involved in the optimal congeniality montage display process in the sixth embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present invention will be described below with respect to the drawings.
[First Embodiment]
FIGS. 1-20C involve a montage game device as a first embodiment of the present invention. In FIG. 1, the game device body 11 is provided with a pocketable type casing having right and left halves openable right and left. The left half has an operation surface 12a which is provided thereon with an ON key 13a and an OFF key 13b which turn on and off a power supply (not shown) to the device; a montage creating key 14 operated when a montage is created; X, Y and Z keys 15a, 15b and 15c depressed to designate respectively persons "X", "Y" and "Z" whose montages are to be created; basic montage select keys 16a, 16b operated to select any one of a plurality of montages in the montage creation; part designation keys 17a, 17b operated to designate that of a plurality of parts constituting a selected montage and to be changed; pattern select keys 18a, 18b operated to select that of a plurality of part patterns and to be changed, each pattern indicative of the designated part; an entry key 19 operated to store and enter data on the created montage to the device; a battle key 20; a congeniality divination key 21; and a start key 22.
The battle key 20 is operated to designate a location where the created battle montage data is to be stored and to set a battle game mode in which a battle game is played on the basis of the entered battle montage data. The congeniality divination key 21 is operated to designate a location where the congeniality divination montage data is stored and to set a congeniality divination game mode in which a congeniality divination game is played on the basis of the entered congeniality montage data. The start key 22 is operated to start a game in the battle game mode or the congeniality divination mode.
The left operation surface 12a of the left casing half of the game device body 11 is provided with a display 23 composed of a liquid crystal matrix. The display 23 is provided with "X" or "Y" or "Z" montage display areas.
The right operation surface 12b of the right casing half is provided with a ten-key unit 24 of keys "0"-"9" operated to input numerical data to the device body 11; an operand key unit 25 composed of "+", "-", "×", "÷" and "="; and an alphabetic key unit 26 composed of keys "A"-"Z" for inputting various data to the device body.
FIG. 2 is a block diagram of the entire electric circuit of the montage game device. The electric circuit is provided with a CPU (Central Processing Unit) 31, to which an input unit 32 is connected. The input key unit 32 is composed of the battle key 20; congeniality divination key 21; start key 22; ten-key unit 24; operand key unit 25, etc. The respective operations of the circuits are controlled on the basis of programs stored beforehand in a built-in program ROM (Read Only Memory) in accordance with a keyed-in operative signal fed from the input unit 32. In addition, the input unit 32, ROM assembly 60, RAM (Random Access Memory) assembly 61, synthesis RAM 41, and display 23 through a display driver 42 are connected to CPU 31.
The ROM assembly 60 is provided with a basic part pattern ROM 33; a battle score ROM 34; a congeniality score ROM 35; an expression part pattern ROM 36; a battle message ROM 37; and a congeniality message ROM 38. The RAM assembly 61 is provided with a battle montage RAM 39 and a congeniality divination montage RAM 40.
FIG. 3A shows a stored state of basic patterns of parts of each of face montages in the basic part pattern ROM. FIG. 3B shows a stored state of basic part patterns of each of whole body montages in the basic part pattern ROM 33.
The basic part pattern ROM 33 for the face montage shown in FIG. 3A stores part image data on the patterns of 5 parts ("contour, "hair style", "eyes", "nose", and "mouth") constituting each of 20 kinds of faces of human beings, animals, spacemen, etc., in correspondence to numbers "01"-"20" in the form of bit map data in a predetermined area 33a. In the particular embodiment, for the "contour" pattern, a "substantially half-oval jaw" is stored at a storage location "01" for the "contour" part; and a "rounded jaw" is stored at a storage location "02" for the "contour" part. For the hair style pattern, a "hair parted at the side" is stored at a storage location "01" for the "hair style" part; and a "long hair" is stored at a storage location "02" for the "hair style" part. Similarly, the respective patterns of the other parts are stored.
Twenty kinds of part patterns of each of a face, trunk, both hands, and both arms and legs of a person are stored in correspondence to the numbers "01"-"20" in a predetermined storage area 33b of the basic part pattern ROM 33 for a whole body montage shown in FIG. 3B.
FIG. 4A shows a stored state of battle scores for the face montages in the battle score ROM 34. FIG. 4B shows a stored state of battle scores for the whole body montage data in the battle score ROM 34.
Battle scores allocated any one of "0"-"9" in one-to-one correspondence to the respective basic part patterns (contour, hair style, nose, eyes, mouth×Nos. "01"-"20") for the face montage in the basic part pattern ROM 33 are stored in respective areas 34a of the battle score ROM 34 for the face montage of FIG. 4A. For example, a battle score "0" is stored in an area 34a of the battle score ROM 34 for the face montage corresponding to the part pattern No. 01 of the "contour" in the basic part pattern ROM 33. Similarly, a battle score "7" is stored in an area 34a of the battle score ROM 34 for the face montage corresponding to a "contour" part pattern No. "02".
Battle scores allocated any one of "0"-"9" in one-to-one correspondence to the respective basic part patterns (face, trunk, body, both arms and hands, both legs×Nos. "01"-"20") for the whole body montage in the basic part pattern ROM 33 are stored in respective areas 34b of the battle score ROM 34 for the whole body montage of FIG. 4B. For example, a battle score "9" is stored in an area 34b of the battle score ROM 34 for the whole body montage corresponding to the part pattern No. "01" of the "face" in the basic part pattern ROM 33. Similarly, a battle score "2" is stored in the area 34b of the battle score ROM 34 for the whole body montage corresponding to the part pattern No. "02" of the "face".
FIG. 5A shows a stored state of congeniality scores for a face montage in the congeniality score ROM 35. FIG. 5B shows a stored state of congeniality scores for a whole body montage in the congeniality score ROM 35.
Congeniality scores allocated any one of "0"-"9" in one-to-one correspondence to the respective basic part patterns (contour, hair style, nose, eyes, mouth×Nos. "1"-"20") for the face montage in the basic pattern ROM 33 are stored in respective areas 35a of the congeniality score ROM 35 for the face montage of FIG. 5A.
Battle congeniality scores allocated any one of "0"-"9" in one-to-one correspondence to the respective basic part patterns (face, trunk, both arms and hands, both legs×Nos. "01-"20") for the whole body montage in the basic pattern ROM 33 stored in the respective areas 35b of the congeniality score ROM 35 for the whole body montage of FIG. 5B.
FIGS. 6A-6C show a stored state of face expression pattern data in the expression part pattern ROM 36 used in a battle game. FIG. 6A show a stored state of first stage display patterns used in a first stage during the battle. FIG. 6B show a stored state of second stage display patterns used in a second stage of the battle. FIG. 6C shows a stored state of victory result display patterns used when the war is won as the result of the battle.
The display patterns prepared for the respective battle stages are stored in the areas 36a-36c in correspondence to the respective patterns of the parts "eyes" and "mouth" stored in the basic part pattern ROM 33.
The first stage display patterns of FIG. 6A are part patterns constituting each of angry faces. The second stage display patterns of FIG. 6B are part patterns constituting each of sad faces. The victory result display patterns of FIG. 6C are part patterns constituting each of faces present when battle was won and a background pattern fitted into the background of the face montage present at that time.
FIGS. 7A and 7B show a stored state of face expression patterns in the expression part pattern ROM 36 used in a congeniality divination game or a battle game. FIG. 7A show a stored state of congeniality coincidence result display patterns used when the result of congeniality divination shows the coincidence of congeniality. FIG. 7B show a stored state of loss result-congeniality non-coincidence result display patterns in the expression part pattern ROM 36 used when the battle is lost and non-congeniality coincidence was obtained as a result of the divination.
The above respective result display patterns are stored in areas 36d and 36e in the basic part pattern ROM 33 in correspondence to the respective basic part patterns "eyes" and "mouth" in the basic part pattern ROM 33. Congeniality coincidence background patterns to be combined with the background of a face montage present when coincidence of the congenialities are stored in the respective other areas 36d-1 of the expression part pattern ROM 36. Defeat or congeniality non-coincidence background patterns each to be combined with the background of a loser's face montage present at the end of the battle and the background of the face montage at congeniality non-coincidence present at the end of the congeniality divination are stored in other areas 36e-1 of the expression part pattern ROM 36.
The congeniality coincidence result display patterns of FIG. 7A are part patterns constituting an delighted face because of coincidence of congenialities. The defeat result-congeniality non-coincidence result display patterns of FIG. 7B are part patterns constituting a sad face due to a lost battle or substantial non-coincidence of congeniality and a background pattern fitted into the background of the face montage at that time.
FIGS. 8A and 8B each show a stored state of whole body expression patterns in the expression part pattern ROM 36 used in either a congeniality divination game or a battle game. FIG. 8A shows a stored state of the battle victory result-congeniality coincidence result display patterns. FIG. 8B shows a stored state of the battle defeat result-congeniality non-coincidence result display patterns.
The respective result display patterns are stored in the respective areas 36f, 36g in correspondence to the respective basic part patterns of the face, and both arms and hands in the basic part pattern ROM 33.
The congeniality coincidence result display pattern of FIG. 8A show the respective part patterns constituting the body of each of both partners when both the partners are congenial and delighted. The defeat result-congeniality non-coincidence display patterns of FIG. 8B are part patterns composing the body of the loser of the battle or one of the partners who are sad about substantial non-coincidence of congenialities to each other.
Although not shown, a first and a second display pattern present during congeniality divination are stored beforehand in the expression part pattern ROM 36.
FIG. 9 shows a stored state of battle victory and defeat messages in the battle message ROM 37.
Victory/defeat messages different depending on a victory, defeat and draw as a result of the battle are stored in the respective areas 37a of the battle message ROM 37. For example, the victory message "I won, wow!" used when the battle was won, the defeat message "I lost, sorry!" used when the battle was lost, and the draw message "Mmm . . .!" used when the battle was drawn are stored beforehand.
FIG. 10 shows a stored state of congeniality messages in the congeniality message ROM 38.
Congeniality messages different depending on the result of congeniality divination are stored in respective areas 38a in the congeniality message ROM 38. Each message has contents corresponding to the difference between the two sums of congeniality scores obtained from the congeniality score ROM 35 in correspondence to the respective part patterns of any two face or whole body montages which are subjected to congeniality divination. If the score difference is 0-3, the messages "Perfectly congenial!" and "I am delighted!" are stored beforehand as congeniality messages to be associated with those respective montages; if the score difference is 4-15, the messages "Almost congenial!" and "We'll be friends!" are stored; and if the difference score is 16-29, the messages "Never congenial!" and "we'll fight it out in a battle game!" are stored.
FIGS. 11A and 11B show a stored state of battle montage data (respective part pattern numbers) and the corresponding battle scores recorded in the battle montage RAM 39 . FIG. 11A shows the X and Y battle face montage data and battle scores. FIG. 11B show the respective X and Y battle whole body montage data and battle scores.
FIG. 11A shows respective pattern numbers "01" (contour), "01" (hair style), "01" (eyes), "02" (nose), and "01" (mouth) of parts (contour, hair style, nose, eyes, mouth) constituting the battle face montage data entered as X by the user and stored in a face montage data storage area 11a in the battle montage RAM 39. FIG. 11A also shows respective battle scores "0", "3", "1" "3, and "1" corresponding to the entered part pattern numbers stored in the storage area 11c.
FIG. 11A shows respective pattern numbers "03" (contour), "20" (hair style), "02" (eyes), "04" (nose), and "02" (mouth) of parts (contour, hair style, nose, eyes, mouth) constituting the battle face montage data entered as Y by the user and stored in a face montage data storage area 11b in the battle montage RAM 39. FIG. 11A also shows respective battle scores "6", "6", "2", "7", and "8" corresponding to the entered part pattern numbers and stored in the storage area 11d.
FIG. 11B shows respective pattern numbers "09" (face), "03" (trunk), "02" (both arms and hands), and "01" (both legs) of parts (face, trunk, both arms and hands, both legs) constituting the battle whole body montage and recorded as X by the user and stored in a whole body montage data storage area 11A of the battle montage RAM 39. FIG. 11B also shows respective battle scores "0", "5", "4" and "3" corresponding to the entered part pattern numbers and stored in the storage area 11C.
FIG. 11b shows respective pattern numbers "07" (face), "09" (trunk), "08" (both arms and hands), and "07 (both legs) of parts (face, trunk, both arms and hands, both legs) constituting the battle whole body montage and recorded as Y by the user and stored in a whole body montage data storage area 11B of the battle montage RAM 39. FIG. 11B also shows respective battle scores "5", "6", "2" and "3" corresponding to the entered part pattern numbers and stored in the storage area 11D.
The total sums of the battle scores of the individual montages are stored in the respective total score areas 11e, 11f, 11E, 11F in the battle montage RAM 39.
A victory or defeat in the battle is determined on the basis of which of the battle total scores of the X and Y montages stored in the areas 11e, 11f, 11E and 11F is larger than another.
FIGS. 12A and 12B each show a stored state of congeniality divination montage data (respective pattern numbers) and congeniality scores recorded in the congeniality divination montage RAM 40. FIG. 12A shows a stored state of respective X and Y congeniality divination face montage data and congeniality score. FIG. 12B shows a stored state of congeniality divination whole body montage data and congeniality scores.
FIG. 12A shows the respective pattern numbers "04" (contour), "04" (hair style), "04" (eyes), "03" (nose), and "04" (mouth) of parts (contour, hair style, nose, eyes, mouth) constituting the congeniality divination face montage data recorded as X by the user and stored in a face montage data storage area 12C in the congeniality divination montage RAM 40. FIG. 12A also shows respective congeniality scores "7", "8", "7", "1" and "2" corresponding to the recorded part pattern numbers and stored in the storage area 12c.
FIG. 12A shows the respective pattern numbers "04" (contour), "03" (hair style), "03" (eyes), "01" (nose), and "03" (mouth) of parts (contour, hair style, nose, eyes, mouth) constituting the congeniality divination battle face montage data recorded as Y by the user and stored in a face montage data storage area 12b of the congeniality divination montage RAM 40. FIG. 12A also shows respective congeniality scores "5", "6", "3", "3" and "4" corresponding to the recorded part pattern numbers and stored in the storage area 12d.
FIG. 12B shows respective pattern numbers "02" (face), "06 (trunk), "09 (both arms and hands), and "05 (both legs) of parts (face, trunk, both arms and hands, both legs) constituting the congeniality divination whole body montage data recorded as X by the user and stored in a whole body montage data storage area 12A in the congeniality divination montage RAM 40. FIG. 12B also shows respective congeniality scores "1", "2", "3 and "2" corresponding to the recorded part pattern numbers and stored in the storage area 12C.
FIG. 12B also shows respective pattern numbers "04" (face), "08 (trunk), "02 (both arms and hands), and "01 (both legs) of parts (face, trunk, both arms and hands, both legs) constituting the congeniality divination whole body montage data recorded as Y by the user and stored in a whole body montage data storage area 12B of the congeniality divination montage RAM 40. FIG. 12B also shows respective congeniality scores "0", "0", "1" and "2" corresponding to the recorded part pattern numbers and stored in the storage area 12D.
The total sums of the congeniality scores of the individual montages are stored in the respective total score storage areas 12e, 12f, 12E, 12F in the congeniality divination montage RAM 40.
The congeniality degree between both the X and Y montages is determined on the basis of which of the respective total congeniality scores of the X and Y montages stored in the areas 12e, 12f, 12E and 12F is larger than the other.
The synthesis RAM 41 synthesizes in the form of bit map data X-Z montages from the respective part patterns read out from the basic part pattern ROM 33 in correspondence to the X-Z montage data (respective part pattern numbers) in the battle game mode or in the congeniality divination game mode.
The display 23 displays side by side the X-Z montages synthesized by the synthesis RAM 41 through the display driver 42 as being used for battle or congeniality divination.
The operation of the present montage game device will be described below.
<Montage Creation>
FIG. 13 is a flowchart indicative of a montage creation process in the montage game device.
When the montage creation key 14 of the input unit 32 is first operated, the CPU 31 sets the montage creation mode (step S1).
In the set montage creation mode, when the battle key 20 is operated to create a battle X or Y montage (step S2a), the battle montage RAM 39 is designated as a storage in which the montage data is to be stored (step S3a).
Next, when the X key 15a is operated to create the X montage which is an opponent (step S4a), an X side montage data storage area 11a or 11A (FIGS. 11A, 11B) in the battle montage RAM 39 is designated (step S5a).
The patterns of parts indicative of montage data constituting a first basic montage and corresponding to the pattern number "01" are read out from the basic part pattern ROM 33 (step S6) and transferred to the synthesis RAM 41, in which a montage is synthesized from the transferred part patterns and then displayed as a battle X montage on the display 23 (step S7).
FIG. 14 is a flowchart indicative of the process of synthesis and display of the montage performed in the course of the montage creation process.
In the synthesis and display process, a set of pattern numbers of parts constituting the first basic montage data is stored as montage data in the battle montage data RAM 39 in the initial setting process. Simultaneously, of the stored pattern numbers of the parts, the pattern number of the part "contour" is first read out (step A1). The part pattern "contour" is read out from the basic part pattern ROM 33 on the basis of the read pattern number of the part "contour", and transferred to and combined in the synthesis RAM 41 (step A2).
Next, of the respective pattern numbers of parts constituting the X montage, the pattern number of a part "hair style" is read out (step A3). A part pattern "hair style" is read out from the basic part pattern ROM 33 on the basis of the read pattern number of the part "hair style", and transferred to and combined in the synthesis RAM 41 (step A4). In this way, the pattern numbers of the parts "eyes", "nose", "mouth" are then read out sequentially. The part patterns of the parts "eyes", "nose", "mouth" are read out from the basic part pattern ROM 33 on the basis of the read pattern number of the parts "eyes", "nose", "mouth" and transferred to and combined in the synthesis RAM 41 (step A5).
Thus, the first basic montage composed of a combination of the part patterns corresponding to the pattern number "01" is displayed on the display 23 (step A6).
When the basic montage select key 16b of the input unit 32 is operated in a state where the first basic montage is displayed on the display 23, the set of part pattern numbers "01" stored in the battle montage data RAM 39 is all changed from "01" to "02" (steps S8, S9).
This causes data on a set of part patterns corresponding to the changed set of part pattern numbers "02" to be read out from the basic part pattern ROM 33 and combined and displayed by the synthesis RAM 41. Thus, a second basic montage composed of all the part patterns corresponding to the pattern number "02" and covering "contour" to "mouth" is displayed on the display 23 (step S7).
Further operation of the basic montage select key 16a, 16b repeats the process at steps S7-S9 to sequentially change and selectively display the 20 kinds of basic montages.
By such operation, the user selects a basic montage similar to an X montage to be created from among the 20 kinds of basic montages and displays that montage on the display 23.
When all or part of that displayed montage is desired to be corrected in a state in which that montage is displayed, the part designation keys 17a, 17b are operated (step S10) to change a particular part of the displayed basic montage to another one. When the part designation keys 17a, 17b are operated, the particular part number is changed from the current stored part number to another (step S11).
When the part pattern select keys 18a, 18b are then operated (step S12), the pattern numbers of the changed part stored in the basic part pattern ROM 33 are changed to another (step S13). This causes a part pattern corresponding to the changed part pattern number to be read out from the basic part pattern ROM 33, and combined in the synthesis RAM 41 and the resulting montage is newly displayed on the display 23 instead of the previous montage (step S13→S7).
Thus, the user can change the pattern of a particular part of the basic montages displayed beforehand on the display 23 to another and display same.
In addition, when the pattern of a further part is desired to be changed to another, the part designation keys 17a, 17b and then the pattern select keys 18a, 18b are required to be operated. (steps S10-S13→S7).
If the entry key 19 of the input unit 32 is operated (step S14) when the display of the X montage which the user has desired has been obtained, the part pattern numbers corresponding to the X montage synthesized in the synthesis RAM 41 are entered as battle X montage data in montage data storage area 11a or 11A of the battle montage RAM 39 (FIGS. 11A, 11B)(step S15).
Similarly, when a Y montage which is an opponent is desired to be created, the montage creation key 14 is similarly operated to set the montage creation mode, the battle key 20 and the Y key 15b are operated to designate a Y side montage data storage area 11b or 11B (FIGS. 11A, 11B) in the battle montage RAM 39 as a storage location where the Y montage data is to be stored (steps S1, S2a, S3a, S4b, S5b). Similarly, repetition of selection of a basic montage by the basic montage select keys 16a, 16b, selection of parts by the part designation keys 17a, 17b and selection of the part patterns by the pattern select keys 18a, 18b causes the respective part patterns corresponding to the desired Y montage to be read out from the basic part pattern ROM 33, and to be combined in the synthesis RAM 41 into a Y montage, which is then displayed on the display 23 (steps S6-S13).
Thus, by operating the entry key 19 of the input unit 32 after the display of the desired Y montage is ascertained, the numbers of the respective part patterns corresponding to the Y montage synthesized in the synthesis RAM 41 are entered as the battle Y montage data in the area 11b or 11B of the battle montage RAM 39 (FIGS. 11A, 11B) (steps S14, S15).
Similarly, when a Z montage which is an opponent is desired to be created, the montage creation key 14 is operated to set the montage creation mode, and the battle key 20 and the Z key 15c are operated. Repetition of designation of a Z side montage data storage area (FIG. 11A or 11B) in the battle montage RAM 39 as a storage location where the Z montage data is to be stored, selection of a basic montage by the basic montage select keys 16a, 16b, selection of parts by the part designation keys 17a, 17b and selection of the part patterns by the pattern select keys 18a, 18b causes the respective part patterns corresponding to the desired Z montage to be read out from the basic part pattern ROM 33, and to be combined in the synthesis RAM 41 into a Z montage, which is then displayed on the display 23. Thus, by operating the entry key 19 of the input unit 32 after the display of the desired Z montage is ascertained, the respective part pattern numbers corresponding to the Z montage synthesized in the synthesis RAM 41 are entered as the battle Z montage data in the respective areas (FIGS. 11A and 11B) of the battle montage RAM 39 (FIGS. 11A, 11B). Those steps are the same as the steps of creation and entry of the X and Y montages, as mentioned above, so that they are not shown in the flowchart.
In this way, the battle X, Y and Z face or whole body montage data (respective part pattern numbers) created for the battle is entered in the battle montage RAM 39 (FIGS. 11A, 11B).
<Congeniality Divination Montage Creation Process>
When an X montage for congeniality divination is desired to be created in the montage creation process of FIG. 13, the following operation is performed.
First, the montage creation key 14 is operated (step S1) to set the montage creation mode. The congeniality divination key 21 and X key 15a are then operated to designate an X side montage storage area 12a or 12A (FIGS. 12A, 12B) of the congeniality divination montage RAM 40 as a storage in which the X montage data is to be stored (steps S2b, S3b, S4c, S5c).
In a manner similar to the above-mentioned battle montage creation, repetition of selection of a basic montage by the basic montage select keys 16a, 16b, selection of parts by the part designation keys 17a, 17b and selection of the part patterns by the pattern select keys 18a, 18b causes the respective part patterns corresponding to the desired X montage to be read out from the basic part pattern ROM 33, and to be combined in the synthesis RAM 41 into the X montage, which is then displayed on the display 23 (steps S6-S13).
Thus, by operating the entry key 19 of the input unit 32 after achievement of the display of the desired X montage is ascertained, the respective part pattern numbers corresponding to the X montage synthesized in the synthesis RAM 41 are entered as the congeniality divination X montage data in the respective montage data storage areas 12a or 12A of the congeiality divination montage RAM 40 (FIGS. 12A and 12B) (steps S14, S15).
Similarly, when a Y montage which is another partner for congeniality divination is desired to be created, the montage creation key 14 is operated to set the montage creation mode. The congeniality divination key 21 and the Y key 15b are then operated to designate a Y side montage data storage area 12b or 12B (FIG. 12A or 12B) in the congeniality divination montage RAM 40 as a storage location where the Y montage data is to be stored (step S1, S2b, S3b, S4d, S5d). In a manner similar to the above-described manner, repetition of selection of a basic montage by the basic montage select keys 16a, 16b, selection of parts by the part designation keys 17a, 17b and selection of the part patterns by the pattern select keys 18a, 18b causes the respective part patterns corresponding to the desired Y montage to be read out from the basic part pattern ROM 33, and to be combined in the synthesis RAM 41 into the Y montage, which is then displayed on the display 23 (steps S6-S13).
Thus, by operating the entry key 19 of the input unit 32 after achievement of the display of the desired Y montage is ascertained, the respective part pattern numbers corresponding to the Y montage synthesized in the synthesis RAM 41 are entered as the congeniality divination Y montage data in the respective montage data storage areas 12b, 12B of the congeniality divination montage RAM 40 (FIGS. 12A, 12B) (steps S14, S15).
In this way, data on the battle X-Z face or whole body montages (respective part pattern numbers) created for the battle are entered in the battle montage RAM 39 (FIGS. 11A, 11B).
When a Z montage which is another opponent is desired to be created, a similar operation is performed: The montage creation key 14 is operated to set the montage creation mode. The congeniality divination key 21 and the Z key 15c are then operated. Repetition of designation of a Z side montage data storage area (FIG. 12A or 12B) in the congeniality divination montage RAM 40 as a storage location where the Z montage data is to be stored, selection of a basic montage by the basic montage select keys 16a, 16b, selection of parts by the part designation keys 17a, 17b and selection of part patterns by the pattern select keys 18a, 18b causes the respective part patterns corresponding to the desired Z montage to be read out from the basic part pattern ROM 33 and to be combined in the synthesis RAM 41 into the Z montage, which is then displayed on the display 23. By operating the entry key 19 of the input unit 32 after achievement of the display of the desired Z montage is ascertained, the respective part pattern numbers corresponding to the Z montage synthesized in the synthesis RAM 41 is entered as the congeniality divination Z montage data in the respective montage data storage areas of the congeniality divination montage RAM 40 (FIGS. 12A, 12B) (steps S14, S15). Those steps are the same as the steps of creation and entry of the X and Y montages, as mentioned above, so that they are not shown in the flowchart.
In this way, the congeniality divination X-Z face or whole body montage data (respective part pattern numbers) are entered in the congeniality divination montage RAM 40 (FIGS. 12A, 12B).
<Battle Game Process>
FIG. 15 shows the former half of a battle game process performed by the montage game device. FIG. 16 shows the latter half of the battle game process. FIG. 17A-17C shows a displayed state of the X and Y montages involved in the battle game process.
When this process is performed, it is assumed that X, Y and Z battle face montage data of FIG. 11A is entered beforehand in the battle montage RAM 39 after the montage creation process (FIGS. 13, 14).
First, when the battle key 20 is operated in the former half of the battle game process of FIG. 15 (step B0), CPU 31 sets the battle game mode. The montages of two persons who are opponents to each other are selected from among the X, Y and Z montages (step B1). For example, if the X and Y montages are selected, the X and Y face montage data (FIG. 11A) entered in montage data storage areas 11a, 11b of the battle montage RAM 39 are read out (step B2).
The respective part patterns corresponding to the X and Y face montage data read out from the battle montage RAM 39 are read out of the basic part pattern ROM 33 (step B3). The read part patterns read out are combined in the synthetic memory 41. Thus, as shown in FIG. 17A, the X and Y face montages for battling purposes are displayed (step B4).
Simultaneously, the face montage battle scores for the part patterns constituting the respective X and Y face montages are read out from the corresponding battle score storage areas 34a (FIG. 4A) of the battle score ROM 34 (step B5) and stored in the respective battle score storage areas 11c, 11d of the battle montage RAM 39 corresponding to the X and Y.
The battle scores of the respective parts stored in the battle score storage areas 11c and 11d are summed for each of the face montages. The respective total sums of the battle scores are stored in the corresponding total sum score storage areas 11e and 11f (FIG. 11A) (step B6).
As shown in FIG. 17A, when a predetermined time, for example, of 3 seconds, has elapsed in a state where the respective face montages of the X and Y who are battle opponents to each other are displayed (step B7), the part patterns "eyes" and "mouth" in the intermediate portion of the first stage are read automatically read out from the part pattern areas (FIG. 6A) of an expression part pattern ROM 36 in correspondence to the respective pattern numbers of the parts "eyes" and "mouth" in each of the face montage (step B8). Thus, the old part patterns "eyes" and "mouth" alone are replaced with those read part patterns in the synthetic memory 41. Thus, as shown in FIG. 17B, expression changes are imparted to the X and Y face montages in the first battle stage and the X and Y face montages in the former half stage of the battle are displayed (step B9).
If a further predetermined time, for example, of 3 seconds, has elapsed in a state in which the X and Y face montages in the former half stage of the battle of FIG. 17B are displayed (step B10), data on the respective patterns of the parts "eyes" and "mouth" for the display of the intermediate portion of the second stage are read out from the part pattern area 36b (FIG. 6B) of the expression part pattern ROM 36 in correspondence to the pattern numbers of the parts "eyes" and "mouth" of each of the face montages (step B11). The old part patterns "eyes" and "mouth" alone are replaced with the read new "eyes" and "mouth" for synthesizing purposes in the synthetic memory 41. Thus, expression changes at the second battle stage are imparted to the respective face montages, and the respective resulting X and Y face montages in the latter half stage of the battle are displayed (step B12).
Thereafter, if another predetermined time, for example, of 3 seconds, has elapsed (step B13), the X and Y battle total sum scores stored in the X and Y total sum score storage areas 11e, 11f (FIG. 11A) of the battle montage RAM 39 at step B6 are read out (step B14). Thus, it is determined whether X is a winner and Y is a loser by comparison between the battle total sum scores (step B15). FIG. 11A shows that X and Y have scores "8" and "29", respectively, so that X and Y are judged to be a loser and a winner, respectively.
If the battle total score of the X montage is determined to be equal to that of the Y montage at step B16 of the victory/defeat determining process, the basic part patterns of the parts "eyes" and "mouth" are again read out from the basic part pattern ROM 33 in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the respective face montages (step B17). Thereafter, the draw message "Mmm . . . " stored beforehand in the battle message ROM 37 is read out (step B18).
The basic patterns of the parts "eyes" and "mouth" corresponding to the respective read X and Y face montages are transferred to the synthetic memory 41, where the previous patterns of the parts "eyes" and "mouth" alone are replaced with the read new transferred part patterns in the X and Y face montages displayed as the latter half stage of the battle at step B12, and the resulting basic X and Y face montages are combined with the draw message "Mmm . . . " (step B19).
Thus, the respective X and Y basic face montages stored beforehand in the battle montage RAM 39 are displayed along with the draw message "Mmm . . . " on the display 23 (step B20).
If the total battle score of the X montage is determined to be larger than that of the Y montage at step B21, that is, that X and Y are determined to be a winner and a loser, respectively, the patterns of the parts "eyes" and "mouth" of the winner X montage for display of the result of the victory are read out from the expression part pattern ROM 36 (FIG. 6C) in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the montage of the winner X (FIG. 6C). The patterns of the parts "eyes" and "mouth" of the montage of the loser Y for display of the result of the defeat and a defeat background pattern are read out from the expression part pattern ROM 36 (FIG. 7B) in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the face montage of the loser Y (FIG. step B22).
Thereafter, the victory message "I won. Wow!" and the defeat message "I lost. Sorry!" stored beforehand in the battle message ROM 37 are read for X and Y side displaying purposes, respectively (step B23).
This causes the patterns "eyes" and "mouth" for the result of the victory and corresponding to the X face montage read out from the expression part pattern ROM 36, and the patterns of the parts "eyes" and "mouth" for the result of the defeat and corresponding to the Y face montage read out from the expression part pattern ROM 36 to be transferred to the synthesis memory 41. In the synthesis memory 41, the old patterns of the parts "eyes" and "mouth" alone of the X face montage are replaced with the corresponding ones transferred for the result of the victory displayed as the latter half stage of the battle at step B12 in the X face montage while the old patterns the parts "eyes" and "mouth" alone of the Y face montage are replaced with the corresponding ones transferred for the result of the defeat displayed as the latter half stage of the battle at step B12 in the Y face montage, and the resulting X and Y montages are combined with the X side victory message "I won. Wow!" and the Y side defeat message "I lost Sorry!", respectively, read out from the battle message ROM 37 (step B24).
Thus, the X side face montage is changed so as to have a delightful expression, which is displayed along with the victory message "I won. Wow!" while the Y side face montage is changed so as to have a sad expression, which is displayed along with the defeat message "I lost. Sorry!" (step B25).
If the total battle score of the Y montage is determined to be larger than that of the X montage at step B21, that is, X and Y are determined to be a loser and a winner, respectively, the patterns of the parts "eyes" and "mouth" for display of the result of the defeat and the defeat background pattern are read out from the expression part pattern ROM 36 (FIG. 7B) in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the face montage of the loser X. The patterns of the parts "eyes" and "mouth" for display of the result of the victory are read out from the expression part pattern ROM 36 (FIG. 6C) in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the face montage of the winner Y (FIG. step B26). The defeat message "I lost. Sorry!" and the victory message "I won. Wow!" stored beforehand in the battle message ROM 37 are read for X and Y side displaying purposes, respectively (step B27).
This causes the patterns "eyes" and "mouth" for the result of the defeat and corresponding to the X face montage read out from the expression part pattern ROM 36, and the patterns of the parts "eyes" and "mouth" for the result of the victory and corresponding to the Y face montage read out from the expression part pattern ROM 36 to be transferred to the synthesis memory 41. In this memory the X and Y side old patterns of the parts "eyes" and "mouth" alone are replaced with the corresponding transferred ones as patterns indicative of the results of the defeat and victory in the X and Y face montages, respectively, shown as the latter half stage of the battle at step B12, and the resulting X and Y face montages are combined with the X side defeat message "I lost. Sorry!" and the Y side victory message "I won. Wow!", read out from the battle message ROM 37 (step B28).
Thus, for example, as shown in FIG. 17C, the X face montage is changed so as to have a sad expression, which is displayed along with the defeat message "I lost. Wow!" while the Y face montage is changed so as to have a delightful expression, which is displayed along with the victory message "I won. Wow!" (step B29).
<Congeniality Divination Game Process>
FIG. 18 shows the former half process of a congeniality divination game performed in the montage game device and FIG. 19 shows the latter half process of the game. FIGS. 20A-20C show displayed states of the X and Y montages in the congeniality divination game.
In this process, it is assumed that X-Z congeniality divination face montage data of FIG. 12A which is obtained in the montage creation process (FIGS. 13 and 14) is stored beforehand in the congeniality divination montage RAM 40.
First, when the congeniality divination key 21 is operated in the former half of the congeniality divination game process of FIG. 18 (step C0), CPU 31 sets the congeniality divination game mode. The montages of two persons who are partners for each other are selected from among the X, Y and Z montages (step C1). For example, if the X and Y montages are selected, the X and Y montage face montage data (FIG. 12A) entered in the congeniality divination montage RAM 40 is read out (step C2).
The respective part patterns constituting each of the X and Y face montages are read out from the basic part pattern ROM 33 in correspondence to the read X and Y face montage data (step C3) and combined to synthesize X and Y face montages in the synthesis memory 41. Thus, as shown in FIG. 20A, the X and Y face montages for congeniality divining purposes are displayed (step C4).
The face montage congeniality scores for the part patterns constituting the respective X and Y face montages are read out from the corresponding congeniality score areas 35a (FIG. 5A) of the congeniality score ROM 35 and stored in the respective X and Y congeniality score storage areas 12c, 12d of the congeniality divination montage RAM 40 (step C5). The stored congeniality scores for the respective parts are summed for each of the face montages. The respective X and Y sum scores are stored in the corresponding sum score storage areas 12e and 12f (FIG. 12A) (step C6).
As shown in FIG. 20A, when a predetermined time, for example, of 3 seconds, has elapsed after the face montages of the X and Y who are partners for each other are displayed (step C7), the patterns of the parts "eyes" and "mouth" for display of the intermediate portion of the first stage for congeniality divination are read out from the expression part pattern ROM 36 in correspondence to the pattern numbers of the parts "eyes" and"mouth" in the respective face montages (step C8), and transferred to the synthesis memory 41. Thus, the old patterns of the parts "eyes" and "mouth" alone are replaced with the new transferred ones in the synthesis memory 41. Thus, for example, as shown in FIG. 20B, expression changes in the first divination stage are imparted to the X and Y face montages, and the X and Y face montages in the former half stage of the divination are shown (step C9).
If a further predetermined time, for example, of 3 seconds, has elapsed after the X and Y face montages are displayed in the former half stage of the divination, as shown in FIG. 20B (step C10), the respective patterns of the parts "eyes" and "mouth" for the display of the second intermediate stage are read out from the expression part pattern ROM 36 in correspondence to the numbers of the patterns of the parts "eyes" and "mouth" of the respective face montages (step C11) and transferred to the synthesis memory 41. The old patterns of the parts "eyes" and "mouth" alone of the montages are replaced and combined with the new transferred patterns of the parts "eyes" and "mouth" read out in the synthesis memory 41. Thus, expression changes at the second divination stage are imparted to the respective face montages, and the respective X and Y face montages are displayed as the latter half stage of the divination (step C12).
Thereafter, if another predetermined time, for example, of 3 seconds, has elapsed (step C13), the total sum congeniality scores stored in the X and Y total sum score storage areas 12e, 12f (FIG. 12A) of the congeniality divination montage RAM 40 at step C6 are read out (step C14). Thus, the degree of congeniality between the X and Y is determined by comparison between the total sum scores (step C15). In FIG. 12A, it is determined that X and Y have total sum scores "25" and "21", respectively, and that the difference between X and Y is "4".
If difference between the congeniality total scores of the X and Y montages is determined to be within 0-3, that is, the degree of congeniality between the X and Y is high at step C16, the patterns of the parts "eyes" and "mouth" for display of the result of the coincidence of congeniality and a congeniality coincidence background pattern are read out from the respective areas 36d (FIG. 7A) of the expression part pattern ROM 36 in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the respective X and Y face montages (step C17). The congeniality messages "Perfect congenial" and "I am delighted" stored in the congeniality message ROM 38 and corresponding to the score difference "0"-"3" stored in the congeniality message ROM 38 are read out (step C18).
The part patterns as the result of congeniality coincidence of "eyes" and "mouth" corresponding to the respective X and Y face montages and the congeniality coincidence background pattern and read out from the expression part pattern ROM 36 are transferred to the synthesis memory 41. In the synthesis memory 41, the old patterns of the parts "eyes" and "mouth" alone of the X and Y montages are replaced with the new transferred part patterns as the pattern indicative of the result of the congeniality coincidence in the X and Y face montages displayed as the latter half stage of the divination at step C12 and the resulting X and Y face montages are combined with the congeniality coincidence background pattern and the congeniality coincidence messages "Perfect congenial!" and "I am delighted!" read out from the congeniality message ROM 38 (step C19).
Thus, for example, as shown in FIG. 20C, delighted expression changes are imparted to the respective X and Y face montages, and the resulting X and Y face montages are displayed along with the congeniality coincidence background pattern and the congeniality coincidence messages "Perfect congenial!" and the "I am delighted!" on the display 23 (step C20).
If difference between the total congeniality score of the X and Y montages is "4"-"15" at step C21, that is, the degree of congeniality between the X and Y is determined to be common, the basic patterns of the parts "eyes" and "mouth" are again read out from the basic part pattern ROM 33 in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the X and Y face montages (step C22). The common congeniality messages "Almost congenial, aren't we?" and "We will be friends" corresponding to the score difference "4"-"15" stored beforehand in the congeniality message ROM 38 are read out (step C23).
This causes the basic patterns of the parts "eyes" and "mouth" corresponding to each of the X and Y face montages read out from the basic part pattern ROM 33 to be transferred to the synthesis memory 41. In this memory 41, the old patterns of the parts "eyes" and "mouth" alone of the X and Y face montages are replaced with the corresponding transferred ones in the X and Y face montages displayed as the latter half stage of the divination at step C12, and the resulting X and Y montages are synthesized with the common congeniality messages "Almost congenial, aren't we?" and "We will be friends!" read out from the congeniality message ROM 38 (step C24).
Thus, the X and Y basic face montages entered beforehand in the congeniality divination montage RAM 40 are displayed along with the common congeniality messages "Almost congenial, aren't we?" and "We will be friends!" on the display 23 (step C25).
If difference between the X and Y total congeniality scores is not less than "16" at step C21, that is, the degree of congeniality between the X and Y is determined to be low, the patterns of the parts "eyes" and "mouth" for display of the result of the congeniality non-coincidence and a congeniality non-coincidence background pattern are read out from the expression part pattern ROM 36 (FIG. 7B) in correspondence to the pattern numbers of the parts "eyes" and "mouth" of the respective X and Y face montages (step C26).
The congeniality non-coincidence messages "Never congenial!" and "We will fight it out at a battle game!" corresponding to the score difference "16"-"29" stored beforehand in the congeniality message ROM 38 are read out (step C27).
This causes the congeniality non-coincidence result patterns of the parts "eyes" and "mouth" and a congeniality non-coincidence background pattern corresponding to each of the X and Y face montages read out from the expression part pattern ROM 36 to be transferred to the synthesis memory 41. In this memory 41 the old patterns of the parts "eyes" and "mouth" alone of the montages are replaced with the corresponding transferred ones as the congeniality non-coincidence result patterns in the X and Y face montages displayed as the latter half of the divination stage at step C12, and the resulting X and Y montages are combined with the congeniality non-coincidence background pattern and the congeniality non-coincidence messages "Never congenial!" and "We will fight it out at a battle Game!", read out from the congeniality message ROM 38 (step C28).
Thus, the X and Y face montages each are changed so as to have a sad expression, which is displayed along with the congeniality non-coincidence background pattern and the congeniality non-coincidence messages "Never congenial!" and "We will fight it out at a battle Game!" (step C29).
In summary, in the present montage game device, the X and Y montage data for battling purposes or congeniality divining purposes is first entered in the battle montage RAM 39 or the congeniality divination montage RAM 40, and the respective part patterns of the entered X and Y montage data are read out from the basic part pattern ROM 33, and combined in the synthesis RAM 41 and the resulting montages are displayed side by side on The display 23.
In the case of a battle game, battle scores corresponding to the respective part patterns of each of the montages are read out from the battle score ROM 34, the read battle scores are summed for that montage, victory/defeat of X and Y is decided by comparison in magnitude between the battle total scores, and the winner's montage is changed so as to have a delighted expression, which is then displayed along with the victory message on the display 23. The loser's montage is changed so as to have a sad expression, which is then displayed along with a defeat message.
In the case of a congeniality divination game, congeniality scores corresponding to the respective part patterns of each of the montages are read out from the congeniality score ROM 35, the read congeniality scores are summed for that montage, and the degree of congeniality between X and Y is determined by the difference between the X and Y total scores. If the difference is small, the X and Y montages are changed so as to have a delighted expression, and then displayed along with the congeniality coincidence message on the display 23. If the difference is large, the respective X and Y montages are changed so as to have a sad expression, and then displayed along with a congeniality non-coincidence message on the display 23.
By the above-mentioned construction, a battle game in which X and Y battles with each other or a congeniality divination game in which the degree of congeniality between X and Y is divined can be played. The result of battling between X and Y and the degree of congeniality between X and Y can easily be gripped objectively depending on a change in the expression of each montage itself or the displayed contents of a message, and hence a very interesting game is realized.
While the present embodiment is constructed such that the result of battling between X and Y and the degree of congeniality between X and Y are displayed, using the total sums of battle scores or the total sums of congeniality scores (see the score storage areas of FIGS. 4A-5B, 11A-12B) corresponding to the part patterns of the respective montages, the present invention is not limited to that embodiment. Alternatively, arrangement may be such that the result of battling and the degree of congeniality between X and Y is displayed, using the total sum of the pattern numbers of the parts of each of the montages (see the storage areas of the part pattern numbers of FIGS. 11A-12B) as the battle score or the congeniality score.
[Second Embodiment]
FIGS. 21 and 22 show a second embodiment of the present invention. In the congeniality divination game in the first embodiment, congeniality scores preset in correspondence to the respective part patterns of each of the X and Y montages are read out from the congeniality score ROM 35, the read congeniality scores are summed for that montage, and the degree of congeniality between X and Y is determined by the difference between the totalized scores. In contrast, the second embodiment is constructed such that in a congeniality divination game congeniality scores are allocated beforehand to all the respective face types of montages, any two congeniality scores are compared and the degree of congeniality between the corresponding montages is determined on the basis of the result of the comparison. The second embodiment also uses the same montage game device as the first embodiment.
FIG. 21 shows a stored state of data in a face type congeniality correspondence ROM used in the second embodiment. The face types of montages are compared using data in the face type congeniality correspondence ROM, and the congeniality between those faces is divined on the basis of the comparison. To this end, a degree of congeniality is preset according to a combination of the X and Y face types in the face type congeniality correspondence ROM.
Also, in the second embodiment, congeniality divination is conducted on the basis of a combination of the face types of montages using a game device similar to that used in the first embodiment.
The congeniality divination game process in this case will be described with respect to FIG. 22.
In this case, it is assumed that X and Y congeniality divination montage data of FIG. 12A which is obtained in the above-mentioned montage creation process (FIGS. 13 and 14) is entered beforehand in the congeniality divination montage RAM 40.
First, when the congeniality divination key 21 is operated at step D1 of FIG. 22, CPU 31 sets the congeniality divination game mode. Thus, the X and Y montage data entered in the congeniality divination montage RAM 40 (FIG. 12A) are read (step D2).
This causes the respective part patterns constituting each of the read X and Y face montages to be read out from the basic part pattern ROM 33 in correspondence to the X and Y face montage data read out from the montage RAM 40 (step D3). The read part patterns are transferred and used to synthesize the X and Y face montages in the synthesis memory 41. Thus, as shown in FIG. 20A, the X and Y face montages are displayed for congeniality divining purposes (steps D3, D4).
After the respective montages are displayed, the receptive face types of the montages are sought from the patterns "contour" and "hair style" of the respective X and Y face montages synthesized in the synthesis RAM 41 at step D5. While the face types (round, elliptic, etc.) can be obtained from the shapes of the patterns "contour" and "hair style" as in the embodiment, similar face types may be stored beforehand for each of the "contour" and "hair style" patterns.
Scores indicative of the degree of congeniality are obtained from the respective areas 200a (FIG. 21) of the face type congeniality correspondence ROM 21 on the basis of a combination of the X and Y face types (step D6). When a combination of X and Y face types is shown in a single circle and a double circle, the scores "0"-"3" are allocated to the combination; when a combination of X and Y face types is shown in a triangle, the scores "4"-"15" are allocated; and when a combination of X and Y face types is shown in a cross, the scores "16" or more are allocated. Thus, when, for example, "round" face types are compared, scores "0"-"3" are allocated to the combination of those face types because this combination is shown by a double circle.
Thereafter, when a predetermined time has elapsed (step D7), part patterns and a message corresponding to an expression which depends on a congeniality score obtained from the face type congeniality correspondence ROM are read out from the expression part pattern ROM 36 and the congeniality message ROM 38 in a process similar to the process at steps C16-C29 of FIG. 19. Thus, the X and Y face montages are displayed, for example, as shown in FIG. 20C (step D8).
While the operation of the battle game or the congeniality divination game in the above embodiments is described as using the X and Y face montages, a battle game and a congeniality divination game similar to those in the above embodiments may be played even when X and Y whole body montages are used.
[Third Embodiment]
FIGS. 23-25 show a third embodiment of the present invention. FIG. 23 shows the outer surface structure of an infrared optical communication type montage game system as the third embodiment. FIG. 24 shows the structure of an electronic structure of a large display device used in the game system. FIG. 25 shows the structure of an electronic circuit of a game device body used in the game system. In FIG. 25, only the structure of one of the device bodies 51a, 51b is shown because the device bodies 51a, 51b have the same structure.
In the above respective embodiments, the single game device body 11 creates, enters and displays X-Z montages used when a battle game or a congeniality divination game is played, and performs a battle game process and a congeniality divination game process based on the created montages. In contrast, in the third embodiment, the game device bodies 51a, 51b which the respective users use have the same functions as the game device body 11 of the first and second embodiments. The respective montage data items created and entered by the respective game device bodies 51a, 51b are sent to the large display device 52 and displayed on its large display 55. A battle game and a congeniality divination game similar to those played in the previous embodiments are played on the display device 52. The same reference numeral is used to identify the same element in Figures directed to the present and previous embodiments and further description of the same element will be omitted.
The X-Z battle or congeniality divination montage data created in the respective game device bodies 51a and 51b is entered in a battle montage RAM 39 or a congeniality divination montage RAM 40 provided in the respective game device bodies 51a and 51b. The entered data is sent as an infrared optical signal through a transmitter 53 of the game device bodies to the external large display device 52 where the respective signals are received by a receiver 54 of the display device 52 and then stored in the battle montage RAM 39 or congeniality divination montage RAM 40.
The respective X-Z montage data items stored in the battle montage RAM 39 and congeniality divination montage RAM 40 of the large display device 52 are read out as required by later setting of a battle game mode or a congeniality divination mode. On the basis of the read montage data, the corresponding part patterns are read out from the basic part pattern ROM 33, and used to synthesize montages in the synthesis RAM 41, and the montages are displayed on the large display 55.
Thereafter, when the start key 22, battle key 20 and congeniality divination key 21 of the input unit 32 are operated, the resulting key signals are input through the transmitter 53 to the receiver 54 of the display device 52. Thus, when the battle game mode is set as in the previous embodiments, the appropriate part patterns are read out from the basic part pattern ROM 33 and the expression part pattern ROM 36 on the basis of data on two target ones of the X-Z respective montages data on which is stored in the montage RAMs 39, 40; predetermined data is read out from the battle score ROM 34 and the battle message ROM 37; and a battle game process is performed using those data items. When the congeniality divination game mode is set, a congeniality divination game process is performed using data on two target ones of the X-Z respective montages stored in the montage RAMs 39, 40, congeniality score ROM 35 and the congeniality message ROM 38 as in the battle game. During the game, data or a signal to be sent from the game device bodies 51a and 51b is input through the transmitter 53 and receiver 54 to the display device 52.
[Fourth Embodiment]
FIGS. 26 and 27 show a fourth embodiment of the present invention. FIG. 26 shows an outer surface structure of a montage game system which has the functions of infrared optical communication and ROM exchange. FIG. 27 shows the structure of an electronic circuit of the system. The same reference numeral is used to identify the same element in the Figures directed to the fourth and first embodiments and further description of the element will be omitted.
In the montage game system of the fourth embodiment, and a game device body 111a of one party is adapted to optically send, on infrared rays, montage data created and entered therein through its transmission-reception unit 56 to a transmission-reception unit 56 of a game device body 111b of the other party. The game device body 111a also is adapted to optically receive, using its transmission-reception unit 56, data on the other party's montage sent optically on infrared rays from the transmission-reception unit 56 of the game device device 111b, and to enter the received data in the battle montage RAM 39 and the congeniality divination montage RAM 40 thereof. The system is further adapted to exchange a coin-like external ROM assembly which includes a basic part pattern ROM 33, battle score ROM 34, congeniality score ROM 35, expression part pattern ROM, battle message ROM 37, and congeniality message ROM 38. Entered montage data to be sent may be data on a combination of a part number and a part pattern number or data on respective part pattern numbers following the sequence of part numbers.
According to the montage game system having such functions, the respective montage data items of one party and the other party are transferrable between the game device bodies 111a and 111b of the one and the other party, respectively. Furthermore, a desired one of coin-like external ROMs 57 which have entered therein different montage data items, for example, of the faces of well-known persons is put into the ROM receiving recess 58, and the desired external ROM 57 is connected to the device body 111a through a connection terminal 58a provided in the recess 58. In such state, montage data items different in content and stored in the coin-like external ROM 57 are transmitted between the game device bodies 111a and 111b through the respective transmission-reception units 56. Thus, for example, a battle game or a congeniality divination game can be played using montage data entered by the one party in the respective RAMs 39, 40 of the game device proper 111a and the montage data received from the game device body 111b of the other party and entered in the RAMs 39, 40 of the game device body 111a. Thus, the battle game and the congeniality divination game are further diversified.
While in the embodiments of FIGS. 23-27 the montage data, etc., is transmitted using infrared optical radio communication, montage data, score data, etc., may be transmitted without using the infrared optical communication but using another radio (electric wave) or cable (telephone line) communication.
While in the respective previous embodiments the results of a battle game, etc., are displayed visually using the display device, the present invention is not limited to those embodiments. Alternatively, the intermediate state and result of a game may be printed out using a printing device such as a label printer or a word processor printer.
[Fifth Embodiment]
FIGS. 28 and 31 show a fifth embodiment of the present invention. In FIG. 28, the same reference numeral is used to identify the same element in the Figures directed to the fifth and first embodiments and further description of the element will be omitted.
CPU 31 is connected to an input unit 32, pattern ROM 33, luck divination score ROM 135, message ROM 137, RAM assembly 61A, synthesis RAM 41, display driver 42 and display 23. The scores of luck in work, love, and money preset in correspondence to the respective part patterns stored in the part pattern ROM 33 are stored in the luck divination score ROM 135.
FIG. 29 shows a stored state of luck scores in the luck divination score ROM 135. For example, the score of luck in work corresponding to a storage area "01" of a "contour" part "1" is stored beforehand as "5"; the score of luck in love is stored beforehand as "3"; the score of luck in money is stored beforehand as "2". The score of luck in work corresponding to a storage area "02" of a "hair style" part "2" is stored beforehand as "3"; the score of luck in love is stored beforehand as "3"; the score of luck in money is stored beforehand as "4".
Luck messages which correspond to the respective total sums of the scores of luck in the work, love, and money obtained in correspondence to the respective part patterns constituting a face montage are stored at the corresponding locations of luck in the work, love and money in the message ROM 137.
FIG. 30 shows a stored state of messages on luck in work in the message ROM 137. If the total sum of scores of luck in work obtained in correspondence to the respective part patterns of a face montage is "5"-"10", a luck message "Make twice as many efforts as others" is stored beforehand in the ROM 137; if it is "11"-"20", a luck message "Your luck is improving is stored beforehand; and if it is "21"-"25", a luck message "Best condition" is stored beforehand. Although not shown, messages on luck in the respective love and money are stored beforehand as in the case of the luck in work.
The RAM assembly 61A is provided with a part pattern number RAM 61A-1 which stores the respective pattern numbers of the parts of a montage entered by the user, a change part RAM 61A-2 which stores a part number, and a score RAM 61A-3 which stores the respective total sums of the scores for luck in each of the work, love and money and corresponding to part pattern numbers stored in the part pattern number RAM 61A-1.
The input unit 32 includes part designation keys 17a, 17b; pattern select keys 18a, 18b; an entry key 19; and a divination key 121 which is operated to divine luck in each of the work, love and money for a face montage created and entered. It further includes an ON key; an OFF key; a montage creation key; and a start key corresponding to those in the embodiment of FIG. 1.
The operation of the present montage game device will be described below. FIG. 31 is a flowchart indicative of the creation and divination of a face montage in the montage game device.
When CPU 31 sets the montage creation mode in accordance with the keying-in operation in the input unit 32 (step 21), the part number "1" which indicates that the part is a "contour" is set initially in the change part RAM 61A-2 (step S22). Then, the part pattern number "01" is set initially in the "contour" area of the part pattern number RAM 61A-1 (step S23).
This causes a first pattern of the part "contour" stored in the part pattern ROM 33 to be read out on the basis of the "contour" part pattern number data "01" stored in the part pattern number RAM 61A-1; to be stored in the synthesis RAM 41; and causes the resulting montage to be displayed at a predetermined position on the display 23 (step S24).
The part designation keys 17a, 17b are operated to update sequentially the part numbers designated by the change part RAM 61A-2. The respective part pattern numbers are selected by the pattern select keys 18a, 18b to be set in the respective part areas of the part pattern number RAM 61A-1. This causes CPU 31 to read out the respective patterns of the parts "hair style", "eyebrows", "eyes", "nose","mouth", etc., stored in the part pattern ROM 33. The synthesis RAM 41 synthesizes from the read patterns face montages, which are then displayed on the display 23 as in the previous embodiments (steps S21-S24).
When the entry key 19 is operated after any face montage is created and displayed, the created face montage data is stored in the part pattern number RAM 61A-1 and the change part RAM 61A-2.
When the divination key is operated to divine the luck of the face montage displayed on the display 23 after the face montage is entered (step S25), CPU 31 ascertains whether the face montage is already entered or now in display (step S26).
If so, data on the respective pattern numbers of the parts of the entered face montage are read out from the part pattern RAM 61A-1 of the RAM assembly 61A. Simultaneously, scores of luck in each of the work, love and money corresponding to the respective part pattern numbers are read out from the luck divination score AROM 135. The respective total sums of the luck scores read out are counted by the operation of CPU 31 and stored in the score RAM 61A-3 of the RAM assembly 61A (step S27).
As described above, when the respective total sums of scores of luck in each of the work, love and money corresponding to the face montage now entered or displayed are obtained in the score RAM 61A-3, the luck messages corresponding to the respective total sums of the luck scores are read out from the message ROM 137 (step S28), and the luck messages are displayed on the display 23 along with the entered face montage, as shown in FIG. 32 (step S29).
According to the present montage game device, scores of luck in work, love and money corresponding to the face montage created and entered or now in display are read out from the luck divination score ROM 135, and summed, and data on the obtained total sums of the luck scores are then stored in the score RAM 61A-3. Thereafter, the respective messages for luck in work, love and money and stored in the message ROM 137 are selectively read out according to the stored total sums of scores for the respective luck items, and displayed on The display 23. Thus, luck divination or physiognomy divination corresponding to the face montage can be performed, using any face montages created by the user.
While the luck scores used in the luck divination are described as the respective total sums of luck scores allocated to the respective part pattern numbers in the present embodiment, they may be predetermined fixed values minus the corresponding values of the luck scores allocated to the respective part pattern numbers, versions of the values of the luck scores allocated to the respective part pattern numbers and, for example, obtained by multiplication, or the total sums of the luck scores allocated to some of the part pattern numbers of a face montage and not to all the part pattern numbers of the face montage.
While in the present embodiment luck or physiognomy divination is shown as being performed on the basis of the face montage, it may be performed on the basis of a whole body montage.
[Sixth Embodiment]
FIGS. 33-37C show a sixth embodiment of the present invention. The same reference numeral is used to identify the same element in the Figures directed to the present and previous embodiments and further description of the element will be omitted.
CPU 31 used in a montage game device of the present embodiment is connected to a ROM assembly 60B, a RAM assembly 61B, an input unit 32, a display driver 42, a display 23 and a synthesis RAM 41.
The ROM assembly 60B includes various control programs for control of CPU 31, a part pattern ROM 33, and a self-congeniality correspondence ROM 60B-2 which stores a table indicative of a relationship in correspondence between each of the part patterns and a part pattern congenial to the former one.
The part pattern ROM 33 of the ROM assembly 60B is a part pattern ROM similar to that of the first embodiment of FIG. 3 and stores in the form of a bit map 50 kinds of part patterns prepared for "contour", "hair style", "eyes", "nose", "mouth", as shown in FIG. 3A
For example, for the "contour" part pattern, an "average face" is stored at address "1" (No. "01"); a "round face" is stored at address "2" (No. "02" ); . . . . . . ; an "elliptic face" is stored at address "49" (No. "49"); and a "sharp-jawed face" is stored at address "50" (No. "50"). For the hair style part pattern, a "hair style with a flowing hair" is stored at address "01"; a "parted-at-the side hair style" is stored at address "02"; . . . . . . ; a "short-bobbed hair style" is stored at address "50" etc. Part patterns of "eyes", "nose", "mouth", "both legs", etc are stored similarly.
A table of the numbers of part patterns and the numbers of part patterns greatly congenial to the former part patterns are stored in corresponding relationship in the self-congeniality correspondence ROM 60B-2 of the ROM assembly 60B, as shown in FIG. 34B.
For example, in the embodiment of FIG. 34B, No. "03" is stored as the number of a part pattern greatly congenial to a part pattern "contour" having No. "01"; and No. "02" is stored as the number of a part pattern greatly congenial to a part pattern "hair style" having No. "49". Similarly, No. "05" is stored as the number of a part pattern greatly congenial to a part pattern "hair style" having No. "01"; and No. "02" is stored as the number of a part pattern greatly congenial to a part pattern "contour" having No. "49".
Similarly, the part patterns "eyes", "nose", "mouth", . . . "both legs", and part patterns greatly congenial to the corresponding former part patterns are stored with their corresponding part pattern numbers.
The "being congenial" referred to here points out congeniality between the part patterns. In this embodiment, it points out the congeniality between a man and a woman. The congeniality between the part patterns in the self-congeniality correspondence ROM 60B-2 is created on the assumption that, for example, larger "eyes" are greatly congenial to smaller "eyes"; and a lower "nose" is greatly congenial to a lower "nose" although congeniality may be created on the basis of other standards.
The RAM assembly 61B includes an individual data RAM (not shown), an entry montage RAM 61A-1, and a self-congeniality montage RAM 61B-2. The individual data RAM stores individual data such as the names of individuals and their telephone numbers keyed in by the input unit 32. The entry montage RAM 61A-1 stores the numbers of the part patterns of an individual's face and body shape.
For example, as shown in FIG. 35A, a part pattern number group GP1 ("02" as a "contour" part pattern number; "02" as a "hair style" part pattern number; "01" as a "eyes" part pattern number; "01" as a "nose" part pattern number; and "01" as a "mouth" part pattern number) is stored in a first individual entry area "X" of the entry montage RAM 61A-1. A part pattern number group GP2 ("05" as a "contour" part pattern number; "06" as a "hair style" part pattern number; "07" as an "eyes" part pattern number; "08" as a "nose" part pattern number; and "09" as a "mouth" part pattern number . . . ) is stored in a second individual entry area "Y". Similarly, part pattern number Groups each are stored for other individuals.
The self-congeniality montage RAM 61B-2 stores in its storage area the numbers of part patterns corresponding to part patterns which are greatly congenial to part patterns stored in the montage entry storage area.
For example, as shown in FIG. 35B, the respective part pattern numbers for an "X" montage are: "02" for the "contour", "02" for the "hair style", "01" for the "eyes", "01" for the "nose", "01" for the "mouth", . . . Thus, No. "49" corresponding to No. "2" is stored in a "contour" congeniality part pattern A 0 area; No. "49" corresponding to No. "2" is stored in a "hair style" congeniality part pattern A 1 area; No. "08" corresponding to No. "01" is stored in an "eyes" congeniality part pattern A 2 area; No. "07" corresponding to No. "01" is stored in a "nose" congeniality part pattern A 3 area; and No. "10" corresponding to No. "01" is stored in a "mouth" congeniality part pattern A 4 area.
Similarly, this applies to "Y": No. "30" corresponding to No. "05" is stored in a "contour" congeniality part pattern A 0 area; No. "31" corresponding to No. "06" is stored in a "hair style" congeniality part pattern A 1 area; No. "32" corresponding to No. "07" is stored in an "eyes" congeniality part pattern A 2 area; No. "33" corresponding to No. "08" is stored in a "nose" congeniality part pattern A 3 area; and No. "34" corresponding to No. "09" is stored in a "mouth" congeniality part pattern A 4 area.
Similarly, the numbers of the individuals' part patterns and the numbers of part patterns greatly congenial to the former part patterns are stored for the individuals.
Various processes performed by the montage game device of the present embodiment will next be described with respect to a flowchart of FIG. 36.
In the present embodiment, prior to congeniality divination, a montage creation and entry process is performed to store montage data (the respective pattern numbers of parts) in the entry montage RAM 61A-1. FIG. 37A shows an X montage F1 displayed by the montage creation and entry process, which is similar to that of the first embodiment of FIG. 13 and its further description will be omitted.
An optimal congeniality montage display process of the sixth embodiment will be performed on the basis of the flowchart of FIG. 36. This process starts in response to the operation of the congeniality mode select key 32 of the input unit 32.
First, at step S30 it is determined whether the congeniality mode select key 21A is operated. If not, a looping operation is performed until the key 21A is operated.
If so at step S30, control passes to step S31, where, for example, the number "02" of a "contour" part pattern in an entry area "X" where the X data is entered is read out from the entry montage RAM 61A-1 and stored in a column of a "contour" area A 0 in the self-congeniality montage RAM 61B-2 and corresponding to the "02".
Control then passes to step S32, where a part pattern number "49" congenial greatly to the "contour" part pattern number "02" read out at step S31 is read out from the self-congeniality montage RAM 61B-2 and stored in a column of an area A 0 of the self-congeniality montage RAM 61B-2 and corresponding to the number "49" (FIG. 35B).
Control then passes to step S33, where the "X hair style" part pattern number "2" is read out from the entry montage RAM 61A-1 and stored in a column of the area A 1 of the self-congeniality montage RAM 61B-2.
Control then passes to step S34, where a part pattern number "49" congenial to the "hair style" part pattern number "2" read out at step S33 is read out from the self-congeniality montage RAM 60B-2 and stored in a column of an area A 1 of the self-congeniality montage RAM 61B-2.
Control then passes to step S35, where the pattern numbers of other parts (eyes, nose, mouth, etc.) of X are read out from the entry montage RAM 61A-1 and stored in respective columns of areas A 2 -A n of the self-congeniality montage RAM 61B-2, and congenial part pattern numbers are read out from the self-congeniality montage RAM 61B-2 and stored in respective columns of areas A 2 -A n of the self-congeniality montage RAM 61B-2.
Control then passes to step S36, where part patterns are read out from the part pattern ROM 33 on the basis of the corresponding part pattern numbers stored in the columns of areas A 0 -A n of the self-congeniality montage RAM 61B-2 and used to synthesize in the synthesis RAM 41 an X face or whole body montage F2 as one of the target montages. The X montage is then displayed on the display 23, as shown in FIG. 37B. Part pattern numbers are read out from the part pattern ROM 33 on the basis of corresponding congenial part pattern numbers read out from the respective columns of areas A 0 -A n of the self-congeniality montage RAM 61B-2 and are used to synthesize in the synthesis RAM 41 a different person's face or whole body montage F2' (in the present embodiment, a female) congenial to the X face or whole body montage F2. The different person's montage is displayed on the display 23, as shown in FIG. 37C. Thus, the series of processes ends.
According to the above processes, a created face or whole body montage and a different face or whole body montage congenial to the former montage (of a man or a female) are displayed. If the montage output device is applied to an electronic pocketbook, for example, it may be used in a manner similar to the congeniality divination. By incorporating elements such as toys mechanically into the pocketbook, the practical value of the pocketbook or the value of the pocketbook as an article of trade is improved.
While in the embodiments the congeniality montage display processes have been described with respect to a person "X", the present invention is not limited to the processes. As long as data on a person is entered in the self-congeniality montage RAM 61B-2, a face or whole body montage of a different person greatly congenial to the former montage can be displayed, of course.
While in the present embodiment description is made in such a manner that the part patterns of a human being as a motif are stored in the part pattern ROM 33, the present invention is not limited to those processes. Part patterns of the face or body of an animal as a motif may be additionally stored in the ROM 33 to display the congeniality between a human being and an animal and between animals.
While in the present embodiment the correlation between part patterns stored in the self-congeniality correspondence ROM 60B-2 has been described as the congeniality between a man and a female, the correlation is not limited to that one, and may be, for example, the congeniality between friends or otherwise that between uncongenial ones to each other.
While in the present embodiment a created face montage, etc., has been described as being displayed on a liquid crystal dot matrix display or the like, the present invention is not limited to the particular case. The created face montage, etc., may be printed out, for example, on a thermosensitive dot printer.
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An image data processor, for use in a device which plays a battle game, a congeniality divination game, etc., includes a designating unit which is operated to designate respective parts of objects in order to display those object images on a display. A determining unit determines superiority or inferiority between the respective displayed object images on the basis of scores corresponding to part images constituting the respective displayed object images. The respective object images are changed depending on the results of the determination and the resulting object images are then displayed on the display. When the designating unit designates any part of the object, a score corresponding to that portion is read out, and data on the appropriate object image is displayed on the display depending on the read out score. When the designating unit designates the respective parts of the object, the display displays a first object image composed of a combination of the part images corresponding to the respective parts of the object and a second object image congenial to the first object image.
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FIELD OF THE INVENTION
This invention relates to a stent delivery catheter system, such as the kind used in percutaneous transluminal coronary angioplasty (PTCA) procedures. More particularly, it relates to a stent delivery catheter employing two retractable sheaths which may be retracted to release a self-expanding stent, a balloon assisted expandable stent or a balloon expandable stent.
BACKGROUND OF THE INVENTION
In typical PTCA procedures, a guiding catheter is percutaneously introduced into the cardiovascular system of a patient and advanced through the aorta until the distal end is in the ostium of the desired coronary artery. Using fluoroscopy, a guide wire is then advanced through the guiding catheter and across the site to be treated in the coronary artery. An over the wire (OTW) balloon catheter is advanced over the guide wire to the treatment site. The balloon is then expanded to reopen the artery. The OTW catheter may have a guide wire lumen which is as long as the catheter or it may be a rapid exchange catheter wherein the guide wire lumen is substantially shorter than the catheter. Alternatively, a fixed wire balloon catheter could be used. This device features a guide wire which is affixed to the catheter and cannot be removed.
To help prevent arterial closure, repair dissection, or prevent restenosis, a physician can implant an intravascular prosthesis, or a stent, for maintaining vascular patency inside the artery at the lesion. The stent may either be a self-expanding stent, a balloon assisted expandable stent or a balloon expandable stent. For the latter type, the stent is often delivered on a balloon and the balloon is used to the expand the stent. The self-expanding stents may be made of shape memory materials such as nitinol or constructed of regular metals but of a design which exhibits self expansion characteristics.
In certain known stent delivery catheters, a stent and an optional balloon are positioned at the distal end of the catheter, around a core lumen. The stent and balloon are held down and covered by a sheath or sleeve. When the distal portion is in its desired location of the targeted vessel the sheath or sleeve is retracted to expose the stent. After the sheath is removed, the stent is free to self-expand or be expanded with a balloon.
In a coronary stent deployment system which utilizes a retractable sheath one problem which is encountered is the interaction of the sheath and the stent upon retraction of the sheath. Typically, as the sheath slides off of the stent, the stent is subjected to potential marring by the sheath. While this problem can be minimized by making the sheath of soft materials, such materials are often unsuitable for use with a self-expanding stent where prolonged storage results in creep deformation of the inner sheath.
It is desirable to provide a medical device delivery system which provides a protective, non-marring inner sheath for the medical device and is capable of retaining the medical device for brief periods of time and which further has an additional outer sheath over the inner sheath which is capable of retaining the medical device for lengthy periods of time, thereby allowing the device to have a suitable shelf life.
SUMMARY OF THE INVENTION
The present invention provides a medical device delivery system in which two sheaths, an inner sheath and an outer sheath, cover a medical device mounted on the distal end of the medical device delivery system. In its various embodiments, the invention contemplates a delivery system in which the inner sheath is either a tear away sheath or a retractable sheath and the outer sheath is either a retractable sheath or a pull away sheath.
In accordance with the present invention, the outer sheath is desirably constructed to be more creep resistant than the inner sheath. The outer sheath may be made of a material having a higher hoop strength than the inner material. The inner material should be capable of retaining the medical device in place on the delivery system for at least a short period of time before it either is retracted or opens due to material failure. The outer sheath should be capable of retaining the medical device for longer periods of time so that the device may have a reasonable shelf life.
To this end, the invention provides a medical device delivery system comprising a manifold at the proximal end of the delivery system. Extending distally from the manifold is an inner tube. At the distal end of the inner tube is a medical device mounting region for concentrically mounting a medical device thereon. Covering the medical device mounting region, at least in part, is a distal inner sheath attached to the inner tube at the distal region of the inner tube. The distal inner sheath is concentrically disposed about the inner tube. The medical device delivery system also comprises a distal outer sheath, concentrically disposed about the inner tube. At least a portion of the distal outer sheath is disposed about at least a portion of inner sheath.
In one embodiment of the invention, the distal inner sheath is a tear away sheath and the distal outer sheath is retractable by means of an outer sheath retraction device. The outer sheath retraction device extends in a distal direction from the manifold. The distal outer sheath extends from the distal end of the retraction device.
In another embodiment of the invention, the distal inner sheath is retractable by means of an inner sheath retraction device. The inner sheath retraction device extends in a distal direction from the manifold. The distal inner sheath extends from the distal end of the inner sheath retraction device. Similarly, the outer sheath is retractable by means of an outer sheath retraction device. The outer sheath retraction device extends in a distal direction from the manifold. The distal outer sheath extends from the distal end of the outer sheath retraction device.
In another embodiment of the invention, the distal inner sheath is retractable by means of an inner sheath retraction device. The inner sheath retraction device extends in a distal direction from the manifold. The distal inner sheath extends from the distal end of the inner sheath retraction device. The distal outer sheath contacts the inner sheath, and extends proximally from the distal region of the inner tube. The distal outer sheath is removed prior to insertion of the device in the body.
In all of the embodiments, the delivery system may further comprise the medical device mounted on the medical device mounting region. Among the contemplated medical device for use with this system are stents and grafts. Desirably, the stent will be self-expanding or a balloon assisted expandable stent.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows a longitudinal cross-sectional view of an embodiment of the inventive medical device delivery system.
FIG. 2 shows a partial cut-away perspective view of the distal end of the embodiment of FIG. 1 .
FIG. 3 shows an enlarged view of region 3 of the medical device delivery system of FIG. 1 .
FIG. 4 shows a longitudinal cross-sectional view of an embodiment of the inventive medical device delivery system.
FIG. 5 shows a longitudinal cross-sectional view of an embodiment of the inventive medical device delivery system.
FIG. 6 shows a perspective view of a stent for use with the inventive medical device delivery system.
FIG. 7 shows a perspective view of a graft for use with the inventive medical device delivery system.
FIG. 8 shows a side elevational view of a vena cava filter for use with the inventive medical device delivery system.
DETAILED DESCRIPTION OF THE INVENTION
While this invention may be embodied in many different forms, there are described in detail herein specific preferred embodiments of the invention. This description is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated.
The present invention provides a medical device delivery system in which the medical device is contained and/or surrounded and/or protected by both an inner sheath and an outer sheath.
In several of the embodiments, the inner sheath is a tear away sheath. The presence of a tear away inner sheath protects the medical device from being marred upon the sliding removal of the outer sheath. After the outer sheath is removed, the inner tear away sheath, no longer contained by the outer sheath, opens as a result of the expanding force of the self-expanding, balloon assisted or balloon expandable medical device.
Turning to the figures, FIG. 1 shows one embodiment of the inventive medical device delivery system generally at 110 . The medical device delivery system 110 has a proximal end and a distal end and comprises a manifold 120 located at the proximal end of delivery system 110 . Extending in a distal direction from manifold 120 is an inner tube 124 having a distal region 128 and a proximal region 132 . At the distal region of inner tube 124 is a medical device mounting region 136 for concentrically mounting a medical device thereon. Delivery system 110 further comprises a distal inner sheath 140 attached to inner tube 124 at distal region 128 . Distal inner sheath 140 is concentrically disposed about inner tube 124 and covers at least a portion, desirably a substantial portion and more desirably the entirety of medical device mounting region 136 to retain a medical device about the medical device mounting region. Inner sheath 140 is fixedly attached to the medical device delivery system and desirably is mounted to the inner tube. As shown in FIG. 2, distal inner sheath 140 is a perforated 137 or scored tear away sheath. A distal outer sheath 144 is concentrically disposed about inner tube 124 and at least a portion of distal outer sheath 144 is disposed about at least a portion of distal inner sheath 140 . The device further comprises an outer sheath retraction device 148 which extends in a distal direction from manifold 120 . Distal outer sheath 144 is seen to extend from the distal end of outer sheath retraction device 148 .
Although there are a variety of outer sheath retraction devices that may be used in the practice of the invention, as shown in FIGS. 1 and 3, a preferred outer sheath retraction device 148 comprises a proximal outer tube 152 , a collapsible sheath 156 extending from the distal end of proximal outer tube 152 and a distal outer tube 160 . The proximal end of distal outer tube 160 extends from the distal end of the collapsible sheath 156 . A slidable pull wire 164 extends from manifold 120 to distal outer sheath 144 . In use, the distal end of retraction device 148 moves in a proximal direction upon sliding pull wire 164 proximally thereby retracting distal outer sheath 144 . Tear away inner sheath 140 may then open as a result of the force of the expansion of the expandable medical device. Because the tear away inner sheath is fixedly attached to the medical device delivery system, the tear away inner sheath is withdrawn from the body of the medical device delivery system is withdrawn.
The stent delivery system may, optionally, further comprise a medical device mounted on the medical device mounting region 136 . While a variety of medical devices are contemplated, in the embodiment shown in FIGS. 1 and 2, the medical device is a self-expanding stent 168 .
In another embodiment of the inventions, as shown in FIG. 4, the delivery system, shown generally at 210 , comprises a manifold 220 , an inner tube 224 having a distal region 228 , a proximal region 232 and a medical device mounting region 236 for concentrically mounting a medical device thereon as in the previous embodiment. Similarly, as in the previous embodiment, delivery system 210 further comprises a distal inner sheath 240 . Distal inner sheath 240 is concentrically disposed about inner tube 224 and covers at least a portion of medical device mounting region 236 . Unlike in the previous embodiment, delivery system 210 further comprises a inner sheath retraction device 241 having a distal end and a proximal end. Inner sheath retraction device 241 , consists of pull collar 243 mounted on proximal end of distal end of inner sheath 240 and a pull wire 245 extending distally from manifold 220 to pull collar 243 .
As in the previous embodiment, a distal outer sheath 244 is concentrically disposed about inner tube 224 . At least a portion of distal outer sheath 244 is disposed about at least a portion of distal inner sheath 240 . Also, the device comprises an outer sheath retraction device 248 comprising a proximal outer tube 252 , a collapsible sheath 256 and a distal outer tube 260 as described for the embodiment of FIGS. 1-3. The collapsible sheath section of the medical device delivery system is similar to that shown in FIG. 3, differing only in the presence of an additional wire, corresponding to a slidable pull-wire operably associated with the inner sheath. Slidable wire 264 extends from manifold 220 to distal outer sheath 244 and in use, the outer sheath retraction device works in a manner identical to that described for the outer sheath retraction device described above. Alternatively, although not shown in FIG. 4, inner sheath 240 may also be retracted via a collapsible retraction device similar to retraction device 248 used to retract outer sheath 244 .
Also shown is an optional medical device in the form of a self-expanding stent 268 mounted on the medical device mounting region 236 .
In another embodiment, the invention comprises a medical device delivery system shown generally at 310 in FIG. 5 . Medical device delivery system 310 , as in the previous embodiments, comprises a manifold 320 , an inner tube 324 having a distal region 328 , a proximal region 332 and a medical device mounting region 336 for concentrically mounting a medical device thereon. Delivery system 310 further comprises a distal inner sheath 340 . Distal inner sheath 340 is concentrically disposed about inner tube 324 and covers at least a portion of medical device mounting region 336 . As in the embodiment of FIG. 4, delivery system 310 further comprises a inner sheath retraction device 341 having a distal end and a proximal end. Inner sheath retraction device 341 , consists of pull collar 343 mounted on proximal end of distal end of inner sheath 340 and a pull wire 345 extending distally from manifold 320 to pull collar 343 .
As in the previous embodiments, a distal outer sheath 344 (in sock form) is concentrically disposed about inner tube 324 . At least a portion of distal outer sheath 344 is disposed concentrically about at least a portion of distal inner sheath 340 . Unlike in any of the previous embodiments, distal outer sheath 344 extends proximally from the distal end of the inner tube and is removable by sliding the distal outer sheath in a distal direction. Distal outer sheath 344 is in contact with distal inner sheath 340 . Mounted concentrically about the inner tube and carrying the pull wire is outer tube 360 . Although distal outer sheath 344 is depicted in FIG. 5 as being closed at the distal end, it may optionally be open at the distal end. In use, distal outer sheath 344 is removed prior to insertion of the medical device delivery system into the body. A removable sheath such as that disclosed in U.S. Pat. No. 5,800,517 to Anderson et al., incorporated herein in its entirety by reference, may be used.
Also shown is an optional medical device in the form of a self-expanding stent 368 mounted on the medical device mounting region 336 .
In another embodiment, not shown, the medical device delivery system is substantially similar to that shown in FIG. 5 differing only in that the retraction device for retracting the inner sheath is a collapsible sheath as shown in FIGS. 1 and 3.
In the various embodiments of the invention, suitable manifolds, as are known in the art, may be employed. In the embodiment containing two retractable sheaths, the manifold must be able to accommodate two retraction mechanism. In the other embodiments in which one retraction device is employed, the manifold must be able to accommodate one retraction device.
The inner tubes employed in the various embodiments may be made of suitable materials as are known in the art including. Preferably, the inner tubes are made of flexible, but incompressible construction such as a polymer encapsulated braid or coil. Such construction is known in the art. The braid/coil may be comprised of stainless steel encased in a polymer such as Polyimide with an inner layer of Teflon.
The pull collars attached to the retractable sheaths may suitably be ringshaped members made of stainless steel affixed to the interior of the retractable sheaths by an appropriate adhesive such as Loctite 4011, a cyanoacrylate. Desirably, the pull collar will be made of a radio-opaque material such as gold.
The outer sheath, desirably will be made of a material which has sufficient strength to contain a self-expanding stent in the stent's unexpanded configuration. It is desirable that the outer sheath be constructed so as to be creep resistant. It is also highly desirable that the inner sheath be constructed to be less creep resistant than the outer sheath.
Some of the benefits of the present invention may also be realized in a system wherein the outer sheath is made of a thicker material than the inner sheath.
Suitable materials for the outer sheath include polyimide, Pebax, polyethylene, Nylon, and metal for the embodiments in which the outer sheath is retractable via a retraction device extending to the manifold. Suitable materials for the sock-like distal outer sheath include polyimide, Pebax, polyethylene, Nylon, and metal. As for the distal inner sheath, suitable materials include PTFE, Pebax, polyurethane, polyethylene, and polyimide for the tear away embodiments and for the retractable distal inner sheath embodiments.
The invention also contemplates the use of porous materials for the inner and outer sheaths thereby allowing for the inflow of bodily fluids into the medical device mounting region. This can be helpful in priming the medical device by forcing out any air in the region of the medical device. Suitable porous materials include Suitable porous materials include expanded polytetrafluoroethylene (ePTFE), polyester and silicone. Desirably, the materials will have a pore size ranging from 0.01 mm to 5.0 mm.
Although the tear away sheath has been described as being mechanically released by the force of the expanding medical device, the invention also contemplates the use of a tear away sheath which is hydrolytically released. The sheath may be ‘glued’ shut via a bio-compatible water soluble material. The sheath may then be opened by supplying water thereto so as to dissolved the ‘glue’. Optionally, the glue may be chosen such that it is stable in the presence of fluids at bodily temperatures by dissolves upon exposure to a fluid of slightly elevated temperature such as water at a temperature of 42° C. Alternatively, the sheath may be glued shut via a material which is releasable via actinic energy such as ultraviolet radiation or gamma radiation supplied thereto.
The distal inner and outer sheaths may be bonded to the inner tube and/or retraction devices by the use of suitable adhesives including Loctite 4011, a cyanoacrylate as well as methacrylate, or H.B. Fuller 3507, a urethane adhesive. Other suitable bonding methods include pressure welding, heat welding and laser welding.
The invention also contemplates the use of various lubricants on at least a portion of one or more of the inner and outer sheaths to facilitate the relative motion of the inner and outer sheaths upon retraction or removal of the outer sheath. As seen in FIG. 2, distal inner sheath 140 has an inner surface facing the inner tube and an outer surface 138 facing distal outer sheath 144 . Similarly, distal outer sheath 144 has an inner surface 146 facing distal inner sheath 140 and an outer surface facing outward. A lubricant may applied to at least a portion of at least one of outer surface 138 of inner sheath 140 or inner surface 146 of outer sheath 144 so as to reduce frictional forces between the two sheathes. The lubricant may be applied selectively to the surfaces or, alternatively, may be applied to the entirety of the surfaces.
Although the inner surface and outer surface to which lubricants may be applied have been highlighted in FIG. 2, it is understood that the invention provides for the similar use of such lubricants on the outer surface of the inner sheath and the inner surface of the outer sheath in the other embodiments as well.
In all of the above embodiments, a lubricant may, optionally, be applied to at least a portion of the inner wall and/or outer wall. Suitable lubricants include silicones, PVP (polyvinyl pyrrolidone), PPO (polypropylene oxide) and PEO. Additionally, BioSlide™ coating produced by SciMed made be used as well. BioSlide™ is a hydrophilic, lubricious coating comprising polyethylene oxide and neopentyl glycol diacrylate polymerized in a solution of water and isopropyl alcohol in the presence of a photoinitiator such as azobisisobutronitrile.
Additional details of the design of embodiments of the inventive medical device delivery system which employ collapsible sheaths, in particular the portion of the device proximal to the inner sheath may be found in the various embodiments disclosed in U.S. Pat. No. 5,534,007 to St. Germain and Olson, incorporated herein in its entirety by reference.
In addition to the use of a collapsible sheath retraction device for retracting the outer sheath, the invention also contemplates the use of other suitable retraction means as are known in the art including slidably sealed retractable sheaths and midshaft seals as described in co-pending commonly assigned U.S. patent application Ser. No. 08/722,834 filed Sep. 27, 1996 now U.S. Pat. No. 5,772,669, and a continuation-in-part application Ser. No. 09/071,484 filed May 1, 1998 now U.S. Pat. No. 5,957930. The entire contents of both applications are hereby incorporated in their entirety by reference. Other contemplated retraction means include sheaths activated directly by pull-collars as described in U.S patent application Ser. No. 09/071,484 filed May 27, 1998, now U.S. Pat. No. 5,7957,930, and screw-like retraction devices as described in U.S. Pat. No. 5,201,757 to Heyn et al. all of which are incorporated herein in their entirety by reference.
Although the medical device shown in the figures have all been described as self-expanding stents, other mechanically expandable stents may be used as well, including balloon expandable stents. A perspective view of one suitable stent is shown in FIG. 6 at 668 . Other medical devices suitable for delivery with the present delivery system include implants such as grafts and vena cava filters. A suitable graft is shown in FIG. 7 at 768 while a suitable vena cava filter is shown in FIG. 8 at 868 .
As shown in the figures, the medical device delivery systems may further comprise other optional features, as are known in the art, such as bumpers 172 , 272 , 372 and 472 and markers 176 , 276 , 376 and 476 . Bumpers 172 - 472 may be made of polyethylene and are affixed to inner tube 124 by adhesive such as H.B. Fuller 3507. Marker bands 176 - 476 are preferably made of a radio-opaque material such as gold although other materials such as stainless steel may be used as well. The markers are included to aid in positioning and may be affixed to inner tube 124 by adhesive such as Loctite 4011.
While several specific embodiments of the present invention have been described, the invention is directed more generally toward the inclusion of two sheaths in any other suitable catheter design not specifically described herein including fixed wire, over-the-wire and rapid-exchange catheters.
In the case of the fixed-wire design, the guidewire is fixedly attached to the medical device delivery system. A fixed-wire delivery system is described in U.S. Pat. No. 5,702,364 to Euteneuer et al., incorporated herein in its entirety by reference, and may be suitably modified for use with the inventive medical device delivery system.
In an over-the-wire embodiment, the inner tube extends proximally to a manifold and a guide wire may be inserted into the inner tube from the proximal end, the guide wire extending to the distal end of the system. The medical device delivery system may then ride on the guidewire.
Similarly, a rapid exchange delivery system is described in U.S. Pat. No. 5,534,007 to St. Germain et al., incorporated herein in its entirety by reference, and may be suitably modified for use with the inventive medical device delivery system. Specifically, the rapid-exchange version may be realized by terminating the inner tube in a guide wire port in a location along the system distal to the proximal end of the system to allow for insertion of a guide wire therein. In the rapid-exchange embodiment, only a portion of the medical device delivery system rides on a guidewire. Typically, the usable length of the medical device delivery system is approximately 135 cm. For a rapid-exchange medical device delivery system, the distance from where the guide wire accesses the inner tube to the distal tip will be approximately 5 cm to 35 cm.
The above Examples and disclosure are intended to be illustrative and not exhaustive. These examples and description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the attached claims. Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims attached hereto.
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A medical device delivery system is disclosed which has a distal inner sheath and a distal outer sheath covering a medical device mounting region and any medical device mounted thereon. The outer sheath is designed to retain the medical device for lengthy periods of time while the inner sheath is designed to retain the sheath for shorter periods of time.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to polishing devices of a type used for polishing teeth. In one of its aspects, the invention relates to a polishing device which can be operated by use, i.e., in the normal course of use of the device, or can be operated by a manual switch.
In still another of its aspects, the invention relates to a sealed battery operated polishing device which can be recharged for long life.
2. State of the Prior Art
In U.S. Pat. No. 3,675,330 to Drapen and Henry, there is disclosed and claimed a tooth polishing device wherein a polishing element is rotatably driven by a motor assembly. In one embodiment, the motor is mounted within a casing which is pivotably mounted within a second casing. A switch is provided within the second casing and bears against the first casing so that when the casing is rotated, as by pressure on the polishing element, the switch is closed to supply electrical current to the motor. A spring between the second casing and the first casing biases the first casing into a position at which the switch is open. The polishing element in the second embodiment is provided at right angles to the axis of the motor drive mechanism so that pressure upon the polishing element in the normal course of operation will operate the switch.
Dayton et al. in U.S. Pat. No. 3,106,732 disclose a work actuated rotary brush in which pressure on the brush itself operates the power drive for the brush. In one embodiment, the motor is axially slidable within the casing to operate a switch. In another embodiment, the brush is at right angles to the drive mechanism and the brush is connected to the drive mechanism through a clutch which is engaged by pressure on the brush. In still another embodiment, a pair of batteries is electrically connected in tandem to the motor within the casing.
Dayton et al. in U.S. Pat. No. 3,220,039 discloses still another type of motor driven tooth brush wherein the brush is at right angles to the handle and drive shaft for the brush. The casing is constructed in much the same fashion as a flashlight with a motor and drive shaft in a front portion of the casing and a battery at a rear portion of the casing. An axially slidable switch completes the circuit between the battery and the motor to operate the rotary brush. The ends of the casing are closed by removable caps for assembly and so that the battery and other working parts of the implement can be replaced.
SUMMARY OF THE INVENTION
According to the invention, an improved polishing device employs a sealed casing to prevent water and other materials from seeping into the casing during operation of the device and from corroding the electrical contacts and other electrical components of the device. The polishing device according to the invention is easily assembled from a number of parts which snap-fit together, eliminating expensive assembly operations. The device also provides a simple manual switch to operate the power supply assembly or the assembly can be operated by pressure on the polishing implement. A battery is sealed into the casing in tandem with the motor so that there is an elongated casing to facilitate handling and use of the device. Rechargeable contacts are provided on the casing for recharging the battery without removal from the casing.
In the improved polishing device, a polishing tool is secured to a power drive means and the power drive means is pivotably mounted within a casing for movement between first and second positions within the casing. Power supply means, including a switch, are coupled to the power drive means for supplying electrical power thereto. The switch includes means for biasing the power drive means to the first position wherein said switch is open. Movement of the power drive means to the second position within the casing closes the switch for supply of power to the power drive means.
The polishing tool is desirably of the type which is at right angles to the shaft of the drive means. The polishing tool is indexed with the power drive means so that pressure on the polishing tool will force the power drive assembly from the first position to the second position within the casing as pressure is applied to the tool, thereby closing the switch.
The switch is preferably a leaf spring type and is mounted directly on the power drive assembly so that a portion of the leaf spring bears against the casing. The leaf spring flexes upon rotation of the power drive means and is forced in contact with a fixed contact member on the power drive assembly.
The power drive means is composed of a plurality of parts which are indexed and snap-fit together into a rigid assembly so that the entire assembly moves as a unit. A flexible sealing gasket is provided between the casing and the power drive means so that the casing is completely sealed, yet the power drive means is movable with respect to the casing.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described with reference to the accompanying drawings in which:
FIG. 1 is a side elevational view in section of a tooth polishing device according to the invention;
FIG. 2 is a sectional view taken along lines 2--2 of FIG. 1;
FIG. 3 is a sectional view taken along lines 3--3 of FIG. 1;
FIG. 4 is a partial sectional view seen along lines 4--4 of FIG. 1;
FIG. 5 is a partial sectional view taken along lines 5--5 of FIG. 1; and
FIG. 6 is an exploded view of the tooth polishing device;
FIG. 7 is a view similar to FIG. 1 of a modified form of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, and to FIGS. 1, 2 and 6 in particular, there is shown a tooth polishing device having a polishing cup 18 secured to a polishing head 20. A drive rod 22 projects rearwardly from the polishing head 20. Such polishing heads are well known devices which are conventionally used on professional dental equipment found in dentists' offices. Such polishing heads 20 have bevel gears (not shown) at the forward portion which are connected to the drive rod 22 to drive the cup 18 about an axis perpendicular to the axis of the drive rod 22 in conventional fashion. The drive rod 22 is conventionally provided with a lower rectangularly shaped end 23 for engagement with a driving mechanism. As illustrated in FIGS. 1 and 2, the polishing head 20 is provided with an annular bottom portion 24.
The polishing head is mounted on a rigid power drive assembly which includes coupling 26, pivot members 38, bearing housing 46 and motor 54. The power is supplied to the drive rod 22 from the drive shaft 60 of the motor 54, through a drive chain which includes a drive gear 62, drive connection 64 and coupler 72. The entire power drive assembly and drive chain pivot as a unit within the casing 16.
The tubular coupling 26 mounts the annular bottom 24 of the polishing head 20 through a friction fit. To this end, the coupling 26 has a reduced forward section 28 in which an O-ring seal 30 is provided. The O-ring seal 30 seals the joint between the coupling 26 and the polishing head 20.
The coupling 26 has a pair of fingers 34 (seen best in FIG. 6) with enlarged lower ends 36 having outwardly tapering surfaces. The annular pivot member 38 is snap-fit into engagement with the coupling 26 through the fingers 34 as illustrated in FIGS. 1 and 2. The lower end of the pivot member 38 has outer tapering surfaces 39 at the inner diameter thereof, with the tapered surfaces 39 complementing the outwardly tapering surfaces of the enlarged lower end 36. Thus, the coupling 26 is retained on the annular pivot member 38 through the fingers 34.
A pair of pivot pins 40 project laterally outwardly from the pivot member 38 to pivotably support the power unit in the casing in a manner which will be described later. The lower portion of the annular pivot member 38 has a connecting annulus 42 with radially projecting tabs 34. The bearing housing 46 has indentations 48 at an upper portion which engage the tabs 44 so that the bearing housing 46 snap-fits into engagement with the pivot member 38. The bearing housing 46 has a central bearing member 50 provided with an axial opening extending therethrough for the drive chain. At the lower portion, the bearing housing 46 has radial tabs 52 for snap-fit engagement with the motor 54.
A front mounting plate 56 is secured to the motor 54 and is provided with three spaced connected projections 58, each of which has an indentation 59 for engagement with the radial tabs 52 of the bearing housing 46. As seen in FIG. 6, the bearing housing 46 has a centering slot 47 at a rear portion thereof for engagement with a centering projection 57 on the front mounting plate 56 so that precise alignment is maintained between the bearing housing 46 and the mounting plate 56. In a similar manner, the bearing housing 46 is provided with a raised lug 49 at a front portion thereof for engagement with a slot 41 in the pivot member 38. In this manner, the position of the motor 54 with respect to the pivot member 38 is assured during assembly.
The drive shaft 60 extending from a front portion of the motor mounts the stepped drive gear 62 and is provided with teeth which drivingly engage the same. Internal teeth (not shown) on the interior surface of the stepped drive gear 62 can be provided to engage the exterior teeth on the drive shaft 60.
A drive connector 64 has an annular bottom portion 66 with a geared internal surface 68. The drive gear 62 drivingly engages the geared inner surface 68 of the drive connection 64 as seen in FIG. 1. The relatively large surface 68 provides a speed reducer for the drive chain. A square upper end 70 is provided at the forward portion of the drive connector 64. A coupler 72 fits on the square upper end 70 and provides a socket for the lower formed end 23 of the polishing head drive rod 22. Thus, the polishing head 18 is driven by the motor 54 through drive shaft 60, stepped gear 62, drive connection 64, coupler 72 and drive rod 22.
Reference is now made to FIG. 3 for a description of the switch used to operate the motor. The switch comprises a pair of poles 76 and 78 which are electrically connected respectively to a spring contact 80 and a fixed contact 82. In normal position, illustrated in FIG. 1, the spring contact 80 is separated from the fixed contact 82 with the bottom of the spring contact 80 resting on the bottom of the casing 16. The spring contact 80 is made from a resilient, conductive material and provides the spring which biases the drive assembly upwardly as viewed in FIGS. 1 and 3. Thus, when the motor 54 is forced downwardly, the fixed contact 82 is brought down into contact with the spring contact 80, thereby completing the electrical circuit for the motor. Power is thereafter supplied to the motor to rotate the polishing cup 18.
Referring again to FIGS. 1 and 2, the casing 16 can be formed in halves 94 and 96 which are substantially symmetrical about the parting line between the two halves. Sockets 98 and 100 are formed in the forward portions of the casing havles 94 and 96 respectively and mount the pivot pins 40 of the pivot member 38. An external groove 102 is formed in a front part of the casing havles 94 and 96 for retaining a tapered annular rubber gasket 104. To this end, the gasket 104 has a slightly oversized radial protuberance 106 which fits into the external groove 102. The forward portion of the gasket 104 sealingly abuts the peripheral abutment 32 of the coupling 26. Further, an inner sealing rim 107 is provided on the rubber gasket 104 for sealingly engaging the forward portion of the pivot member 38. Thus, a seal is maintained between the forward portions of the casing halves 94 and 96 and the coupling 26 and the pivot member 38. Because of the flexible nature of the rubber gasket 104, the seal is maintained between the casing and the coupling 26 as the coupling 26 rotates with respect to the casing 16.
A battery 116 is mounted behind the motor. To this end, the rear portions of the casing havles 94 and 96 have radial positioning lugs 108, a front positioning lug 110, a bottom positioning lug 114, and a rear positioning lug 112. The battery 116 is connected electrically to the poles 76 and 78 through leads 116a and 116b which extend from terminals 118 and 119 respectively.
At the rear-most portion of the casing havles 94 and 96, lateral openings 120 are provided for recharging contacts 124. Radial positioning lugs 122 extend inwardly from the sides of the casing havles 94 and 96 and retain the recharging contacts 124 in position. To this end, slots 126 having retaining lugs 127 in the recharging contacts 124 are provided. The positioning lugs 122 extend through the slots 126 and the retaining lugs 127 frictionally engage and grip the positioning lugs 122. Leads 124a and 124b extend from respective recharging contacts 124 to terminals 118 and 119 of the battery 116.
Referring now specifically to FIGS. 1 and 5, a manual actuator is shown for manually turning the motor on so that it runs continuously, if desired, with or without pressure on the polishing cup 18. A knob 130 is provided in opening 128 in the forward portion of the casing havles 94 and 96. A knob 130 is provided in opening 128 in the forward portion of the casing havles 94 and 96. An O-ring seal 136 provides a seal between the casing havles 94 and 96 and the knob 130. An actuator 132 having a downward projection 134 is secured to the bottom of the knob 130. As seen in FIG. 5, when the motor is in the position illustrated in FIGS. 1 and 2, the projection 134 will lie to one side of the bearing housing 46. As the knob 130 is rotated about its axis, the downward projection 134 bears against the bearing housing 46 to force the motor 54 downwardly as viewed in FIG. 1, thereby forcing the fixed contact 82 into electrical engagement with the spring contact 80. In this position, the knob 130 will be held by friction so that the power drive assembly is locked in the energized position.
When the parts have been assembled in the manner illustrated, the casing halves are welded together to seal the casing shut. The entire unit is thus sealed against water, dirt, etc. The battery 116 is standard 1.25 volt battery which is of the rechargeable type. The battery is recharged through the recharging contacts 124. Recharging current is applied to the contacts 124 by a battery recharging circuit (not shown). Such recharging circuits are well known.
The motor 54 is a standard DC motor, for example, a 1.5 volt motor. Desirably the motor is of the "stall" type such that the motor will cease operation when a predetermined resistance torque is applied to the output shaft. Thus, if an excessive amount of pressure is applied to the teeth by the polishing cup 18, the motor will stop and polishing will be discontinued.
In operation, the motor 54 is actuated to rotate the polishing cup 18 either by applying upward force on the cup 18 as viewed in FIG. 2, (as would be common in an ordinary polishing operation) or by turning the knob 130 in the manner described above. In either case, the motor 54, being secured to the pivot members 38 through the bearing housing 46 and the front mounting plate 58, will pivot downwardly within the casing 16 about the pivot pins 40 of the pivot member 38. This downward movement will cause the fixed contact 82 to come into electrical engagement with the spring contact 80 to thereby complete the electrical circuit between the battery 116 and the motor 54. Thus, the motor, having electrical power supplied thereto, will drive the drive shaft 60, the stepped drive gear 62, the drive connection 64, the drive rod 22, and the cup 18. After the polishing operation is complete, and pressure is released on the cup 18 (or the knob 130 is returned to its initial position), the motor 54 will be forced upwardly back into the position illustrated in FIG. 1 by the spring contact 80 which bears against the bottom surface of the casing 16. Thus, the electrical connection between the spring contact 80 and fixed contact 82 will be broken, thereby cutting off the supply of current to the motor 54.
In FIG. 7, like numerals have been used to designate like parts. In FIG. 7, the polishing device is substantially the same as shown in FIGS. 1-6 except that the battery of the first embodiment has been replaced by a rectifying diode circuit 140 and a cord 142 for supply of 110 volts AC. The rectifying diode circuit is mounted on holders 144 which are molded into the casing 16. The motor 54a is a 110 volt DC motor.
The polishing device according to the invention provides a compact sealed unit made inexpensively from snap-fit plastic parts which can be easily and quickly assembled. The parts themselves are inexpensively manufactured from plastic materials, such as polyvinylchloride, polyethylene, polypropylene, and the like. For example, except for the motor 54, battery 116 and electrical components, and the polishing head 20, all parts can be made from molded plastic or rubber. In order to add strength to the drive mechanism, the coupler 22 can be made of metal.
The polishing device has a sealed casing yet provides for relative movement between the casing and the drive mechanism so that the drive mechanism can be actuated by appropriate pressure on the polishing cup 18. Further, the polishing device according to the invention provides an alternate mode of operation, namely one in which the polishing head is operated automatically when pressure is applied to the polishing cup 18 and one which can be operated manually so that the device is continuously operated regardless of the pressure on the polishing cup 18.
The invention also provides a novel speed reducer so that the polishing cup does not build up excessive friction. The novel speed reducer is conveniently mounted coaxially with a bearing support which is a part of the power drive assembly.
Reasonable variation and modification are possible within the scope of the foregoing disclosure, the drawings, and appended claims without departing from the spirit of the invention.
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A tooth polishing device wherein a polishing tool is secured to a power drive assembly and the power drive assembly is pivotably mounted in a casing for rotational movement within the casing. A power supply means includes a switch and is coupled to the power drive assembly for supplying electrical power thereto. The switch includes a biasing means, for example, a leaf spring contact, biasing the power drive means to one rotational position within the casing. The switch is open when the power drive is in the one position and is closed when the power drive means is moved rotationally to a second position. The spring contact is mounted on the motor of the power drive assembly and bears against the bottom portion of the casing. The casing is sealed, and is provided with a battery for operating the power supply assembly. Recharging contacts are provided in the casing for recharging the battery when the polishing device is not in use. The battery and power supply are mounted in tandem within the casing which is elongated in shape to facilitate holding and operation of the polishing device. A novel gear reducer is provided in the power drive assembly.
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BACKGROUND
[0001] This invention relates generally to resistance exercise equipment and, more particular, to a wearable resistance exercise apparatus that employs a resistance pulley system and that can be used to perform resistance exercises when in position on a wearer.
[0002] Resistance exercise equipment is a popular tool used for conditioning, strength training, muscle building, and the like. Various types of resistance exercise equipment are known, such as free weights, exercise machines, and resistance exercise bands or tubing. Various limitations exist with the prior art exercise devices. For example, many types of exercise equipment, such as free weights and most exercise machines, are not portable. With respect to exercise bands and tubing, they may need to be attached to a stationary object, such as a closed door or a heavy piece of furniture. This becomes a problem when, for example, the user wishes to perform resistance exercises in a location where such stationary objects are not readily found, such as outdoors. For the prior art devices that do not need to be attached to stationary objects, such as other types of bands or tubing, such prior art systems typically provide only one level of resistance. This is a disadvantage for a user who wishes to increase or decrease the level of resistance for the user's resistance exercises. For such users, it becomes necessary to acquire more than one set of resistance exercise bands or tubing.
[0003] Therefore, it would be desirable to provide an apparatus and method that overcomes the above problems. The apparatus and method would provide for resistance exercise equipment that is portable, that may be used on its own without the need to employ other types of equipment, and that allows for adjustable resistance levels.
SUMMARY
[0004] A wearable resistance exercise apparatus has at least one pulley. A cable is coupled to the at least one pulley. At least one handle is located at the end of the cable and adapted to be gripped by a user. A wearable support member is provided, wherein the at least one pulley is located on the wearable support member. At least one exercise accessory is coupled to the wearable support member
[0005] The features, functions, and advantages can be achieved independently in various embodiments of the disclosure or may be combined in yet other embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Embodiments of the disclosure will become more fully understood from the detailed description and the accompanying drawings, wherein:
[0007] FIG. 1 is a front view of a wearable resistance exercise apparatus, consistent with an embodiment of the present invention;
[0008] FIG. 2 is a back view of the exercise apparatus of FIG. 1 ;
[0009] FIG. 3 is front view of a pulley device, consistent with an embodiment of the present invention;
[0010] FIG. 4 is a front, perspective, mirror image view of the pulley device of FIG. 3 ;
[0011] FIG. 5 is a cross-sectional view of a tension adjusting device, consistent with an embodiment of the present invention;
[0012] FIG. 6 is a bottom view of the pulley device of FIG. 4 ;
[0013] FIG. 7 is a bottom view of the pulley device of FIG. 4 , with a portion thereof being shown in phantom;
[0014] FIG. 8 is a top view of the pulley device of FIG. 4 .
[0015] FIG. 9 is a magnified view of another embodiment of the tension adjusting device;
[0016] FIG. 10 is a front view of another embodiment of the wearable resistance exercise apparatus having magnified view of different attachments;
[0017] FIG. 11A is a perspective view of the wearable resistance exercise apparatus having the pivot board shown in FIG. 10A ;
[0018] FIG. 11B is a perspective view of the wearable resistance exercise apparatus having a pivot board, the pivot board being used for another exercise;
[0019] FIG. 11C is a front view of the picot board used in FIG. 11A-11B ;
[0020] FIG. 11A is a side view of the wearable resistance exercise apparatus having the swing seat as shown in FIG. 10 ;
[0021] FIG. 11B is a rear view of the wearable resistance exercise apparatus having the swing seat of FIG. 10 ;
[0022] FIG. 12A is a front view of another embodiment of the wearable resistance exercise apparatus; and
[0023] FIG. 12B is a rear view of the wearable resistance exercise apparatus of FIG. 12A .
DETAILED DESCRIPTION
[0024] Referring first to FIGS. 1 and 2 , an embodiment of a wearable resistance exercise apparatus 10 consistent with an embodiment of the present invention is shown. In this embodiment, the exercise apparatus includes the following main components: two pulley devices 20 , cables 22 which are coupled to the pulley devices 20 , handles 24 which are coupled to the ends of the cables 22 , and a wearable support member 12 , to which the pulley devices 20 are attached. In this embodiment, the exercise apparatus 10 further includes tension adjusting devices 30 , which are coupled to the front of the wearable support member 12 . Also in this embodiment, the wearable support member 12 includes front closures 14 .
[0025] In this embodiment, the wearable support member 12 is a vest. However, other forms of wearable support members, such as jackets, jumpsuits, or the like may be used. Preferably, the wearable support member 12 is composed of a heavy duty material, so that use of the pulley devices 20 , as herein described, do not cause the wearable support member 12 to stretch, sag or tear. Preferably, the wearable support member 12 has front closures 14 , so that it may be remain securely in position on a wearer during use of the exercise apparatus 10 . It may be desired to use side or back closures in addition to or instead of the front closures 14 .
[0026] In one embodiment, the handles 24 are attached to the cables 22 with fasteners, such as a snap hooks or carabineers. It may be desired to use hollow handles, which may be slipped over the cables 22 .
[0027] Referring now to FIGS. 3 and 4 and FIGS. 6-8 , an embodiment of a pulley device 20 , consistent with an embodiment of the present invention is shown. In this embodiment, the pulley device 20 includes a backplate 26 having a plurality of openings (not shown) through which coupling members 28 , such as bolts, may be inserted in order to couple the pulley device 20 to the wearable support member 12 (as best seen in FIG. 2 ). Preferably, the backplate 26 is composed of a rigid material, such as metal, so that it is capable of supporting the weight of the pulley device 20 . A tension cable 32 extends from the pulley device 20 to a tension adjusting device 30 (as best seen in FIG. 1 ).
[0028] In this embodiment, the tension adjusting devices 30 are positioned on the front of the wearable support member 12 . In this way, they are within easy reach of a wearer of the exercise apparatus 10 , who can adjust tension without needing to remove the wearable support member 12 by rotating the tension adjusting devices 30 . However, it may be desired to position the tension devices 30 elsewhere, such as on the back or sides of the wearable support member 12 .
[0029] Referring now to FIG. 5 , the structure of an embodiment of a portion of an exercise apparatus 10 is shown, with particular attention to the tension adjustment feature. A worm screw 34 is provided, with the worm screw 34 being rotatable by a turning of its corresponding tension adjusting device 30 (not shown), with the rotation being communicated through tension cable 32 (not shown). Rotation of the worm screw 34 alters the load on load spring 36 . Where it is desired to increase resistance, the tension adjusting device 30 should be turned in the direction that will cause increased load on the load spring 36 . To decrease resistance, rotation should occur in the opposite direction.
[0030] An increase in load on the load spring 36 causes anterior movement of a clutch plate 38 , which provides increased tension on the corresponding pulley device 20 . This will create increased resistance for the user. A decrease in load on the load spring 36 causes posterior movement of a clutch plate 38 , which provides decreased tension on the corresponding pulley device 20 . This will create decreased resistance for the user.
[0031] Referring now to FIG. 9 , another embodiment of the pulley device 20 ′ is shown. In this embodiment, the pulley device 20 ′ is removable and may be attached to different areas of the wearable support member 12 . As shown in FIGS. 1 and 2 , the wearable support member 12 may have one or more attachment loops 40 . The attachment loops may be formed on different areas of the wearable support member 12 .
[0032] The pulley device 20 ′ has a “U” shape frame 42 . A channel 44 is formed in the “U” shaped frame 42 . The wheel and axle unit 46 is positioned in the channel 44 with the axle portion secured in the “U” shaped frame 42 . A hinge mechanism 48 is kingly coupled to the “U” shaped frame 42 . The hinge mechanism 48 allows the pulley device 20 ′ to be removably attached to different areas of the wearable support member 12 .
[0033] Referring now to FIG. 10 , the exercise apparatus 10 may have a plurality of attachment devices. As shown in FIG. 10 , the exercise apparatus 10 may have an exercise computer 50 , an exercise board 56 , one or more pockets 78 , heating and or cooling elements 80 , a massage device 82 and/or a swing seat 66 .
[0034] The exercise computer 50 may be built into the wearable support member 12 . Alternatively, the exercise computer 50 may be removably attached to the wearable support member 12 . The exercise computer 50 is an electronic device that will provide feedback on your exercise routine such as: length of exercise time; calories burned; heart rate; tension on the pulley device 20 / 20 ′; time of day; store digital recordings such as music, exercise instructions, etc. and the like. The above listing is given as an example and should not be seen in a limiting manner.
[0035] If the exercise computer 50 is used to measure heart rate, the wearable support member 12 may have a built in heart rate strap 52 . The heart rate strap 52 may be used to measure the wearer's heart rate and to transmit this information to the exercise computer 50 .
[0036] If the exercise computer 50 is used to store digital recordings such as music, exercise instructions, etc., the wearable support member 12 may have built in headphones 54 . The built in head phones 54 may be used to allow the wearer of the wearable support member 12 to listen to the digital recordings.
[0037] The exercise computer 50 may also be stored in one or more pockets 78 formed on the wearable support member 12 . The pockets 78 may further be used o store other items such as an MP3 player, food, keys, and the like.
[0038] The wearable support member 12 may further have heating and or cooling elements 80 and or a massage device 82 formed therein. The heating and cooling elements 80 may be sued based on the weather conditions to keep the user at an optimal temperature during a workout. The massage device 82 may be used to relax the muscles after a workout.
[0039] Referring now to FIGS. 11A-11C , the exercise apparatus 10 may have an exercise board 56 . The exercise board 56 may be coupled to the pulley device 20 / 20 ′ to allow the user of the exercise apparatus 10 to do additional exercises. In accordance with one embodiment, the exercise board 56 is formed of a board member 56 A. The board member 56 A may be configured to be slightly curved in nature. A middle section 60 of the board member 56 A may have a wider width than the end sections 58 of the board member 56 A.
[0040] An opening 62 may be formed on each of the end sections 58 . The openings 62 may be used to allow the tension cable 22 and handles 24 to be inserted there through. By altering the position of the exercise board 56 , different exercises may be performed for different parts of the body. For example, as shown in FIG. 11A , the exercise board 56 may be positioned on the back of the user to perform shoulder presses. Further, as shown in FIG. 11B , the user may place the exercise board 56 on a surface such as a floor to allow a user to stand on the exercise board 56 to perform calf raises and or leg extensions. The above are just a few examples of exercises that may be performed and should not be seen in a limiting manner.
[0041] Referring now to FIGS. 12A-12B , the wearable resistant exercise apparatus 10 may have a swing seat 66 . The swing seat 66 may be movably attached to the wearable support member 12 . The swing seat 66 may be used for shoulder exercises. In accordance with one embodiment, the swing seat may be comprised of a body member 68 . The body member 68 may be formed of a flexible material. A flexible material may allow the body member 68 to conform to the body of the user as shown in FIGS. 12A-12B . Located on each end section 70 of the body member 68 may be a strap member 72 . The strap member 72 may be coupled to an adjustment device 74 . The adjustment device 74 may be used to adjust a length of the strap member 72 . Located on one end of each strap member 72 may be an attachment mechanism 76 . The attachment mechanism 76 may be used to rotatably couple each strap member 72 to the wearable support member 12 .
[0042] Referring now to FIGS. 13A-13C , another embodiment of the wearable support member 12 ′ is shown. Like in the previous embodiments, the wearable support member 12 ′ is a vest. However, other forms of wearable support members, such as jackets, jumpsuits, or the like may be used. Preferably, the wearable support member 12 ′ is composed of a heavy duty material, so that use of the pulley devices 20 / 20 ′ do not cause the wearable support member 12 ′ to stretch, sag or tear. Preferably, the wearable support member 12 ′ has front closures 14 ′, so that it may be remain securely in position on a wearer during use of the exercise apparatus 10 . It may be desired to use side or back closures in addition to or instead of the front closures 14 ′. A top section of the wearable support member 12 ′ may be formed of a mesh material 12 A.
[0043] While the invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and details may be made therein without departing from the spirit and scope of the invention. For example, it may be desired for the wearable support member 12 to include only one pulley device 20 to which two handles 24 are attached. It may also be desired for the wearable support member 12 to include only one pulley device 20 to which only one handle 24 is attached. In this latter embodiment, a user would be required to either grasp the single handle 24 with both hands, or exercise using one hand at a time.
Statement of Operation
[0044] In order to position the wearable resistance exercise apparatus 10 so that it may be used to perform resistance exercises, a user would put the exercise apparatus 10 on the user's upper body, so that the pulley devices 20 are positioned over the user's back and the tension adjusting devices 30 are positioned over the user's chest. The user would set a desired level of resistance by manipulating the tension adjusting devices 30 . The user would then perform resistance exercises by gripping the handles 24 and pulling them in a manner intended to stimulate muscle building.
[0045] For example, a user may wish to grasp the handles 24 and bring both hands directly forward, in a rowing or bench press type of motion. A user may wish to bring the handles 24 in an arc-type of motion until they contact each other in front of the user's body, in a fly type of motion. A user could extend both hands upward from a point beginning behind the neck, in a triceps extension type of motion. Numerous other variations are also possible.
[0046] A user may wish to utilize a single resistance setting for an exercise session. Alternatively, a user may wish to perform multiple sets of a particular exercise, and may wish to increase resistance between sets to perform a pyramid-style workout. The user may also wish to change resistance between different exercises.
[0047] While embodiments of the disclosure have been described in terms of various specific embodiments, those skilled in the art will recognize that the embodiments of the disclosure can be practiced with modifications within the spirit and scope of the claims.
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A wearable resistance exercise apparatus has at least one pulley. A cable is coupled to the at least one pulley. At least one handle is located at the end of the cable and adapted to be gripped by a user. A wearable support member is provided, wherein the at least one pulley is located on the wearable support member. At least one exercise accessory is coupled to the wearable support member.
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BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates generally to clamps and more specifically to an industrial clamp employing a swinging and linear motion.
Various industrial clamps have an arm which uses a linear and rotary motion. Examples of such conventional devices are disclosed within U.S. Pat. No. 6,059,277 entitled “Retracting Power Clamp” which issued to Sawdon et al. on May 9, 2000, and U.S. Pat. No. 5,165,670 entitled “Retracting Power Clamp” which issued to Sawdon on Nov. 24, 1992. Both of these patents are incorporated by reference herein. Other industrial clamps are known which have a piston rod and an externally mounted arm. The arm is linearly extendable along the piston rod axis and is rotatable only along a transverse plane perpendicular to the piston rod axis. These clamps, known as the 1500 Series and 2500 Series clamps from BTM Corp., are also pneumatically driven with a sealed body. While such traditional devices have significantly improved the art, additional and enhanced movement is often desirable in order to clear workpiece flanges or other obstructions during clamping or unclamping.
In accordance with the present invention, a clamping apparatus is provided that has a body and an elongated member that is extendable from the body. In another aspect of the present invention, a clamp has a workpiece engaging arm mounted adjacent an end of the elongated member. A further aspect of the present invention causes the elongated member to linearly extend and rotate when advanced. In yet another aspect of the present invention, a camming surface is provided in the body of the apparatus. An additional aspect of the present invention provides for improved fastening of the arm to the elongated member. A method of operating the clamp is also disclosed.
The clamp of the present invention is advantageous over conventional devices in that the present invention has an increased and enhanced range of motion during clamping and unclamping in order to clear workpiece flanges and other adjacent obstructions. The present invention is further advantageous by use of an automatically movable opening cover to minimize undesired contamination of the clamp body; this reduces dirt, dust, weld splatter and other external debris from otherwise entering the shaft opening, which could increase friction between moving parts and reduce durability of the clamp. The unique constructions and movement of the present invention cover allow the clamp to remain fully sealed when the workpiece arm is retracted, thereby retaining internal grease and excluding external contaminants. Furthermore, the camming surface design allows for simplified and reduced cost manufacturing and assembly while minimizing body openings that would otherwise need to be sealed. Moreover, the arm-to-shaft mounting arrangement of the present invention provides superior adjustability and fastening. Additional advantages and features of the present invention will become apparent from the following description and appended claims, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are perspective views showing the preferred embodiment clamp of the present invention in different movement positions;
FIGS. 3-5 are side elevational views showing the preferred embodiment clamp in various positions;
FIG. 6 is a side elevational view, taken 90 degrees to that of FIG. 3 , showing the preferred embodiment clamp in a retracted position with a switch plate removed;
FIG. 7 is an exploded perspective view showing the preferred embodiment clamp, but with an alternately configured arm;
FIGS. 8-10 are enlarged and fragmentary side elevational views, taken within circle 8 of FIG. 3 , showing the preferred embodiment clamp in different positions with a side plate removed;
FIG. 11 is a diagrammatic side view showing a first alternate embodiment clamp of the present invention;
FIG. 12 is a diagrammatic side view showing a second alternate embodiment clamp of the present invention; and
FIG. 13 is a fragmentary and diagrammatic side view showing a third alternate embodiment clamp of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1-3 , the preferred embodiment of a clamp apparatus 21 of the present invention is used to clamp or otherwise engage a workpiece 23 , such as an automotive vehicle panel, against a work surface 25 or fixture in an industrial manufacturing plant. Workpiece 23 typically has one or more sheets of steel with upturned flanges 27 , downturned flanges 29 or alternately shaped surfaces which need to be secured together for welding, assembly or machining operations. A bracket 31 is mounted to any side surface of a body or housing 33 of clamp 21 by way of screws 35 or other removable fasteners. An arm of an articulated robot 37 or stationary, factory-floor mounted structure is secured to bracket 31 for respectively moving or maintaining the position of clamp 21 relative to one or more of workpieces 23 .
As can best be observed in FIGS. 2 , 3 and 6 - 8 , clamp 21 has a single piece or unitary housing 33 cast and then machined from a single block of aluminum. A longitudinal bore 51 is machined within the center of body 33 and is accessible through an external opening 53 in a first end of body 33 . A first camming surface 57 , having a longitudinally extending leg 59 and a diagonally offset leg 61 , is machined through an outside wall 63 of body 33 and openly communicates with bore 51 . During manufacturing, a milling head is inserted through a first camming slot defined by first camming surface 57 and through the corresponding portion of bore 51 in order to machine a recessed, matching second camming surface 65 within an opposite second side wall 67 of body 33 . A second camming slot defined by second camming surface 65 , however, is recessed in and does not protrude all the way through the outside surface of side wall 67 such that a separately attached plate and seal are not required on the second side wall 67 . Second camming surface 65 identically mirrors the shape of first camming surface 57 . This preferred construction and manufacturing procedure allows for a unitary or one piece body to have a pair of opposed and integral camming surfaces as compared to prior devices which had bifurcated housings with somewhat less durable sealing and were prone to tolerance variations between halves leading to potential cam follower binding when assembled. A steel cover plate 69 is removable secured by screws 71 to an external side of body 33 to cover the first camming slot.
A piston cylinder 81 is machined into an end of body 33 opposite the end containing external opening 53 . Piston cylinder 81 preferably has a generally oval cross sectional shape although a circular cross sectional shape can alternately be employed. Piston cylinder 81 is in communication with and coaxial with bore 51 . An aluminum end cap 83 and elastomeric O-ring seal 85 are fastened by way of screws 87 to the end of body 33 adjacent piston cylinder 81 . Pneumatic ports 89 and 91 are machined in the external surface of body 33 for attaching hoses and fittings to allow the entry and exit of pneumatic pressure into piston cylinder 81 .
An oval shaped piston 93 and an elongated piston rod 95 coupled thereto longitudinally advance and retract in response to the selective use of pneumatic pressure through ports 89 and 91 . Sets of elastomeric seals 97 and 99 are secured within grooves of piston 93 in order to seal piston against the internal surface of piston cylinder 81 . An O-ring seal 101 is inserted within a cavity of body 33 adjacent bore 51 in order to seal piston rod 95 to body 33 . Piston rod 95 at least partially slides in a linear longitudinal direction within bore 51 .
A partially circular-cylindrical and elongated shaft 121 has a first bifurcated end 123 with a first hole 125 and a second hole 127 . A reduced thickness end 129 of piston rod 95 rotatably fits within a channel formed within bifurcated end 123 of shaft 121 . A pin 131 is located within holes 125 and 133 so as to drivably couple piston rod 95 to shaft 121 . Another pin 141 fits within second hole 127 of shaft 121 to retain steel rollers 143 and 145 which serve as cam followers along camming surfaces 63 and 65 , respectively.
An external end 151 of shaft 121 has a reduced diameter and a pair of opposed flats 153 . A steel cover 155 is essentially a flat rectangle with an enclosed hole defined by a pair of lateral flat surfaces joined by rounded surfaces. The flat surfaces of the hole align with flats 153 of shaft 121 in order to locate cover relative to shaft 121 in a key-hole like manner throughout all shaft movement positions. End 151 of shaft 121 has at least a partially threaded section for receiving a jam nut 157 . A compression spring 159 is disposed between nut 157 and cover 155 and serves to bias cover 155 against lower shoulders of flats 153 which coincide with the adjacent end of body 33 when shaft 121 is in its retracted position.
A workpiece engaging arm 171 has a proximal end segment within which is located a main aperture 173 with an opening axis concentric to the elongated axis of shaft 121 when assembled. A through-slot 175 connects main aperture 173 to an external surface of arm 171 . Furthermore, a fastening hole 177 is transversely oriented within arm 171 to intersect slot 175 . This arrangement allows arm 171 to be adjustably attached to shaft 121 by manually orienting arm 171 in any 360° position along a plane transverse to the elongated axis of shaft 121 . End 151 of shaft 121 is preferably patterned with a continuous thread to match an internal thread in main aperture 173 of arm 171 , however, a knurl pattern, spine pattern or even a smooth circular-cylindrical configuration can be employed on either or both mating surfaces. After arm 171 has been manually oriented relative to shaft 121 and end 151 has been inserted through main aperture 173 , a screw 179 is inserted into hole 177 . Screw 179 has threads that match corresponding threads within the far section of fastening hole 177 , but has clearance to the oversized adjacent section of fastening hole 177 . Screw 179 spans or bridges across slot 175 whereby manual rotation of screw 179 serves to compressibly tighten the main aperture of arm 171 around the circumference of shaft 121 in order to firmly secure one to the other. Arm 171 is preferably machined from steel and has an L-side view shape, but alternately, may have a straight configuration such as that shown in FIG. 7 which optionally allows for gripper pads (not shown) or other attachments to be secured to a distal end thereof.
A steel switch plate 191 is fastened to an external side of body 33 over a channel 193 machined into the body. An electrical proximity-type switch 195 , preferably obtained from Turk Corp., is carried on switch plate 191 for indicating the fully retracted and advanced positions of the rollers, piston rod, shaft or any of the other associated movement mechanisms. Proximity sensors 197 and 199 are part of the switch and plate assembly.
Moreover, a compression spring 201 and detent ball 203 are compressed within a cavity in body 33 . This provides a mechanical detenting action against the adjacent roller 143 when the roller is in its retracted position, which corresponds with the workpiece clamping position in the preferred embodiment; this encourages arm 171 to remain in its workpiece clamping position even when fluid pressure is undesirably lost or absent. Alternately, a compression spring contained within piston cylinder 81 can be employed instead of spring 201 in order to bias piston 93 toward its retracted position.
The operation of the present invention clamp apparatus 21 will now be described in greater detail. FIGS. 1 , 3 and 8 show piston 93 , piston rod 95 , shaft 121 and arm 171 in a retracted position wherein arm 171 clamps against workpiece 23 and cover 155 is biased against the adjacent end of body 33 . In this position, cover 155 is essentially sealed against body 33 to deter external contaminants from entering the shaft opening. Referring now to FIGS. 4 and 9 , piston 93 automatically drives piston rod 95 , shaft 121 , cover 155 and arm 171 to a linearly extended and coaxial position. Rollers 143 and 145 are still within longitudinally extending leg 59 of each camming surface 57 and 65 , respectively. Additionally, cover 155 is linearly moved away from the adjacent end of body 33 . Subsequently, FIGS. 2 , 5 and 10 illustrate the fully advanced position wherein piston 93 has automatically driven piston rod 95 , shaft 121 , cover 155 and arm 171 to a rotated position along the same longitudinal plane as the initial linear movement. Rollers 143 and 145 act with the corresponding offset camming surfaces of body 33 in order to cause this rotation in response to the further linear piston driving motion. This allows arm 171 to fully clear flanges 27 of workpiece 23 and to allow simplified vertical movement of workpiece 23 without undesirably contacting the disengaged and advanced clamp arm.
FIG. 13 shows an alternate embodiment clamp 221 of the present invention. This clamp is the same as the preferred embodiment clamp except that cover 255 has a generally flat first surface adjacent and generally perpendicular to an elongated direction of a shaft 321 , and the cover further has a second surface generally perpendicular to the flat surface such that the cover essentially conceals an intersection between offset adjacent and external surfaces of a housing 133 . This configuration allows for a longer external opening circumscribing the side and end intersection of body 133 to allow for even greater swinging rotation of shaft 321 and an attached arm 371 . This embodiment also compresses a compression spring 259 directly between arm 371 and cover 255 without the use of an intervening nut 157 .
A second alternate embodiment clamp 401 can be observed in FIG. 11 . The construction of clamp 401 in this embodiment is essentially the same as that for the preferred embodiment, but inverted. Clamp 401 also includes a cover (not shown). An arm 471 , however, is differently configured with a scoop-like tapered, distal end 473 which rotates from an advanced position to an intermediate position in order to scoop beneath a workpiece 475 . Subsequently, arm 471 is retracted toward a body 433 in a linear direction in order to lift workpiece 475 . Clamp 401 can lower and then gently release workpiece 475 by reverse linear and then rotary movement.
Referring now to FIG. 12 , a third alternate embodiment clamp 501 of the present invention is shown. This embodiment employs a pair of inverted clamps 503 and 505 which are the same as that with the second alternate embodiment except that their respective bodies 533 and 535 are joined together by a frame 537 which also serves to space apart the clamps by a predetermined distance. Frame 537 can be movably carried by a robotic arm or stationarily fixed to a factory floor mounted structure. In operation, the opposed rotary and linear movement of the facing arms 571 and 573 allows for rotated engagement of a workpiece and then linear lifting of the workpiece 575 when the arms are moved from their advanced positions to their retracted positions in a simultaneous and automatic manner.
While various embodiments of the swinging and linear motion clamp have been disclosed, it should be appreciated that additional alternate constructions may fall within the scope of the present invention. For example, linkages and/or differently configured cam and cam follower mechanisms can be employed to achieve the presently disclosed clamp motion although many of the advantages of the present invention may not be realized. Furthermore, many other cover shapes and shaft openings can be used. It is envisioned that the camming and body construction and method of manufacturing same can be employed in other types of clamps having different arm motions and even without the preferred automatically moving cover. A separately attached piston cylinder can be provided in place of the preferred integral one discussed herein. It should also be appreciated that hydraulic fluid pressure or even electromagnetic actuation can be used although many of the advantages of the present invention may not be realized. While various materials, shapes and manufacturing processes have been disclosed, it will be appreciated that others can be also employed. It is intended by the following claims to cover these and any other departures from the disclosed embodiments which fall within the true spirit of this invention.
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A clamping apparatus has a body and an elongated member that is extendable from the body. In another aspect of the present invention, a clamp has a workpiece engaging arm mounted adjacent an end of the elongated member. A further aspect of the present invention causes the elongated member to linearly extend and rotate when advanced.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] 100011 The present application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 61/724,293, filed on Nov. 8, 2012, the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to the polymerization and copolymerization of monomers in the presence of fluorinated propylene solvents. More particularly, the present invention relates to the use of polymerization mediums suitable to polymerize one or more monomers to form polymers and/or copolymers, with a tetrafluoropolypropylene being used as a solvent or diluent for the one or more monomers.
DESCRIPTION OF RELATED ART
[0003] Methyl chloride is commonly used as a solvent or diluent in the process of producing polyalpha-olefins such as polyisobutylene. For example, slurry polymerization processes in methyl chloride are used in the production of high molecular weight polyisobutylene and isobutylene-isoprene butyl rubber polymers. Likewise, polymerizations of isobutylene and para-methylstyrene are also conducted using methyl chloride. Similarly, star-branched butyl rubber is also produced using methyl chloride.
[0004] Typically, such polymerization processes use methyl chloride at low temperatures, generally at about −90° C., as the diluent for the reaction mixture. Methyl chloride is employed for a variety of reasons, including that it dissolves the monomers and the catalyst, e.g., aluminum chloride, but not the polymer product.
[0005] However, there are a number of problems associated with the polymerization in methyl chloride, for example, the tendency of the polymer particles in the reactor to agglomerate with each other and to collect on the reactor wall, heat transfer surfaces, impeller(s), and the agitator(s)/pump(s). The rate of agglomeration increases rapidly as reaction temperature rises. Agglomerated particles tend to adhere to and grow and plate-out on all surfaces they contact, such as reactor discharge lines, as well as any heat transfer equipment being used to remove the exothermic heat of polymerization, which is critical since low temperature reaction conditions must be maintained.
SUMMARY OF THE INVENTION
[0006] The present invention relates to polymerization mediums suitable to polymerize one or more monomers to form polymers and copolymers thereof, a fluorinated polypropylene being used as a solvent or diluent for the one or more monomers. The polymerization mediums are especially suitable for slurry polymerization processes.
[0007] In one aspect, a polymerization medium is provided that includes, consists essentially of, or consists of, one or more catalysts, a tetrafluoropropylene, and one or more monomers including at least one alpha-olefin.
[0008] In another aspect, a polymerization process is provided which uses such a polymerization medium in a reactor to produce polymers and/or copolymers.
[0009] In yet another aspect, a polymerization medium and process is provided which uses trans-1-chloro-3,3,3-trifluoropropene in place of a tetrafluoropropene as set forth above.
DETAILED DESCRIPTION
[0010] There is concern for the environment in terms of global warming and ozone depletion. Use of tetrafluoropropylenes in the present invention addresses such issues. For example, trans-1,3,3,3-tetrafluoroprop-1-ene (or “trans-HFO-1234ze”) has zero ozone depletion potential (ODP), and a global warming potential (GWP) of 6, which is quite low.
[0011] The toxicity and flammability of hydrofluorocarbons and hydrofluoro-olefins is also of potential concern. Hydrofluoro-olefins, in particular, are often toxic and flammable; however, tetrafluoropropylenes of the present invention also address this issue as well. For example, trans-HFO-1234ze is bath non-toxic and is not highly flammable. Additionally, trans-HFO-1234ze, can reduce the flammability of some monomers (e.g., isobutylene) when used in combination with those monomers.
[0012] Monomers Which may be used in accordance with the present invention include monomers which can be polymerized using a Lewis acid dispersed in a diluent. Alpha-olefins, such as isoprwylene, are especially preferred; however, any monomer which may be cationically polymerized (e.g., olefins, benzenes, styrenes, vinyl ethers, etc.; may also be used in accordance with the present invention.
[0013] Particularly preferred tetrafluoropropylenes include: trans-1,3,3,3-tetrafluoroprop-1-ene; cis-1,3,3,3-tetrafluoroprop-1-ene; 2,3,3,3-tetrafluoropropene; and mixtures thereof. In the alternative, trans-1-chloro-3,3,3-trifluoropropene may be used instead of tetrafluoropropylene, and achieve many of the same benefits as tetrafluoropropylenes.
[0014] Some tetrafluoropropylenes in accordance with the present invention can also be useful in that they can form compositions which are azeotropic or azeotrope-like. As used herein, the term “azeotropic or azeotrope-like” is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures. From fundamental principles, the thermodynamic state of a fluid is defined by pressure, temperature, liquid composition, and vapor composition. An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the stated pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant-boiling and cannot be separated during a phase change.
[0015] Azeotropic compositions are constant boiling compositions, and azeotrope-like compositions are constant boiling or essentially constant boiling. In other words, for azeotropic and azeotrope-like compositions, the composition of the vapor formed during boiling or evaporation is identical, or substantially identical, to the original liquid composition. Thus, with boiling or evaporation, the liquid composition changes, if at all, only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which, during boiling or evaporation, the liquid composition changes to a substantial degree. All azeotropic or azeotrope-like compositions of the present invention within the indicated ranges, as well as, certain compositions outside these ranges, are azeotrope-like.
[0016] Azeotropic or azeotrope-like compositions in accordance with the the invention may include additional components that do not form new azeotrope-like systems, or additional components that are not in the first distillation cut. The first distillation cut is the first cut taken after the distillation column displays steady state operation under total reflux conditions. One way to determine whether the addition of a component forms a new azeotrope-like system so as to be outside of this invention is to distill a sample of the composition with the component under conditions that would be expected to separate a non-azeotropic mixture into its separate components. If the mixture containing the additional component is non-azeotrope-like, the additional component will fractionate from the azeotrope-like components. If the mixture is azeotrope-like, some finite amount of a first distillation cut will be obtained that contains all of the mixture components that is constant boiling or behaves as a single substance.
[0017] It follows from this that another characteristic of azeotropic or azeotrope-like compositions is that there is a range of compositions containing the same components in varying proportions that are azeotrope-like or constant boiling. All such compositions are intended to be covered by the terms “azeotropic or azeotrope-like” and “constant boiling.” As an example, it is well known that at differing pressures, the composition of a given azeotrope will vary at least slightly, as does the boiling point of the composition. Thus, an azeotrope of A and B represents a unique type of relationship, but with a variable composition depending on temperature and/or pressure. It follows that, for azeotrope-like compositions, there is a range of compositions containing the same components in varying proportions that are azeotrope-like. All such compositions are intended to be covered by the term azeotrope-like as used herein.
[0018] It is well-recognized in the art that it is not possible to predict the formation of azeotropes, as indicated, for example, in (U.S. Pat. No. 5,648,017 (column 3, lines 64-65) and U.S. Pat. No. 5,182,040 (column 3, lines 62-63), both of which are incorporated herein by reference. Applicants have discovered unexpectedly that HFO-1234ze and isobutylene form azeotropic and azeotrope-like compositions.
[0019] According to certain preferred embodiments, the azeotropic or azeotrope-like compositions of the present invention comprise, and consist essentially of, or consist of, effective amounts of trans-HFO-1234ze and isobutylene. The term “effective amounts” as used herein refers to the amount of each component which, upon combination with the other component, results in the formation of an azeotropic or azeotrope-like composition. Any of a wide variety of methods known in the art for combining the components to form a composition can be adapted for use in the present methods to produce an azeotropic or azeotrope-like composition. For example, trans-HFO-1234ze and isobutylene can be mixed, blended, or otherwise contacted by hand and/or by machine, as part of a batch or continuous reaction and/or process, or via combinations of two or more such steps. In light of the disclosure herein, those of skill in the art will be readily able to prepare azeotropic or azeotrope-like compositions according to the present invention without undue experimentation.
[0020] In examples where azeotropic or azeotrope-like compositions of the present invention comprise, consist essentially of, or consist of, isobutylene and HFO-1234ze, the HFO-1234ze can be present in an amount from about 82% by weight of the composition to about 96% by weight of the composition, and more preferably, between about 85% by weight of the composition to about 91% by weight of the composition. As illustrated more fully in Example 1 below, the azeotrope has been found to occur When the trans-HFO-1234ze is present in an amount between about 85% by weight of the composition to about 91% by weight of the composition, i.e., at about a concentration of 88% by weight. The boiling point of the azeotrope was experimentally measured to be at about −20.23° C. at a pressure of about 1 atmosphere.
[0021] As used herein, the term “about” refers to an approximate amount that falls within an acceptable range of experimental error. For example, with respect to temperature, the term “about” can mean the stated temperature plus or minus 0.05° C.
[0022] An azeotropic or azeotrope-like composition of the present invention can be used in polymerization mediums suitable to polymerize one or more monomers to form a polymer, or alternatively, some polymerization mediums in accordance with the present invention which are not azeotropic or azeotrope-like can be transformed into an azeotropic or azeotrope-like composition of the present invention through the simple addition of fluorinated propylene or monomer already present in the composition. For example, a polymerization medium in accordance with the present invention can comprise at least one catalyst, isobutylene and trans-HFO-1234ze. Preferably, the at least one catalyst comprises a Lewis acid, including but not limited to Lewis acids comprising aluminum, boron, gallium, or indium. For example, alkyl aluminum halides, boron halides, and organo-boron halides can be suitable catalysts. Some additional non-limiting examples of suitable Lewis acids are provided in U.S. Patent Application Publication No. 2005/0101751, the disclosure of which is hereby incorporated by reference.
[0023] Azeotropic or azeotrope-like compositions of isobutylene and trans-HFO-1234ze can be used in polymerization processes to produce polymers of one or more monomers. Such a polymerization process can include, for example, providing isobutylene by itself or in combination with other monomers, and contacting the isobutylene or the monomer mixture in a reactor with at least one catalyst in the presence of HFO-1234ze in an amount which forms an azeotropic or azeotrope-like composition of the present invention.
[0024] The compositions in accordance with the present invention improve the performance of the polymerization process, as well as the quality of a polymer product made therewith. As an initial matter, the compositions may be beneficially used to remove monomer from the reaction mixture. For example, at the end of a polymerization process, if an azeotropic or azeotrope-like composition is present, or is subsequently formed, the evaporation of solvent (e.g., trans-HFO -1234ze) facilitates the evaporation of monomer (e.g., isobutylene) from the mixture.
[0025] In addition, de compositions in accordance with the present invention may be used to address the problem with product agglomeration present in existing polymerization processes which use methyl chloride as a solvent. See, e.g., U.S. Pat. No. 7,423,100, column 42, paragraph 25. The compositions in accordance with the present invention could be used to improve product agglomeration properties during polymerization, i.e., by reducing, or possibly completely eliminating, the agglomeration of product.
EXAMPLE 1
[0026] An ebulliometer composed of a vacuum jacketed tube with a condenser on top of which was further equipped with a quartz thermometer. 16.36 grams of HFO-1234ze was charged into - the ebulliometer and the boiling point was observed. Isobutylene was - then added in small increments, and the boiling point of each of the compositions was observed as the weight percentage of isobutylene was increased. A temperature depression was observed at about −20.23° C., indicating a binary minimum boiling azeotrope. The results are shown in Table 1.
[0000]
TABLE 1
Wt % trans-HFO-1234ze
Wt % isobutylene
T (° C.)
100.00
0.00
−19.46
99.76
0.24
−19.49
98.85
1.15
−19.63
95.62
4.38
−20.01
90.99
9.01
−20.19
87.82
12.18
−20.23
84.72
15.28
−20.17
82.05
17.95
−20.11
78.05
21.95
−20.00
74.57
25.43
−19.88
70.12
29.88
−19.71
65.84
34.16
−19.53
61.53
38.47
−19.35
58.85
41.15
−19.25
56.67
43.33
−19.16
54.26
45.74
−19.03
52.07
47.93
−18.97
49.25
50.75
−18.80
EXAMPLE 2
[0027] An ebuiliometer composed of a vacuum jacketed tube with a condenser on top of which was further equipped with a quartz thermometer. 8.06 grams of isobutylene was charged into the ebulliometer and the boiling point was observed. HFO-1234ze was then added in small increments, and the boiling point of each of the compositions was observed as the weight percentage of HFO-1234ze was increased. No temperature depression was observed over the range of compositions tested. The results are shown in Table 2.
[0000]
TABLE 2
Wt % isobutylene
Wt % trans-HFO-1234ze
T (° C.)
100.00
0.00
−7.40
97.34
2.66
−8.71
86.48
13.52
−13.61
75.61
24.39
−16.84
66.12
33.88
−17.84
53.41
46.59
−18.63
47.89
52.11
−18.91
44.12
55.88
−19.12
[0028] From the foregoing, it will be appreciated that although specific examples have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit or scope of this disclosure. It is therefore intended that the foregoing detailed description be regarded as illustrative rather than limiting, and that it be understood that it is the following claims, including all equivalents, that are intended to particularly point out and distinctly claim the claimed subject matter.
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The present invention relates to the polymerization and copolymerization of monomers in the presence of fluorinated propylene solvents. More particularly, the present invention relates to the use of polymerization mediums suitable to polymerize one or more monomers to form polymers and/or copolymers, with a tetrafluoropolypropylene being used as a solvent or diluent for the one or more monomers.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims foreign priority benefits under 35 U.S.C. §119(a)-(d) to DE 10 2011 086 803.8, filed Nov. 22, 2011, which is hereby incorporated by reference in its entirety.
[0002] 1. Technical Field
[0003] The present invention relates to a process for repairing worn cylinder liners of internal combustion engines using a plasma spraying process.
[0004] 2. Background
[0005] It is known to coat the cylinder bearing surface of a cast-aluminum engine block with an iron alloy by carrying out arc wire spraying. Known arc wire spraying processes include twin-wire arc spray (TWAS) process, in which two wires are fed to a spray head in such a manner that the electric current is transmitted across the wires.
[0006] Coatings may also be applied by means of plasma spraying, in which a metal powder or a filler wire are melted and nitrogen is fed to the material mixture by means of metallic nitrogen compounds in order to harden the coating.
[0007] Present-day internal combustion engines and the engine blocks thereof can be cast from a metal or light metal, e.g. aluminum, aluminum blocks in particular having an iron or metal coating on the cylinder bores thereof. The metal coating can be sprayed on by thermal processes. The processes mentioned above are known as thermal spraying processes. It is advantageous to coat the cylinder bores by means of the plasma spraying process because it is thus possible to produce a coating which has a positive effect on a reduced wear factor and on an increased service life of the engine combined with a relatively low oil consumption as compared with conventional linings provided by means of gray cast iron alloys.
[0008] Nevertheless, present-day engine blocks, which are produced for example from a light metal, still have linings made of cast iron metal alloys, for example made of a gray cast iron, such that for example considerable wear arises, for example in the top dead center region but also in other regions of the cylinder liner. If such wear arises, an attempt might be made to provide for repair measures, or to replace the damaged cylinder block; this is not only very costly, but can also have a disadvantageous effect on the entire drive train, since replacement components may not immediately harmonize with existing components and, in certain circumstances, protracted setting work is required.
[0009] US Patent Application US2011030663A1 teaches that effective and economical repair by means of thermal spraying may be complicated owing to the aluminum lip which abuts the axial end of the cylinder liner and owing to the region between the aluminum lip and the surface region on the cylinder liner to be coated. US2011030663A1 furthermore discloses that only the worn region of the cylinder running surface is machined with the hammer or percussion brush, in which case the adjacent regions would not be damaged or machined and would remain in the, for example, honed state. Regions comprising different materials are thus produced in the cylinder liner and make uniform machining more difficult.
SUMMARY
[0010] In an embodiment disclosed herein, a method of repairing a damaged region of a cylinder liner comprises machining the damaged region to produce a reduced-thickness region, roughening a surface of the reduced-thickness region, applying a coating to the reduced-thickness region and to an un-machined region adjacent to the reduced-thickness region, and finish-machining the coating to produce a desired internal diameter, the coating being substantially completely removed from the un-machined surface.
[0011] The coating may further extend axially beyond the un-machined region to coat a lip of an engine block immediately adjacent to an axial end of the liner.
[0012] The coating may be applied by a plasma spraying process, such as a plasma transfer wire arc coating process.
[0013] The machining step may produce an angled or chamfered transition between the reduced-thickness region and the un-machined region.
[0014] The roughening step may comprise a hammer brushing process.
[0015] The finish-machining step may comprise honing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Embodiments of the present invention described herein are recited with particularity in the appended claims. However, other features will become more apparent, and the embodiments may be best understood by referring to the following detailed description in conjunction with the accompanying drawings, in which:
[0017] FIG. 1 is a fragmentary view of engine block made of a light metal in which a cylinder liner has been cast, the cylinder liner having wear in the top dead center region, and
[0018] FIGS. 2 to 5 show sequential stages in a process for repairing the cylinder liner.
DETAILED DESCRIPTION
[0019] As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
[0020] FIG. 1 shows a fragmentary portion of an engine block 1 which may be made of a light-weight metal such as aluminum alloy. Cylinder liners 2 made of a different metallic material, for example made of gray cast iron, have been cast into the engine block 1 , as is well known in the art. The cylinder liner 2 is spanned by a light metal lip 3 (which is part of the engine block 1 ) on the head side, i.e. at the top in the plane of the drawing. Oil is captured between the cylinder liner 2 and the light metal block 1 , as is indicated by means of the channel-like configuration 4 . A piston, not shown, is accommodated in a conventional way in the cylinder liner 2 .
[0021] FIG. 1 shows a portion of the engine block including a portion of an axial end of a cylinder bore, in which the cylinder liner 2 comprises a top dead center region 5 and a head region 6 disposed above the top dead center region. The cylinder liner 2 extends downward along the axial length of the cylinder bore as far as a foot region of the cylinder, which is not shown in the drawing.
[0022] The cylinder liner 2 exhibits wear 7 , by way of example, in the top dead center region 5 . The head region 6 exhibits little or no wear and so is not in need of repair.
[0023] In a first step of a repair process, as shown in FIG. 2 , the material thickness of the cylinder liner 2 is reduced my removing material from the inside of cylinder liner 2 around the full circumference thereof and preferably from the top dead center region 5 , and also encroaching partially into the head region 6 , and as far downward as the foot region (not shown). In this case, it is expedient for the material thickness of the head region 6 immediately adjacent to (in the axial direction) the worn or damaged top dead center region 5 to remain partially unchanged. The light metal lip 3 may also remain un-machined in the step, as shown in FIG. 2 . That is, the original internal diameter of the light metal lip 3 and of the head region 6 of the liner immediately axially adjacent thereto remains unchanged by the machining step.
[0024] The material removal step may be performed so as to form a transition 8 between the top dead center region 5 (in which material is removed) and the head region 6 where no material is removed. Transition 8 may take the form of an incline or internal chamfer, for example, preferably having a continuous inclination in the form of an inclined plane. The transition 8 can also be formed with an outwardly pointing curvature, virtually in the form of a hollow.
[0025] It is advantageous that not the entire thickness of cylinder liner 2 is removed during the machining step, but rather a bearing lining structure remains, in order to bear the repair coating which is to be applied in the manner described hereinbelow.
[0026] In a subsequent step, the reduced-thickness region of the liner, i.e. from the top dead center region 5 downward as far as the foot region, is roughened. The transition 8 may also be roughened in the process.
[0027] Roughening, as used in the present disclosure, is defined as machining in order to roughen the surface in preparation for application of a repair coating. To this end, in the repair process disclosed herein, use is preferably made of the combined hammer brushing process, using a hammer brush or percussion brush. Grooves 9 are thus produced in the cylinder liner 2 . The grooves 9 can also have undercuts. Roughening may be achieved, for example, by means of a combined hammer brushing process such as that disclosed in US2011030663A1, the disclosure of which is incorporated herein by reference.
[0028] Once the surface has been roughened, the repair coating 10 is applied in a subsequent step, as shown in FIG. 4 . To this end, it is possible to use a thermal spraying process, e.g. plasma spraying, by way of example a PTWA internal coating process.
[0029] The repair coating 10 is sprayed on with an excess thickness, where excess thickness in this case means that the repair coating 10 is initially applied in a greater thickness than is desired in the completed, repaired liner. When the coating 10 is sprayed on, the head region 6 , the channel 4 and the light metal lip 3 are also coated. Since some or all of the surfaces of the head region 6 , the channel 4 and the light metal lip 3 have not been roughened, an insufficient bond will be formed in these un-roughened areas. The overspraying of the oil-carrying channel 4 , too, does not cause further harm since the repair coating 10 is removed anyway, as shown in FIG. 5 relating to the subsequent step. In the roughened region of the cylinder liner 2 , the bond between the repair coating 10 and the roughened region is clearly identifiable.
[0030] Between the cast lining, which usually consists of a gray cast iron, and the light metal of the cylinder liner, an oil volume, albeit a small oil volume, is captured in a gap between both components, such that it is impractical to carry out a repair by way of a conventional procedure by means of known plasma spraying or plasma transfer wire arc (PTWA) internal coating processes, since the captured oil will issue from the gap on account of the action of the plasma flame, and therefore properties which are required for the bonding of the coating which is sprayed on to the base material are no longer ensured. The coating would therefore be more likely to fail at the transition between the light metal and the metallic lining.
[0031] Once the repair coating 10 has been applied to the excess thickness, it is finish-machined, in which case, as shown in FIG. 5 , the original, desired internal diameter of the cylinder liner 2 is restored. In particular, the coating adhering to the head region 6 , bridging the channel 4 and adhering to the light metal lip 3 is substantially completely removed. The term “substantially completely removed” is intended to mean that although some small trace or remnant of the coating may remain, the original diameter of the head region 6 and lip 3 is not significantly decreased. In this respect, the initial coating of these regions also caused no harm, even though oil, for example, would have reduced the bond. The finish-machined repair coating 10 thus adjoins the head region 6 in a flush manner.
[0032] The finish-machining step may comprise honing, for example. Since the repair coating is continuous from the transition 8 as far as the foot region, material transitions to different materials are also avoided in the repaired cylinder liner, such that a simple finish-machining tool or honing tool can be used instead of a special honing tool
[0033] It is noted that the term “finish-machining” as used in this context does not necessarily imply that no further smoothing, polishing, or other treatment of the liner surface will be carried out. Rather, the term refers to the machining step that produces the nominal internal diameter of the cylinder liner.
[0034] Although material losses which would be avoidable are therefore to be expected, such a procedure is advantageous in terms of economy of machining, since the spraying tool can be operated in a continuous pass without regard to transition points. Since no regard is paid to transition points, a considerable gain in time which more than compensates for the disadvantage of material loss is made. It is also advantageous that a permanently unchanged original internal diameter of the cylinder liner can thus be produced, without it being necessary in turn to pay regard to (material) transitions.
[0035] The repair coating produced on the cylinder liner by way of the disclosed repair process may have the same properties as a coating which has been sprayed from the outset onto a light metal wall in order to thereby form the cylinder liner. In this respect, with the disclosed repair process, it is possible for a cylinder liner originally produced from gray cast iron to have the advantages of a coating applied by, for example, a PTWA internal coating process, while retaining the fundamental gray cast iron lining.
[0036] It is of course possible for all cylinder liners of the engine block to be processed by the repair process according to the invention. It is also possible to process wear-free cylinder liners of the engine block, which is to be processed anyway, by the repair process according to the invention.
[0037] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.
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A method of repairing an inner surface of a cylinder liner housed in an engine block. Material is removed from the inner surface to produce a reduced-thickness region, the reduced-thickness region extending axially relative to the cylinder and stopping short of an end of the liner to leave a region of original diameter between the reduced thickness region and the end of the liner. The surface the reduced-thickness region is then roughened, for example by hammer brushing. A plasma coating is applied to the reduced-thickness region and to at least a portion of the region of original diameter. The coating is then finish-machined to produce a uniform internal diameter equal to an original internal diameter of the region of original diameter prior to the application of the coating.
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RELATED APPLICATIONS
This is a divisional of U.S. patent application Ser. No. 09/627,597 filed on Jul. 28, 2000 in the names of Alexandra Gordon and Charles W. Grimes for “Packaging Device for Disc-Shaped Items and Related Materials and Method for Packaging Such Disks and Material”, U.S. Pat. No. 6,371,289, which, in turn, was a divisional of U.S. patent application Ser. No. 09/161,064 filed on Sep. 25, 1998 in the names of Alexandra Gordon and Charles W. Grimes for “Packaging Device for Disc-Shaped Items and Related Materials and Method for Packaging Such Disks and Material”, U.S. Pat. No. 6,216,857.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates, in general, to a device for packaging and displaying a circular or disc-shaped media and other materials and a method for packaging such disc-shaped media and other materials and, in particular to containers and methods for initially packaging and thereafter repeatedly storing disc-shaped media together with or without other materials. Still more particularly, the present invention relates to a new and improved container for initially packaging and thereafter repeated storing of disc-shaped media and other materials in stacked relationship, having a first chamber and a second chamber stacked on top of one another for respectively receiving and securely retaining the disc media and the other materials.
Still more particularly, the present invention further relates to a new and improved method for initially packaging and thereafter repeated storing of media and other materials in stacked relationship, wherein in a preferred embodiment the disc-shaped media is inserted into a cavity within a first member, and the other materials are placed inside an open ended second member through an opening therein, and the first member is then attached about the second member so as to close the opening in the second member.
2. Background of the Invention
Packaging and storage devices for media are generally known. Disc-shaped media, such as CD's, DVD's or CD-ROM's, encounter special problems in handling, packaging and storage due to their delicate, flat recorded surfaces. Such disc media is generally sold in plastic cases which are sometimes referred to as “jewel boxes.” Such cases are generally rectangular and have a mounting hub for holding the disc media by its center aperture. Such cases are usually kept after purchase of the disc media and utilized for re-packaging, of the disc media between usage. Such jewel boxes are impractical packaging containers for shipping because of their small dimensions and easy breakage, and they thus require substantial additional packaging material or placement in larger shipping containers.
Disc media is routinely sold with other materials (whether directly related to the content of the disc media, i.e., ancillary, or otherwise). At the present time, disc media in such “jewel boxes” is commonly packaged together with ancillary materials in larger rectangular shaped cardboard boxes for shipping, sale and packaging. The “jewel boxes” are necessary to reliably protect the disc media from contact with the ancillary materials in the larger cardboard boxes. Such plastic case/cardboard box combination package arrangements are not only expensive, they also do not lend themselves to easy and secure repeated re-storage of the disc media and ancillary materials. They are often damaged during initial opening and repeated re-storage. They are often unable after initial opening to securely re-store the disc media (in the jewel box) and the other materials together in the cardboard packaging in a manner to preclude contact with each other. They frequently become unsightly after initial opening and repeated re-storage. They are, themselves, difficult to handle and store.
Other types of packaging and storage devices are needed to organize, protect, ship, display at retail and store disc media sold and/or shipped in combination with ancillary materials.
A need also exists for devices which can effectively and efficiently organize, protect, ship, display at retail and store disc shaped media with other materials.
An opportunity exists that is not being commercially exploited at the present time to distribute disc-shaped recording media with materials that are either ancillary or wholly unrelated to the content of the disc media. This opportunity is not being exploited due to the lack of an effective container design and method for efficiently organizing, protecting, shipping, displaying at retail and storing disc-shaped media packaged with other materials.
SUMMARY OF THE INVENTION
One important object of this invention is to provide a container in which and a method whereby disc-shaped media and ancillary materials can initially be packaged together in stacked relationship and, after removal and use, they can easily be re-stored in stacked relationship in a manner so as to avoid contact there between.
Another object of this invention is to provide a container and a method of packaging that eliminates the need for a separate case (i.e., the need for a “jewel box”) for the disc media.
Another object of this invention is to provide a container and a method of packaging whereby during initial storage, shipping, retail presentation and re-packaging disc media is securely held against movement and protected.
Another important object of this invention is to provide a shipping container in which and a method of shipping whereby disc-shaped media and other materials can be packaged, presented, conveyed, distributed and stored.
Another important object of this invention is to provide an aesthetically unique and compelling device and method for presenting at retail disc-shaped media and other materials which may or may not be related to the content of the media.
Another object of this invention is to provide a container and a method of packaging whereby the internal wall of the first chamber of the container is cylindrical in shape and of a diameter slightly larger than the external diameter of the disc media to thus retain the disc media in the container against movement in the plane of the disc media.
Another object of this invention is to provide a container and a method of packaging whereby either an annular ring or protrusions mounted on the internal wall of the first chamber define an opening slightly larger in internal diameter than the external diameter of the disc media into which the disc media can be inserted to thus retain the disc media in the container against movement in the plane of the disc media.
Another object of this invention is to provide a container and a method of packaging whereby either an annular lip or protrusions extend from the internal wall of the first chamber of the container and define an opening slightly smaller in internal diameter than the external diameter of the disc media on which the disc media can seat to thus retain the disc media in the container against movement in a. first direction perpendicular to the plane of the disc media.
Another object of this invention is to provide a container and a method of packaging, whereby the container has a removal lid that attaches to the container when the disc media is either initially positioned or subsequently re-stored on the seat and that retains the disc media against movement in a second, opposite direction perpendicular to the plane of the disc media.
Another object with this invention is to provide a container and a method packaging whereby the seat and lid are removable and the seat and lid can be combined to create a permanent storage and restoring package for the disc media alone.
Another object of this invention is to provide a container and a method of packaging whereby an annular ring or protrusions mounted on the internal wall of the first chamber define an annular post slightly smaller in exterior diameter than the diameter of the center hole of the disc media to thus retain the disc media on the post in the container against movement in the plane of the disc media.
Another object of this invention is to provide a container and a method of packaging whereby a protective insert is placed in the container before the disc media to protect the disc media from contact with the other materials.
Another object of this invention is to provide a container and a method of packaging whereby a replaceable protective insert is placed in the container before the disc media to protect the disc media from contact with the other materials, which insert can be removed to access the ancillary materials and can be replaced after the ancillary materials are re-stored in the container and before the disc media is re-stored in the container.
Another object of this invention is to provide a container and method of packaging whereby the disc media support members are removable so as to afford complete and unfettered access to the second chamber beneath the disc media.
Another object of this invention is to provide a container and method of packaging whereby the first chamber is within the removable lid.
Another object of this invention is to provide a container and method of packaging whereby the first chamber is within the removable lid and the disc media support member is a center post fixedly attached to and extending from the inside center of the lid.
Another object of this invention is to provide a container and method of packaging whereby the removable lid has both a first chamber for the disc media and a second chamber for other materials and wherein there is a third chamber in the container.
A further object of this invention is to provide a container and method of packaging whereby the container has first and second chambers and the second chamber in which the other materials are stored has a second opening besides the opening through the first chamber.
A further object of this invention is to provide container and a method of packaging whereby the container has a closure mechanism for the second opening that is separate and distinct from the closure mechanism for the opening into the second chamber through the first chamber.
A further object of this invention is to provide a container and method of packaging whereby the container has an exterior shape for the first chamber such that the first chamber can serve as a base for the container.
Yet another important object of this invention is to provide a container and method of packaging whereby the container has an exterior shape for the second chamber such that the second chamber can serve as a base for the container.
A still further object of this invention is to provide a container and method of packaging for disc shaped media and other materials whereby the top and bottom covers are detachable and can be combined to create a smaller container for the disc shaped media.
To accomplish these and other objects, the container of this invention in its preferred form is a cylinder provided with a removable lid and first and second chambers. The first chamber is immediately beneath the lid and has an inner structure defining circumferential support for disc media. The inner structure is a one-piece annular collar member, with an upstanding annular ring with an interior wall having a diameter slightly larger than the outside diameter of the disc media, and an annular lip that defines an annular opening having a diameter slightly smaller than the outside diameter of the disc media, such that the disc media sits on the annular lip and is restrained against movement in the plane of the disc media by the ring and against movement in directions perpendicular to the plane of the disc media by the lip and the lid. The inner structure further includes an annular clip that extends over the rim of the container wall in nesting configuration, and which is locked on the container wall when the lid is affixed to the container, but which can be removed after the lid and disc media are removed to facilitate unencumbered access to the second chamber of the container beneath the first chamber. The second chamber is the same diameter as the first chamber and is of sufficient height to accommodate other materials that may or may not have relevance to the disc media. The bottom of the second chamber remote from the lid is flat and serves as the base of the container.
In the preferred method of packaging, other materials are inserted into a first portion of an open ended cylindrical container through the open end, inner support elements are then inserted into the container through the open end, a protective element is then inserted into the container through the open end, disc media is then inserted into the container through the open end into a second portion of the container in protected engaging relation with the inner support elements within the container, and a lid is then applied to the container to both secure the disc media within the second portion of the container and to seal the container.
The above, as well as additional objects, features and advantages of the invention will become apparent in the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features believed characteristics of the invention are set forth in the appended claims. The invention itself, however, as well as the preferred mode of use, further objects and advantages thereof, will best be understood by reference to the following detailed description of illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
FIG. 1 is an exploded perspective view of the novel disc packaging device of the present invention with the lid and disk media removed, illustrating the use of a one-piece annular collar member with an annular ring and lip;
FIG. 2 is a cut-away, cross-sectional side view of a portion of the novel disc packaging device of FIG. 1 when the lid is on the container, along line AA illustrating the resultant first and second chambers thereof;
FIG. 2A is an alternative embodiment of the device shown in FIG. 2, wherein a protective element is inserted between the first and second chambers;
FIG. 2B is an alternative embodiment of the device shown in FIG. 2A, showing an alternative method of insertion of the protective element between the first and second chambers;
FIG. 2C is a further alternative embodiment of the device shown in FIG. 2A, showing, a further alternative method of insertion of the protective element between the first and second chambers;
FIG. 3 is a top plan view of the novel disc packaging device of the present invention illustrating the alternative use of abutments and protrusions affixed to the inside wall of the container;
FIG. 3A is a cut-away, cross-sectional side view of a portion of the device shown in FIG. 3, along line B—B, with a disc media and other materials inserted and the lid affixed;
FIG. 3B is a cut-away, cross-sectional side view of an alternative embodiment of the novel disc packaging device of the present invention illustrating the alternative use of the upstanding rim of the base and the inside wall of the cover in place of the abutments and protrusions of FIG. 3;
FIG. 3C is a cut-away, cross-sectional side view of an alternative embodiment of the novel disc packaging device of the present invention illustrating the alternative use of the outer surface of the cover and the inner surface of a supplementary cover in place of the abutments and protrusions of FIG. 3;
FIG. 4 is a top plan view of the novel disc packaging device of the present invention illustrating the alternative use of a center annular post support for the disc media suspended from spokes;
FIG. 4A is a cut-away, cross-sectional side view of the device shown in FIG, 4 , along line C—C, with a disc media and other materials inserted and the lid affixed;
FIG. 5 is a top plan view of the novel disc packaging device of the present invention illustrating fingers that extend from a frame carried by the side wall of the container and that provide center support for the disc media;
FIG. 5A is a cut-away, cross-sectional side view of the device shown in FIG. 5, alone, line D—D, with a disc media and other materials inserted and the lid affixed;
FIG. 6A and 6B are cross-sectional views of alternate embodiments of the packaging device of the present invention depicting two different methods of mounting the disc media support member to the device outer wall;
FIG. 7 is a cut-away, cross-sectional side view of an alternative embodiment of the present invention with disc media and other materials inserted, the protective element inserted and the lid closed, in which the first chamber in which the disc media is stored is in the cover;
FIG. 7A is a cut-away, cross-sectional side view of an alternative embodiment of the device shown in FIG. 7, wherein the disc media is inserted into a protective envelope that is affixed to the inner surface of the cover;
FIGS. 8 and 8A are side perspective, partially cut-away, cross-sectional views of alternative embodiments of the present invention, illustrating the use of the “lid” of the embodiment shown in FIG. 7 as the base, thereby allowing the portion of the invention defining the second chamber to be of an irregular shape (FIG. 8) or to have deformable construction (FIG. 8 A);
FIG. 9 is a cut-away, cross-sectional side view of an alternative embodiment of the present invention in which the disk media is located in the lid and the lid and the container include second and third chambers, respectively, for storing other material;
FIG. 10 is a cut-away, cross-sectional view of another embodiment of the present invention in which the second chamber in the container for storing other materials includes a second opening separate and distinct from the lid and a removable cover such that access to the second chamber can be attained without removing the lid;
FIGS. 11 and 11A are cut-away, cross-sectional side views of another embodiment of the device shown in FIG. 10 in which the method of mounting shown in FIG. 6A is utilized and wherein the removable cover for the second chamber can be mated with the removable cover for the first chamber to form a mini-packaging device shown in FIG. 11A;
FIG. 12 is a cut-away, cross-sectional side view of an alternative embodiment of the device shown in FIGS. 11 and 11A in which the method shown in FIG. 3B for retaining the disc media is utilized and in which the two covers threadably engage the base and, when removed, can be threaded together to create a mini-packaging unit;
FIG. 12A and 12B are cut-away, cross-sectional side views of alternative embodiments of the device shown in FIG. 12, wherein the two covers slidably engage after removal (FIG. 12A) or threadably engage after removal (FIG. 12 B);
FIG. 13 is a cut-away, cross-sectional side view of another embodiment of the present invention in which a concave cavity on the exterior side of the cover for the device forms the first chamber for the disc media and a seal encloses the disc media within the concave cavity;
FIG. 14 is an exploded perspective view of a further alternative embodiment of the novel disc packaging device of the present invention with the lid, disk media and protective element removed, illustrating the use of a sealed base; and
FIG. 15 is an exploded perspective view of a further alternative embodiment of the novel disc packaging device of the present invention in which the disk media is sealed within the lid, and the base is separately sealed, and the lid and base are detachably joined together by an outer packaging skin that can be severed with a pull string.
DETAILED DESCRIPTION OF THE INVENTION
With reference now to the figures and in particular with reference to FIG. 1, there is shown a front view of the disc packaging device 10 of the present invention. As illustrated, disc packaging device 10 includes a lower base component or container 12 and an upper cover component or lid 14 . Lower base component 12 and upper cover component 14 are utilized to form a generally cylindrical packaging device of dimension slightly larger than the disc shaped recording media to be stored. End plates 16 and 18 cooperate with lower base component 12 and upper cover component 14 to fully enclose the cylindrical packaging space defined thereby.
The lower base component 12 of the embodiment of this invention shown in FIGS. 1 and 2 includes a side wall 20 . The side wall can be constructed from either cardboard (i.e., natural fiber material) or plastic (i.e., man-made synthetic material) or other material suitably rigid for the base component to retain its shape, including metal, e.g., as in a vacuum sealed, canned product.
The base component 12 can be designed to threadably receive the bottom plate 16 which is of conventional design, made of stiff cardboard, plastic, metal or some similarly rigid material and used as a cover-all screw cap on a very wide variety of containers. Alternatively the bottom plate 16 can nest inside the side wall 20 where it is held by friction, stapling, gluing or some other means. The side wall 20 has an upper section 22 and the upper section 22 can be threaded to accommodate the upper cover component 14 although in the embodiment shown in FIGS. 1 and 2 the cover is made of plastic and snaps on in a conventional manner.
As best seen in FIG. 2, the upper section 22 is defined by an outer wall 24 , an inner wall 26 and a rim 28 . The cover component 14 has a side wall 30 defined by an outer wall 32 , an inner wall 34 and a rim 36 . The diameter of the inner wall 34 of the cover component is slightly greater than the diameter of the outer wall 24 of the base component. In the embodiment shown in FIGS. 1 and 2, there is an inner structure 40 which provides circumferential support for a disc shaped media 42 stored within the packaging device 10 . The structure 40 comprises an annular collar 44 having an annular ring 46 and an annular lip 48 . The inner structure 40 nests within the lower base component 12 . The annular collar 44 has an outer diameter greater than the diameter of the inner wall 26 of the base component such that the annular collar extends beyond the inner wall 26 and sits on top of the base rim 28 . The annular ring 46 has an outer diameter less than the diameter of the inner wall 26 , such that the annular ring nests inside the inner wall 26 . The annular lip 48 has an inner diameter less than the outer diameter of the disc shaped media 42 . Thus, the disc shaped media will rest on the annular lip, inside the annular ring. In this way, movement of the disc shaped media in the plane of the disc shaped media is precluded by the annular abutment 46 . Movement of the disc shaped media perpendicular to its plane is prevented in one direction by the annular lip 48 . When the cover component 14 is affixed to the base component 12 , the cover plate 18 acts to preclude movement of the disc shaped media in the opposite perpendicular direction to the plane of the disc shaped media.
In the embodiment disclosed in FIG. 2A, a protective member 50 is attached to the annular lip 48 . The protective member can be made of plastic film or any other conventional material to provide a barrier between the disc shaped media and other materials 52 which can be stored in the base component 12 of the packaging device 10 . The protective member can be permanently affixed to the annular lip or it can be affixed at the time of assembly and shipment and removed by the consumer after purchase, i.e., at a time when further “rough handling” that would cause interaction between the disc shaped media and the other materials is less likely to occur.
In an alternative embodiment disclosed in FIG. 2B, the protective element is removable and sized to seat on the annular lip 48 between the annular lip 48 and the disc shaped media. The protective element is round like the disc shaped media and has a central opening into which one's finger can be inserted to engage, lift and remove the protective element and subsequently engage, lift and replace the protective element.
In an alternative embodiment disclosed in FIG. 2C, the protective element 50 B is flexible and is removably inserted within the lower base component beneath the annular lip 48 and on top of the other materials 52 placed therein. The protective element is sized to correspond to the interior wall 26 and has a central opening into which one's finger can be inserted to engage, lift and remove the protective element and subsequently engage, lift and replace the protective element. Alternatively, the protective element can be provided with a lift tab or some other conventional means whereby it can be grabbed and removed.
In the alternative embodiment shown in FIGS. 3 and 3A, the inner structure 40 is modified. The annular collar 44 with annular ring 46 and annular lip 48 is replaced, by discrete abutments 54 and discrete protrusions 56 . Collectively, the abutments 54 and protrusions 56 are positioned within the lower base component 12 around the circumference of the inner wall 26 spaced below the rim 28 , affixed to the inner wall 26 , so as to perform the same function as the annular ring 46 and annular lip 48 . Specifically, the abutments 54 preclude movement of the disc shaped media in the plane of the disc shaped media i.e., performing the same function as the annular ring 46 . Similarly, the protrusions 56 are positioned about the inner wall 26 and collectively preclude movement of the disc shaped media in a direction perpendicular to plane of the disc shaped media i.e., performing the same function as the annular lip 48 .
FIG. 3B shows a further alternative embodiment wherein the disc shaped media is seated on the rim 28 and movement of the disc shaped media perpendicular to its plane is prevented in one direction by the rim 28 . When the cover 14 is affixed to the base component 12 , movement of the disc shaped media in the plane of the disc shaped media is precluded by the inner wall 34 of the cover 14 and inner surface 14 a of the cover 14 acts to preclude movement of the disc shaped media in the second, opposite perpendicular direction to the plane of the disc shaped media.
FIG. 3C shows a further alternative embodiment wherein the disc shaped media is seated on the outside surface 14 b of the cover 14 and movement of the disc shaped media perpendicular to its plane is prevented in one direction by a supplementary cover 144 that snaps onto the cover 14 . When the supplementary cover 144 is affixed to the cover 14 , movement of the disc shaped media in the plane of the disc shaped media is precluded by the inner wall 144 a of the supplementary cover 144 and the inner wall 144 b of the supplementary cover 144 acts to preclude movement of the disc shaped media in the second, opposite perpendicular direction to the plane of the disc shaped media. The supplementary cover 144 can include a chamber 144 d and a protective element 50 b can be inserted to prevent contact between the disc shaped media and whatever materials 52 a are placed in the chamber 144 d.
In the alternative embodiment seen in FIGS. 4 and 4A, the inner support structure 40 is replaced with an inner support structure 58 that provides center support for the disc shaped media as opposed to the circumferential support provided by inner structure 40 . In the embodiment shown in FIGS. 4 and 4A, the alternative inner structure 58 includes an annular ring 60 and spokes 62 extending therefrom. As seen in FIG. 4A, the annular ring 60 has a raised portion 64 on which the disc media 42 sits, The spokes 62 each have a finger portion 66 which extends upwardly and outwardly such that when the structure 58 is inserted into the base component 12 , the fingers 56 frictionally engage the inner wall 26 and sit on the upper rim 28 . The structure 58 can include webbing between the fencers 56 (ala the webbing in a duck's foot) comprised of a thin material to provide protection for the disc shaped media 42 from the other materials 52 . Inside the annular ring 60 would be left open to allow the consumer, after removing, the cover 14 , to insert their finger into the annular ring and to thereby remove both the disc shaped media 42 and the structure 58 .
FIGS. 5 and 5A show a further alternative inner structure 68 comprising an annular collar 70 from which fingers 72 extend inwardly. At the ends of the fingers 72 are upstanding projections 74 . The annular collar 70 nests inside the inner wall 26 and sits on the rim 28 in the same manner as the inner structure 40 in the embodiment shown in FIGS. 1 and 2. The upstanding projections 74 cooperate to provide a center support structure for the disc shaped media.
As seen in FIGS. 6A and 6B, the fingers 72 in the embodiment shown in FIGS. 5 and 5A do not necessarily need to be suspended from an annular collar. Alternatively, the could be clipped to the side wall 20 as seen in FIG. 6A or they could be screwed into the side wall 20 as shown in FIG. 6 B.
In an alternative embodiment shown in FIG. 7, a center support structure is provided for the disc shaped media in the upper cover component 14 . Specifically, projections 80 extend from the inside wall 82 of the end plate 18 . These projections 80 cooperate to provide secure support for the disc shaped media in the cover component 14 . A protective element 84 can be provided which is either removably nested within the cover as shown or which can be inserted at the time of manufacture and removed and discarded by the consumer after purchase. The cover 14 can engage the base component 12 in any variety Of conventional ways, e.g., snap on, telescope on, screw on, etc.
In a further alternative embodiment shown in FIG. 7A, the disc shaped media is encased within an envelope 84 a made of plastic or some other suitable material and which is affixed to the inside wall 82 of the end plate 18 . The envelope is either removably or permanently affixed, e.g., by gluing, with double-sided tape, or by other conventional means. The envelope can itself constitute a re-useable packaging container for the disc shaped media that either remains affixed to the plate 18 or can be removed from the plate 18 , e.g., so that the cover 14 can be discarded. Or the disc shaped media can be packaged within a packaging sleeve (not shown) ail of which can then be inserted into the envelope and then removed from the envelope once the envelope is opened.
FIGS. 8 and 8A show further alternative embodiments of the present invention. In FIG. 8, the fact that the disc shaped media is stored within the cover component 14 allows for an alternative construction of the container 12 . In this alternative embodiment, the cover 14 serves as the “base”. The alternative base 90 , in which the other materials, in this case, a doll 92 , are stored, has an end wall structure 94 which frictionally encases the inner wall 96 and seals the chamber in the base 90 . Alternatively, wall 94 can be provided with threads so that it will threadably engage corresponding threads on the inside wall 96 . The cover 14 and base 90 can be attached in the same manner as heretofore been discussed in connection with other embodiments.
In the embodiment showing in FIG. 8A, the cover 14 once again carries the disc shaped media 42 and thereby allows the base 12 to be of a deformable construction 98 . The deformable member 98 has a rigid internal support structure 100 which is designed to frictionally or threadably engage the cover 14 .
In the alternate embodiment shown In FIG. 9, the disc shaped media is stored in a first chamber 102 in the lid 14 defined by an annular support 40 similar in construction to the embodiment of FIG. 7, except that the lid includes a second chamber 104 defined by an outer wall 106 for other materials and the base 12 includes a third chamber 108 . In the alternate embodiment shown in FIG. 10, which is similar in construction to the embodiment of FIG. 4, there is provided an additional opening 110 in the container 22 and a cover 116 for closing the opening 110 . The cover 116 can be removed to gain access to the chamber 104 without removing the cover 14 .
In the alternative embodiment shown in FIGS. 11 and 11A, an inner structure 40 a is provided that is a slightly modified version of the inner structure 40 shown in FIG. 2, in that it includes an annular wall 45 that extends around the entire circumference of the annular collar 44 and engages the outer surface of the wall of the base 12 , and the cover 14 is configured to engage not the base 12 , but rather, the annular wall 45 . An additional opening 110 is provided as in the embodiment of FIG. 10, and a cover 116 a is provided that is a slightly modified version of the cover 116 of FIG. 10, in that it includes not only an outer annular wall 116 b for engaging the outer surface of the wall of the base 12 , but also an inner annular wall 116 c for engaging the inner surface of the wall of the base 12 . The circumferential dimension of the outer surface 116 d of the wall 116 b of the cover 116 a is identical to the circumferential dimension of the outer surface 45 d of the wall 45 , such that the covers 14 and 116 a can be removed and the cover 14 which matingly engaged the wall 45 will matingly engage the outer wall 116 b of the cover 116 a , as shown in FIG. 11 A. In this way, as also shown in FIG. 11A, the covers 14 and 116 a can be used together as a mini-packaging device for the disc shaped media 42 . In the embodiment shown, the inner wall 116 c helps to securely retain the disc shaped media against movement. However, it is understood that the benefits of the invention could be achieved without such inner wall, or utilizing one of the other retaining methods disclosed herein.
In the alternative embodiment shown in FIG. 12, the disc shaped media seats on the rim 28 as in the embodiment shown in FIG. 3B, but the cover 14 x does not snap onto the base 12 , but rather, threadably engages it. Furthermore, the bottom 12 x of the base 12 is flared outwardly and contains internal threads that are of the same dimension as the internal threads of the cover 14 x . The cover 116 x includes mating external threads such that the cover 116 x can be threaded into the flared bottom 12 x of base 12 . In this way, the covers 14 x and 116 x can be removed from the base 12 and threadably engaged to form a mini-packaging unit for the disc shaped media.
In the alternative embodiments of FIGS. 12A and 12B, the need to flare out the bottom of the base 12 is eliminated. In FIG. 12A, the base 12 y receives a bottom cover 116 y that includes an overlapping portion 117 y , the outer surface 118 y of which is of equal dimension to the outer surface 118 y of which is of equal dimension to the outer wall of the base 12 y , such that covers 14 y and 11 y can be slidably engaged to form a mini-storage unit for the disc media. In FIG. 12B, the base 12 z has an external threaded portion 119 z and an internal threaded portion 120 z each of which extends beyond the center line “C” of the wall of the base 12 z . In this way, when the covers 14 z and 116 z are removed, they can be threadably engaged to form a mini-storage unit for the disc media.
FIG. 13 shows a further alternative embodiment, wherein the cover 244 nestingly seats within the base 12 and the disc shaped media 42 is placed within the concave recess 246 of the cover 244 . A seal 248 made of plastic or other suitable material is applied to the cover 244 to hold the disc shaped media within the cover 244 until the seal is removed by the user. The disc shaped media can be retained against movement within the cover 244 as a result of contact with the side walls 250 , bottom wall 252 and seal 248 , or by utilization of any of the other methods taught herein.
FIG. 14 shows a further alternative embodiment wherein the base 12 is a separately manufactured container of miscellaneous content, that includes a slightly concave end 251 , the depth 252 of which exceeds the combined thickness of a disc shaped media 42 and a protective element 50 which are seated within the concave end 251 and held there by cover 14 which snaps onto base 12 . In an alternate embodiment, a protective element is not used or the disc shaped media is packaged in an envelope (not shown).
FIG. 15 shows a further alternative embodiment wherein the disc shaped media is mounted and sealed within cover 14 , e.g., as taught herein in connection with other embodiments, and cover 14 is attached to base 12 by paper packaging material skin 301 that binds the cover 14 and base 12 together. Cover 14 is separated from base 12 by pulling string 302 which tears the skin 301 and brakes the circumferential attachment between cover 14 and base 12 .
It would be understood that in each embodiment, a container device is provided in which disc shaped media can be packaged, distributed, displayed at retail and, if desired, restored with other materials and that, in effecting such usage, discrete chambers are provided for the disc media and for the other materials so as to prevent contact between the disc media and the other materials. In the embodiments shown in FIGS. 1 through 6B, the inner structure, whether it is the annular collar of FIG. 1, or the discretely positioned abutment/protrusion clips of FIG. 3, or the upstanding rim in FIG. 3B, or the lid and supplemental lid of FIG. 3C, or the “spider” structure of FIG. 4, or the “trap” structure of FIG. 5, in each case is located in and helps define a first chamber in the lower base component 12 . Underneath this first chamber is a second chamber. The first chamber receives and securely holds, despite repeated removal and re-packaging, the disc shaped media. The second chamber receives the other materials and keeps these materials separate from the disc shaped media. The need for a separate “jewel case” for the disc shaped media is thus completely eliminated.
It would be understood that the shape of the container can be varied without departing from the scope of the present invention, e.g., the cylindrical base 12 can be square or rectangular so long as the outer wall of the collar 40 corresponds and the collar includes spacers from the outer wall of the collar to the annular ring and annular lip of the present invention. Similar adjustments could be made to the other embodiments as would be apparent to those skilled in the an having reviewed this disclosure. The abutment/protrusions clips of FIG. 3 could be mounted on a non-cylindrical shaped base, as could the spider structure of FIG. 4 or the trap structure of FIG. 5 .
It would be understood by those skilled in the art that the function of the annular ring of FIG. 1 or the abutments of FIG. 2 could be performed by an appropriately dimensioned inner wall 26 of the container 12 .
It would be further understood that while several methods of attaching the annular collar of FIG. 1, the abutment/protrusion clips of FIG. 2, the spider structure of FIG. 3 and the trap structure of FIG. 4 have been shown, those skilled in the alt after having reviewed this disclosure could devise other means of attachment without departing from the scope of the present invention.
It would be further understood by those skilled in the art that the device and method of this invention can accommodate one or more disc shaped media, e.g., through the insertion of protective elements therebetween.
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An elongated packaging device is provided for packaging at least one disc-shaped item such as, for example, a recording media disc such as a CD, a CD-ROM or a DVD, together with other materials relating to such disc or otherwise in a stacked relationship. The packaging device comprises a first member having a first chamber and a first opening providing access thereto, said first chamber including means to receive and retain a disc-shaped media, and a second member for the storage of materials other than the disc-shaped media, said second member including a second chamber and a second opening providing access thereto. A method is further provided for packaging such disc-shaped item and other material within the packaging device.
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CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the priority of German Patent Application, Serial No. 102 57 466.9, filed Dec. 9, 2002, pursuant to 35 U.S.C. 119(a)-(d), the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a conveyor system for transporting articles, in particular containers for baggage pieces. The present invention further relates to a control method for such a conveyor system.
[0003] It is known to use conveyors for transporting articles, such as baggage pieces, for example at airports. One or more baggage pieces are, for example, placed in a suitable container. The conveyor, which is typically understood to include a conveying element with a drive, a conveyor belt, cross members, etc., is here composed of several conveyer sections, each of which includes an endless conveyor belt and a drive motor. The conveyor sections are connected sequentially in such a way that the conveyor belts transfer the containers that are transported by the conveyor belts in the transport direction, so as to enable the baggage pieces in the containers to be transported from a start position to a target position. In addition, the conveyor can also serve as an intermediate storage unit for the baggage pieces. A baggage piece deposited the evening before departure date can travel continuously in a circle during the night. The conveyor deposits the baggage pieces at the target position only shortly before the scheduled departure time for subsequent loading onto the aircraft.
[0004] The transport speed of the conveyor sections thereby depends on the transported articles. The different transport speeds reduce the capacity of the intermediate storage unit and make data tracking and/or handling of an individual item difficult.
[0005] To improve this situation, the conveyor belts in a conveyor section are either shortened so as to transport as a smaller number of articles on the conveyor belt, or controlled drives with a feedback of the rotation speed are employed. Servo motors with a stabilized rotation speed can also be used. Conveyors of this type are relatively expensive.
[0006] [0006]FIG. 3 shows a conventional conveyor system 1 including an upstream conveyor 2 and a downstream conveyor 3 at various points in time t 1 to t 9 . The transport direction is indicated by the arrow 4 . In the schematic illustration of FIG. 3, the conveyor 2 is depicted by a conveyor belt 6 , whereas the conveyor 3 is depicted by the conveyor belt 7 . Articles 5 , transported on a conveyor belt 6 , 7 and placed on conveyor sections, are also indicated schematically by black boxes. The articles 5 can be separate baggage pieces or containers that hold one or several baggage pieces. Each conveyor belt 6 , 7 is here driven by an unregulated, uncontrolled, load-torque-dependent asynchronous motor (not shown) with a fixed, unchangeable desired rotation speed n soll .
[0007] The process starts at time t 1 , when nine evenly distributed articles 5 are transported from the conveyor belt 6 in the transport direction 4 to the downstream conveyor belt 7 . Because the actual rotation speed n ist (t) of the asynchronous motor depends on the load torque, the speeds of the conveyor belts 6 , 7 at time t 1 are different. In other words, the empty conveyor belt 7 runs faster than the conveyor belt 6 which carries the weight of the nine articles 5 . At time t 2 , the first article 8 in the transport direction 4 is transferred to the downstream conveyor belt 7 , so that at time t 2 , eight articles 5 are transported on the first conveyor belt 6 . The actual rotation speed n ist (t) of the asynchronous motor and hence also the actual transport speed v ist (t) of the conveyor belt 7 is reduced relative to the actual rotation/transport speed at time t 1 due to the weight of the first article 8 . Consequently, the actual rotation speed n ist (t) of the asynchronous motor and hence also the actual transport speed v ist (t) of the conveyor belt 6 have increased relative to the corresponding rotation/transport speed at time t 1 , since only eight articles 5 are transported.
[0008] At time t 3 , the conveyor belt 7 transports two articles 5 and the conveyor belt 6 seven articles 5 . The actual transport speed v ist (t) of the conveyor belt 6 increases further relative to the transport speed at time t 2 , whereas the actual transport speed v ist (t) of the downstream conveyor belt 7 is further reduced since it received the second article 9 . Due to the change in the actual transport speed v ist (t) of the conveyor belt 7 from the time t 2 to the time t 3 , the first article 8 has been transported at a faster pace by the conveyor belt 6 than the second article 9 . As a result, the resulting spacing 10 between the first article 8 and the second article 9 on the conveyor belt 7 is greater than the spacing that existed between the first article 8 and the second article 9 at the time t 1 on the conveyor belt 6 .
[0009] After the transfer of the third article 11 , as seen in the transport direction 4 from the conveyor belt 6 to the conveyor belt 7 , the actual transport speed v ist (t) of the conveyor belt 6 again increases, whereas the trailing conveyor belt 7 again slows down. As a result, the spacing between the second article 9 and the third article 11 is smaller than the spacing 10 .
[0010] At time t 5 , the actual transport speed v ist (t) of the conveyor belt 6 is approximately equal to the actual transport speed of the conveyor belt 7 . At the times t 6 , t 7 , t 8 , t 9 , the actual transport speed v ist (t) of the conveyor belt 6 increases from one point in time to the next, while the actual transport speed v ist (t) of the conveyor belt 7 decreases accordingly, so that two articles 5 collide with each other on the conveyor belt 7 , as illustrated for the time t 9 .
[0011] It would be desirable and advantageous to provide a more cost-effective conveyor belt system and a method for operating such conveyor belt system which obviates prior art shortcomings and is able to provide a constant throughput and also function as an intermediate storage unit.
SUMMARY OF THE INVENTION
[0012] According to one aspect of the invention, a conveyor system for transporting articles, in particular for transporting containers holding baggage pieces, includes at least two sequentially arranged endless conveyor belts to define an upstream conveyor belt and a downstream conveyor belt for transport of articles in a transport direction from the upstream conveyor belt to the downstream conveyor belt, a drive unit having a first drive motor operatively connected to the upstream conveyor belt and a second drive motor operatively connected to the downstream conveyor belt, and a control unit for regulating a rotation speed of the first drive motor in dependence on a weight determination commensurate with a presence or absence of articles positioned on the upstream conveyor belt, and for regulating a rotation speed of the second drive motor in dependence on a weight determination commensurate with a presence or absence of articles positioned on the downstream conveyor belt.
[0013] According to another aspect of the invention, a method for controlling a conveyor system for transporting articles, in particular for transporting a container holding baggage pieces, with at least two sequentially arranged endless conveyor belts to define an upstream conveyor belt and a downstream conveyor belt for transport of articles in a transport direction from the upstream conveyor belt to the downstream conveyor belt, includes the steps of driving each conveyor belt with a drive motor having a rotation speed that depends on a load torque, determining a weight of the articles located on the conveyor belts, and controlling a rotation speed of the drive motors in dependence on the weight of articles positioned on the conveyor belts.
[0014] According to another feature of the present invention, the actual rotation speed of the drive motor which depends on the load torque and hence also the actual conveyor speed of the conveyor belt is held constant by a controllably changing the desired rotation speed when the load torque changes. This eliminates the need for a feedback of the actual rotation speed, or an equivalent parameter.
[0015] According to one variation of the present invention, the weight can be determined based on the number of the articles located on the conveyor belt.
[0016] According to another variation of the invention, the weight may be determined by the number of the articles multiplied by the average weight of the articles. If the individual weight of the articles is not known, then an average weight is used which can be determined empirically or statistically. This feature is particularly advantageous for conveyors transporting containers, because the containers are significantly heavier than the articles held in the containers, so that a determination of the weight of the articles themselves is less critical.
[0017] The same actual conveyor speed can be set for each conveyor belt section by increasing the desired rotation speed of the drive motor that drives the conveyor belt section with the higher transported weight so as to compensate for any decrease in the actual rotation speed due to the increased weight.
[0018] The desired rotation speed of the drive motor can be controlled cost-effectively by implementing the drive motor as an unregulated asynchronous motor that is controlled by a frequency converter. The desired rotation speed can be adjusted by changing the frequency of the converter and/or the motor voltage.
[0019] Advantageously, the two conveyor belts form a storage unit for storing or “parking” the articles.
BRIEF DESCRIPTION OF THE DRAWING
[0020] Other features and advantages of the present invention will be more readily apparent upon reading the following description of currently preferred exemplified embodiments of the invention with reference to the accompanying drawing, in which:
[0021] [0021]FIG. 1 shows a schematic illustration of a conveyor assembly according to the present invention with two conveyor sections;
[0022] [0022]FIG. 2 is a block circuit diagram of a control path of a conveyor section according to FIG. 1; and
[0023] [0023]FIG. 3 shows a schematic illustration of a conventional conveyor assembly with two conveyor sections.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0024] Throughout all the Figures, same or corresponding elements are generally indicated by same reference numerals. These depicted embodiments are to be understood as illustrative of the invention and not as limiting in any way. It should also be understood that the drawings are not necessarily to scale and that the embodiments are sometimes illustrated by graphic symbols, phantom lines, diagrammatic representations and fragmentary views. In certain instances, details which are not necessary for an understanding of the present invention or which render other details difficult to perceive may have been omitted.
[0025] Turning now to the drawing, and in particular to FIG. 1, there is shown a schematic illustration of a conveyor system according to the invention, generally designated by reference numeral 100 and including an upstream conveyor section 20 and a downstream conveyor section 30 . The transport direction is indicated by arrow 4 . The conveyor section 20 is essentially represented by a conveyor belt 60 and the conveyor section 30 by conveyor belt 70 . Load-torque-dependent asynchronous motors (not shown) drive the conveyor belts 60 , 70 .
[0026] A frequency converter 21 (FIG. 2) supplies electric power to the asynchronous motors with a changeable frequency f soll (t) and/or a changeable voltage U soll (t) that regulate the desired rotation speed n soll (t) of the asynchronous motor. The desired rotation speed n soll (t) of an asynchronous motor operatively coupled with a conveyor belt 60 , 70 is adjusted depending on the total weight of the articles 5 transported by a corresponding conveyor belt 60 , 70 . The change in the actual rotation speed □v caused by a change in the load torque is compensated according to the characteristic torque curves of the asynchronous motors. For this purpose, the frequency converter 21 associated with the respective asynchronous motor changes the frequency and/or voltage supplied to the asynchronous motor to compensate for the change □v in the actual rotation speed.
[0027] The articles 5 received from and transferred to each conveyor section 60 , 70 are detected and/or counted by a suitable sensor electronics, such as a barcode scanner or a light barrier. In this way, the type and/or the quantity of articles 5 located on a respective conveyor section 60 , 70 is always known.
[0028] At time t 1 , the desired rotation speed n soll (t) of the asynchronous motor of the conveyor belt 60 is set to be greater than the desired rotation speed n soll (t) of the asynchronous motor of the downstream conveyor belt 70 . Since the conveyor belt 60 is loaded by the weight of the nine articles 5 , the actual rotation speed n ist and hence also the actual transport speed v ist of the conveyor belt 60 correspond to the actual rotation speed n ist and hence also the actual transport speed v ist of the conveyor belt 70 which does not yet carry any articles. At a result, both conveyor belts 60 , 70 run synchronously at the same speed.
[0029] At time t 2 , a first article 8 is transferred to the downstream conveyor belt 70 so that the conveyor belt 60 now carries eight articles 5 . Compared to the time t 1 , the conveyor belt 60 is regulated with a smaller desired rotation speed n soll (t), since the total transported weight has been reduced. Conversely, the desired rotation speed n soll (t) of the asynchronous motor of conveyor belt 70 is higher than at time t 1 , since the increased weight of the first article 8 loads the conveyor belt 7 . The changes in the desired rotation speeds n soll (t) of the asynchronous motors is selected so that the actual transport speed v ist does not change from time t 1 to time t 2 . As a result, the two conveyor belts 60 , 70 still operate at the same speed.
[0030] At time t 3 , a second article 9 is transferred to the downstream conveyor belt 70 . As the conveyor belts 60 , 70 run synchronously with the same actual transport speed v ist , the two leading articles 8 , 9 are spaced equidistantly from each other at the same identical spacing they had at time t 1 .
[0031] The load torques M R (t) for the two conveyor belts 60 , 70 , which change at the times t 3 , t 4 , t 5 , t 6 , t 7 , t 8 and t 9 , whereby the load torque M R (t) at the upstream conveyor belt 60 successively decreases and likewise increases at the downstream conveyor belt 70 , do not affect the actual transport speeds v ist of the respective conveyor sections 20 , 30 because the respective asynchronous motors are controlled so as to compensate for these changes .
[0032] [0032]FIG. 2 shows schematically a block circuit diagram for controlling the articles 5 that are transported on the conveyor section 20 , 30 of the conveyor belt 60 , 70 . A controller 19 controls the frequency converter 21 which affects the load-torque-dependent drive motor 22 via the supply voltage and/or frequency, so that the drive motor 22 supplies a desired rotation speed n soll (t) to a conveyor belt 60 , 70 , which transports the articles 5 with a transport speed v.
[0033] A predetermined desired transport speed v soll is provided to the controller 19 as a constant control parameter; the control parameter links an estimated or calculated load torque M E (t), which basically represents the true load torque M R (t), with the desired transport speed v soll and generates therefrom an auxiliary voltage U Hilf (t) and an auxiliary frequency f Hilf (t) for a control element connected downstream, i.e. the frequency converter 21 . The frequency converter 21 operating as a control element transforms the auxiliary voltage U Hilf (t) and the auxiliary frequency f Hilf (t) into a voltage U ist (t) and a frequency f ist (t) for the drive motor 22 . The drive motor 22 assumes under the actual load torque M R (t) an actual rotation speed n ist , which drives the conveyor belt 60 , 70 with an actual transport speed v ist . The motor rotation speed n ist depends on the load torque, i.e., the actual transport speed v ist is a function of the voltage U ist (t) and the frequency f ist (t), which was determined by the controller 19 as a function of the articles 5 to be transported by the conveyor belt 60 , 70 .
[0034] The estimated or calculated load torque M E (t) of each control path can hereby be determined by different methods. If the individual weights of the articles 5 on a conveyor belt 60 , 70 are known, then the total weight can be easily determined from the sum of the individual weights. If only some of the weights are known while others are unknown, average values are assumed for the weights of the articles 5 whose weight is not known, whereafter the sum is computed. If none of the weights of the articles 5 are known, the total weight can be determined by multiplying the quantity of the articles 5 transported on the conveyor belts 60 , 70 by an average weight of the articles. For each total weight, the change in the actual rotation speed □v as compared to the unloaded actual rotation speed can be determined from the characteristic torque curve of the asynchronous motor, and the actual rotation speed derived from the characteristic curve can then be supplied to the controller 19 .
[0035] While the invention has been illustrated and described in connection with currently preferred embodiments shown and described in detail, it is not intended to be limited to the details shown since various modifications and structural changes may be made without departing in any way from the spirit of the present invention. The embodiments were chosen and described in order to best explain the principles of the invention and practical application to thereby enable a person skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated.
[0036] What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims and includes equivalents of the elements recited therein:
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A system and method is described for transporting articles, in particular for transporting container holding baggage pieces. At least two endless conveyor belts are sequentially arranged to define an upstream conveyor belt and a downstream conveyor belt for transport of articles in a transport direction from the upstream conveyor belt to the downstream conveyor belt. The conveyor belts are driven by drive-motors, in particular asynchronous motors, with the rotation speed of each drive motor being regulated depending on the weight of the articles located on the conveyor belt associated with the particular drive motor. The drive motors can be controlled by adjusting the frequency and/or voltage of the supplied electric power.
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This is a continuation-in-part of copending U.S. Patent application Ser. No. 759,599, filed Sept. 16, 1991, now U.S. Pat. No. 5,196,026.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to implants designed to be surgically inserted between the layers of the cornea to correct refractive errors. More particularly, the invention relates to corneal implants that can serve as a substitute for conventional spectacles or contact lenses.
2. Description of the Related Art
There have already been proposed artificial lenses for implantation in the eye. Such implants have hitherto been intended, not as corrective lenses, but as a substitute for the natural lens of the eye. For example, when an eye develops a cataract, the natural lens becomes fogged or opaque, thereby impairing vision. When such a cataract is treated, the lens is removed, leaving the eye aphakic. Although it is possible to correct for aphakia using spectacles, the degree of correction requires spectacles so thick as to make them both cumbersome and unattractive. For these reasons, lenses have been designed for correction of aphakia wherein the substitute lens is inserted into the eye during the operation to remove the cataract or at a second operation. Such substitute lenses are of fixed focal length and, as the natural lens has been removed, the eye is no longer capable of accommodation, that is to say, the focal length cannot change to focus at different distances. It is accepted in this field that such implanted lenses are not prescribed as an alternative to conventional spectacles for a person suffering only from myopia or presbyopia.
Another implant that has been used in the past with some success has been the artificial cornea described in U.S. Pat. No. 2,714,712, and generally resembling what is known as a kerato-prosthesis. These implants are designed as a replacement for the natural cornea itself where the cornea has become fogged or opaque, and are not intended to be a substitute for conventional spectacles or contact lenses.
It is known to resort to surgery in order to correct for defects in eyesight. The various procedures for refractive corneal surgery to correct vision problems such as myopia have not gained general acceptance in ophthalmology. These include radial keratotomy introduced in modern times (1972) by Fyodorov of the USSR, keratomileusis introduced in 1961 by Barraguer of Columbia, keratophakia which uses shaped donor corneas as lens, epikeratophakia which uses an epigraft of homologous tissues, keratotomy to correct astigmatism, and removing clear lens. Such surgery does not have a fully predictable outcome, and furthermore any non-spherical flattening of the cornea on healing results in an eyesight defect that cannot be corrected by the use of spectacles or contact lenses.
The human cornea is a transparent avascular tissue about 10-12 mm in diameter. The cornea functions as a protective membrane and as a "window" through which light rays pass en route to the retina. The average adult cornea is about 0.65 mm thick at the periphery and about 0.54 mm thick in the center (optic zone). From anterior (front) to the posterior (back), it has 5 distinct layers: the epithelium which is 5 or 6 cell layers thick; a clear acellular Bowman's layer; the stroma (which constitutes about 90% of the thickness of the cornea); the thin Descemet's membrane; and, the single layer endothelium. Sources of nutrition for the cornea are the blood vessels of the limbus, the aqueous humor and tears. The superficial cornea also gets most of its oxygen from the atmosphere.
The zone in the cornea through which incident light passes is known variously as the "optic zone" or "pupillary aperture," and both terms will be used interchangeably herein. The size of the normal pupil varies at different ages and from person to person, but normally is about 3-4 mm--smaller in infancy, tending to be larger in childhood, and again progressively smaller with advancing age. Vaughan, D., et al., General Ophthalmology, 2d ed., Appleton & Lange, Norwalk, CT, 1989, Ch. 15; Choyce, Cataract, 7 (June 1985). The size of the pupillary aperture, of course, varies inversely with the amount of incident light.
Disks of many different materials have been inserted into corneal stromal pockets, initially to control corneal edema, but more recently to correct refractive errors. Hydrogel and polysulfone lenses have been more successful than other types of lenses so far tried.
Previous corneal implants for the correction of refractive errors have enjoyed only limited success, in part because of the large diameter of the lenses used and in part because of the composition of such lenses. As will be detailed in the review of the related art below, the ophthalmologically more desirable high refractive index polymeric lenses previously used tend to prevent access of fluids, nutrients and gases such as oxygen to the tissue anterior to the implant and to the corneal tissue posterior to the implant. On the other hand, high water content, low refractive index lenses such as hydrogel lenses, while reducing or eliminating the problem of nutrient and gas transport, are generally not able to provide the necessary corrections in refractive error of the eye. Previous corneal implants have also not been able to provide multifocal refractive correction.
The large diameter of previous corneal implant lenses has also required a less-than-satisfactory surgical approach to implantation. In general, previous corneal inlays have required cutting a large pocket into the cornea and inserting in this pocket the lens which resides predominantly behind Bowman's membrane. With this type of insertion, the large implanted lens distorts the cornea, thereby producing a change in optical power. The disadvantage of such a procedure has been that the distortion is usually in the posterior side of the cornea. Such posterior distortion, however, produces only a very small change in optical power because the difference between the refractive index produced is only the small difference between the inlay/cornea and the aqueous humor.
Choyce, D.P., U.S. Pat. No. 4,607,617, issued Aug. 26, 1986, relates to an implant designed to be inserted between the layers of a cornea of an eye to correct eyesight defects, comprising a polysulfone plastic material of a high refractive index (typically 1.633), of a thickness in the range of 0.1 to 0.4 mm, and capable of being sterilized by steam autoclaving prior to insertion. As the implant is entirely embedded in the cornea, it is said not to be exposed to the atmosphere or to the aqueous humor. The polysulfone material is said to be "relatively permeable to body fluids", although it is not clear that this is so. The lens is inserted by a procedure comprising forming an incision in the outer layer of the cornea, separating layers of the cornea to form a pocket, inserting into this pocket a lens inlay, and resealing the incision. Although Choyce neither discloses nor suggests a specific diameter for the lens inlay, reference to FIG. 7b of the specification shows that this diameter is substantially greater than the optic zone of the cornea, which, as noted above, normally is about 3 mm to 4 mm in diameter. This fact, plus the fact that it is known that high refractive index plastic inlay lenses are poorly permeable to fluids, nutrient materials and necessary gases such as oxygen, limits the usefulness of this inlay lens. Further, this corneal inlay does not provide multifocality.
Grendahl, D.T., U.S. Pat. No. 4,624,699, issued Nov. 25, 1986, relates to a corneal inlay for implantation made of a plastic material such as polysulfone or PMMA. Recognizing that prior art polysulfone inlay lenses are poorly permeable to nutrients, fluids and gases, a property of concern to medicine, the inventor attempts to overcome these disadvantages by providing a corneal inlay with a plurality of holes or slots for passage of nutrients through the cornea. The inlay lens is said to have a diameter of approximately 3 mm to 7 mm, preferably 4.5 mm to 6.5 mm, more preferably slightly less than 6 mm in diameter (column 2, lines 21-26). Inlay lenses of such diameter will generally completely cover the optic zone of a normal human cornea, creating the problems of nutrient and gas supply described above. There is no disclosure or suggestion in this patent that the inlay lens could be smaller than the opening of the optic zone, nor is there reference to any property of the lens other than a single focal distance.
Lindstrom, R.L., U.S. Pat. No. 4,851,003, issued Jul. 25, 1989, discloses corneal inlay lenses applied under the cornea and about the stroma. The lens is fenestrated, and includes a plurality of fixation holes around the periphery and a coating on the anterior surface by a material that enhances the growth of corneal epithelial cells into and about the holes. The coating is composed of biological materials such as fibronectin, laminin, a glycosaminoglycan, or a type IV collagen. Although the diameter of the inlay lenses is not specifically disclosed, the dimensions of the holes (up to 1 mm), taken together with FIG. 6 which shows the epicorneal lens implanted below the epithelium, indicates that the diameter of the inlay lens is at least 5-7 mm, and thus substantially greater than the optic zone of the cornea. Such lenses also do not provide a patient with multiple focalities.
Thus, the prior art inlay lenses are less than satisfactory in important ways. Where large (e.g., 5 mm to 7 mm) hydrogel lenses are used, wherein the water content is high (about 72%) and the index of refraction low (about 1.38), problems of permeability to nutrients and gases are generally less severe, but the dioptic power is low. Where large polymeric lenses are used, wherein the water content is quite low and the refractive index high (e.g., 1.45 to 1.633), the optic power is satisfactory, but the permeability is poor. Such non-permeability to essential nutrients and gases tends to cause "starvation" in the anterior segments of the stroma, ultimately resulting in extrusion of the inserted lens. Although the permeability problem is reduced by placing holes or slots in polymeric lenses (see Grendahl above), such holes interfere with vision. Further, none of the prior art inlay lenses provide for multiple focality, which is highly desirable in many patients.
There remains, therefore, an important need for intra-corneal lenses of a refractive index sufficiently high so as to avoid the need to distort the cornea in order to obtain the desired optical power, of a size sufficiently small so as to simplify surgical insertion, of a diameter that permits essential nutrients and gases readily to reach the anterior of the cornea, and of a type that permits either unifocality or multiple focalities.
Such an intra-corneal inlay lens has been invented, and it and its uses are disclosed below.
SUMMARY OF THE INVENTION
The invention provides a biocompatible, solid, transparent, low or high refractive index corneal inlay lens adapted to be inserted singly or multiply between the layers of the cornea to correct refractive errors, wherein the lens is of a diameter less than that of the optic zone under normal ambient light conditions or preferably under bright light conditions. The size of the lens permits the passage of nutrients and gases from the posterior aspect of the cornea through to the anterior aspect. The lens is of a composition relative to that of the surrounding tissues such that multiple refractive indices may be created and multiple focal corrections are possible.
In accordance with a first aspect of the invention, there is disclosed a corneal lens of a diameter less than that of the corneal optic zone under normal light or bright light conditions, the diameter and compositions of such lens being such that areas of different refractive indices are created in the optic zone, thereby providing multiple focality.
In accordance with yet another aspect the invention, the inventive lenses are used to provide vision corrections in patients.
These and other aspects and objects of the invention will become apparent by reference to the specification below and the appended claims.
DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are representations of the anatomic relationship of the inlay lenses of the invention to the cornea. In the figure, "a" is the sclera, "b" the cornea, "c" the inlay lens, and "d" the incision for inlaying the corneal lens.
FIGS. 2A through 2D show meniscus lenses of the invention. In the figures, "e" is edge thickness, "d" the diameter, and "c" the center thickness.
FIGS. 3A through 3F show biconvex lenses of the invention. Designations "e", "d" and "c" are as in FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
The invention provides bicompatible, solid, low or high refractive index corneal implant corrective lenses of novel dimension, adapted to be surgically inserted into stromal pockets via a very small incision in the corneas of patients suffering from refractive error. Advantageously, the lenses of the invention provide multiple refractive indices and multiple focalities.
A surgical implantation procedure involves making a stromal cut parallel to the limbus of about 2 mm to about 3 mm in length to about 50% to about 95% thickness, preferably about 75% thickness, using a blunt spatula to make a pocket in the stroma to the center of the corneal optic zone (pupillary aperture), inserting the corrective lens into the pocket, then permitting the incision to reseal peripherally to the lens.
The lenses are of a diameter smaller than that of the optic zone of the cornea under normal ambient light or, preferably, under bright light conditions, and are of a size such that the implanted lens or lenses, regardless of composition, water content or index of refraction, will not substantially impede the movement of fluids, nutrients and gases to all layers of the cornea. Typically, the lenses are of a diameter of from about 1 mm to about 3 mm.
The transparent inlay lenses of the invention are solid with no holes or slits, and may be uncoated or coated. Such lenses create regions of different refractive indices within the optic zone, one created by the lens itself and the other by the neighboring stroma tissue, thereby providing a useful multifocal capability. The brain is capable of sorting out the different signals and using the information appropriately. This embodiment is not limited to a single small diameter lens; a mosaic of two or more such lenses may be implanted in the same plane, thereby providing for additional multiple focality.
Multiple focality may be achieved under all lighting conditions where both distance and near vision would be expected to be useful. This would correspond to a minimal pupil size of about 2.0 mm.
The area of the cornea related to near vision should be no more than about 75-80% of the entire functional pupil size in order to retain multiple focal vision under bright light conditions ("blc"). For example, if the patient's pupil diameter under blc is 2.0 mm, then an inlay lens that creates additional power (i.e., the inlay creates an area in the cornea devoted to near vision) should have a diameter of about 1.75 mm. The area devoted to near vision under blc is about 2 4 mm 2 , while the total area of the optic zone is about 3.14 mm 2 . Therefore, about 77% of the optic zone of this pupil is devoted to near vision.
Similarly, if the patient's pupil diameter is 2.5 mm under blc, then an inlay with a diameter of 2.16 mm could be used. The pupil size under blc is seldom less than about 2 mm and seldom greater than 3 mm, so for the general population, inlays with a diameter of from about 1.75 mm to about 2.6 mm would be adequate. However, in those rare cases in which, due to trauma, surgery or disease, the pupil size under blc is substantially greater than 3.0 mm, then the size of the desired inlay can be computed and adjusted accordingly so that no more than about 75-80% of the entire functional pupil size is devoted to near vision created by the implantation of the inlay lens or lenses.
Presbyopes will benefit from the multiple focality of the cornea which is produced by the cornea's central zone being altered by the small lens of the invention for near vision, while the unaltered peripheral zone remains responsible for distance vision. Myopic patients can benefit in the reverse way by implanting a negative lens in the center, rendering the small central zone optically less powerful. Hyperopia and aphakia may also be treated with these lenses.
An enormous number of refractive corrections are possible with the lenses of this invention. Positive and negative lenses of all useful diopters may be employed. The lenses may be of a refractive index greater or less than that of the neighboring corneal tissue. Thus this invention can be used to correct presbyopia, myopia, hyperopia, aphakicia, and perhaps other corrections as well.
Meniscus and biconvex lenses are preferred. FIG. 2 shows the designs of meniscus lenses of the invention. FIG. 2A shows meniscus designs when the R.I. of the lens is greater than that of the surrounding corneal tissue, while FIG. 2B shows meniscus designs when the R.I. of the lens is less than that of adjacent corneal tissue. In both figures, "d", the lens diameter, ranges between about 1 mm and about 3 mm, preferably between about 1.75 mm and about 2.6 mm, "e" the edge thickness, ranges between about 0 005 mm and about 0.05 mm; and, "c", the center thickness ranges between about 0.01 mm and about 0.25 mm. The refractive power, P, varies depending on the type of lens design (meniscus or biconvex) and the type of lens material. From d, e, c, and P, anterior and posterior radii of the lens can be calculated by standard methods.
FIG. 3 shows the design of the biconvex lenses of the invention. FIG. 3A shows biconvex design where the R.I. of the lens is greater than that of the adjacent corneal tissue, while FIG. 3B shows biconvex designs when the R.I. of the lens is less than that of the surrounding corneal tissue. Dimensions "d", "e" and "c" are defined in FIG. 2.
Referring to FIG. 2A, in the left hand sketch there is shown a positive "(+)" lens in which P=+0.5 to +20.00. In the right hand sketch of FIG. 2A, there is shown a negative "(-)" lens in which P=-0.5 to -20.0 diopters. In the left hand sketch of FIG. 2B, there is shown a (-) lens in which P=-20.0 to -0.5 diopters, whereas the anterior radius and posterior radius can both range from flat (infinite) to about 5 mm. In the right hand sketch of FIG. 2B, there is shown a (+) lens in which P=+20.0 to +0.5 diopters.
Referring to FIG. 3, in the left hand sketch of FIG. 3A, the radii of the anterior and posterior surfaces are equal, whereas in the middle sketch the anterior radius is greater than that of the posterior radius, and in the right hand sketch the anterior radius is less than that of the posterior radius; all lenses are (+), and P=+0.05 to +20.0 diopters. The three sketches in FIG. 3B are the counterparts of those in FIG. 3A, but because of the opposite relationships of the R.I.s, all lenses are (-), and P=-20.0 to -0.05 diopters.
Biconcave lenses may also be used. The relationships between the R.I. of the lenses and that of the adjacent corneal tissue are as described in FIGS. 2 and 3. Likewise, the availability of (+) or (-) corrective lenses and powers are also as described in FIGS. 2 and 3.
As noted above, because of their small diameter or configuration, the lenses made in accordance with this invention avoid the problems of fluid, nutrient and gas passage attendant upon prior art corneal implant lenses, no barriers to transport being present. Thus, the invention provides a great deal of flexibility in the selection of lens composition, refractive index and water content.
Lenses may be composed of gels such as hydrogels, polymeric materials, cellulose esters and silicones. One may use hydrogels of low water content or high water content. In one embodiment, one may use a hydrogel lens of low water content, a diameter of about 2 mm, a center thickness of about 0.02-0.05 mm, a R.I. of 1.42 to 1.43, and a power of +2.5 D in the stroma to correct for presbyopia. High water content materials of R.I. slightly greater than or less than the R.I. of the stroma may also be used by an appropriate choice of design. Also suitable are non-water containing polymeric material such as the high R.I., relatively rigid polysulfones (e g , UDEL™, Union Carbide Corp., R.I. typically 1.633) whose high R.I. allows corrections of up to +10 D with a lens 0.04 mm thick, and a correction of -10 D with a differently shaped lens with a thickness of only 0.01 mm at its center. Other suitable polymeric materials include polyethersulfones (VICTREX™, ICI), polyarylsulfones, PERSPEX CQ™ or PERSPEX CQUV™ (ICI) (R.I. 1.49), polycarbonates, silicones, fluoropolymers, polymethyl methacrylates (PMMA), cellulose acetate or butyrate, or other like materials.
The following examples are merely exemplary of the invention and are in no way intended to limit the scope of the invention which is defined by the specification and the appended claims.
EXAMPLE 1
______________________________________INSERTION OF A PMMA LENTICULE INTHE CORNEA OF RABBITS' EYES______________________________________Physical Parameters:Design: MeniscusMaterial: PMMADiameter: 2.0 mm; edge thickness: 0.02 mm; centerthickness: 0.022 mm; Base curve: 7.6 mm; P: +2.5D.Sterilization:gamma radiation 2.5-3 Mrad due to thethinness of the lenticule; the slightyellowng of the PMMA is negligible.Implant Procedure:1.1 Surgical Procedure Made a 2 mm incision approximately 75% of the stromal thickness about 1 mm central from the limbus in clear cornea. Using a blunt spatula, made a pocket to the center of the cornea.1.2 Intraoperatve Drug Treatment The resulting wound was then rinsed with irrigating solution.1.3 Lens Placement Prior to placing the lens, several drops of irrigating solution were placed on the eye. The appropriate lens was poured into a wire strainer and rinsed with sterile saline. Several drops of irrigating solution were placed on the lens. The lens was carefully picked up wth a non-toothed forceps and inserted in the pocket. The lens was then moved to the center of the cornea. Care was taken to ensure that the lens is well centered.1.4 Completion Flushed the eye well with irrigating solution. Sutured if necessary. Applied two (2) drops of postoperative drug solution.1.5 Postoperative Treatment Gave Maxidex 2X daily (weekend treatment is once daily), and antibiotics as necessary.______________________________________
EXAMPLE 2
______________________________________INSERTION OF HYDROGEL LENTICULE IN THECORNEA OF RABBITS' EYES______________________________________Physical Parameters:Design: MeniscusMaterial: Hefilcon A (hydrogel with water content:45%; Refractive Index: 1.425)Diameter: 2.0 mm; edge thickness: 0.02 mm; centerthickness: 0.023 mm; Base curve: 7.6 mm; P: +2.5D.Sterilization method:Autoclaving______________________________________
The implant procedures and post-operative treatment were as in Example 1.
EXAMPLE 3
______________________________________INSERTION OF A HYDROGEL LENTICLE IN THECORNEA OF CATS' EYES______________________________________Physical Parameters:Design: BiconvexMaterial: Hefilcon A (hydrogel with water content:45%; Refractive Index: 1.425)Diameter: 2.0 mm; edge thickness: 0.02 mm; centerthickness: 0.04 mm; Anterior radius: 7.0 mm;Posterior radius: 9.8 mm; P: +2.5D.Sterilization method:AutoclavingImplant Procedure:3.1 Surgical Procedure Made a 2 mm incision approximately 90% of the stromal thickness about 1 mm central from the limbus in clear cornea. Using a blunt spatula, made a pocket to the center of the cornea.3.2 Intraoperative Drug Treatment The resulting wound was then rinsed with irrigating solution.3.3 Lens Placemnt Prior to placing the lens, several drops of irrigating solution were placed on the eye. The appropriate lens was poured into a wire strainer and rinsed with sterile saline. Several drops of irrigating solution were placed on the lens. The lens was carefully picked up with a non-toothed forceps and inserted in the pocket. The lens was then moved to the center of the cornea. Care was taken to ensure that the lens is well centered.3.4 Completion Flushed the eye well with irrigating solution. Sutured if necessary. Applied two (2) drops of postoperative drug solution.3.5 Postoperative Treatment Gave Maxidex 2X daily (weekend treatment is once daily), and antibiotics as necessary.______________________________________
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A low or high refractive index corneal inlay optical lens adapted to be inserted singly or multiply between the layers of a cornea to correct refractive errors in eyesight, wherein the implanted lens is a solid transparent uncoated lens having no apertures therethrough, of a diameter less than that of the optic zone of the eye under normal light or bright light conditions, such that the movement of fluids, nutrients and gases throughout the corneal layers is unimpeded, and wherein the composition of the lens or lenses relative to that of the surrounding stromal tissue are such that multiple refractive indices may be created and multiple focal corrections are possible.
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BACKGROUND OF THE INVENTION
This invention relates to a process for producing coated europium acrivated strontium borate phosphors. More particularly it relates to a process for producing europium activated strontium borate phosphors coated with a strontium containing coating.
A phenomenon observed during the lamp lehring process with eropium activated stontium borate, using both the organic and water based binder systems, is the formation of brown phosphor discoloration and glazing of the glass. This phenomenon is associated with the surface activity of the phosphor where it is exposed during the lehring phase of lamp manufacturing. The brown discoloration appears to be associated with carbon being trapped on the phosphor surface.
Elimination of the boric acid and preventing an interaction of the phosphor with the binder would be desirable.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention, there is provided a process for producing a europium activated strontium borate phosphor having a strontium containing coating. The process involves washing a europium activated strontium borate phospher with a solution of strontium hydroxide to produce a first washed phosphor followed by removing the first washed phosphor from the resulting wash solution. The first washed phosphor is washed with a wash solution selected from the group consisting of ammonium fluoride in alcohol, ammonium biflouride in alcohol, and a strontium salt in ammonium hydroxide, followed by removing the resulting second washed phosphor from the resulting wash solution. The second washed phosphor is then heated to produce the coated phosphor.
DETAILED DESCRIPTION OF THE INVENTION
For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims in connection with the above description of some of the aspects of the invention.
The starting phosphors of this invention are typically europium activated strontium borates. The preferred starting phosphor is Type 2051 manufactured by the Chemical and Metallurgical Division of GTE.
The starting phosphor is first washed in a solution, preferably saturated solution of strontium hydroxide. This is generally done in a number of wash steps to produce a first washed phosphor. The washing is done primarily to remove residual boric acid which is present on the surface of the phosphor particles as a result of the phosphor manufacturing process. In this washing step, strontium hydroxide reacts with the boric acid to produce strontium hexaborate which is more soluble than the strontium borate phosphor itself.
In accordance with a preferred embodiment, the strontium hydroxide washing operation is carried out while deagglomerating the phosphor. The deagglomeration results in a homogeneous washing and in the subsequently applied coating being homogeneous. Preferably the washing with deagglomeration is done by milling such as in a ball mill for a sufficient time to accomplish removal of the major portion of the boric acid from the phosphor and to accomplish the deagglomeration of the phosphor. The preferred length of time of washing in a ball mill is about 1/2 hour. Actual mill times are determined by the hardness of the phosphor. Phosphor hardness is a function of firing time, firing temperature and composition. Thus milling times are a function of parameters independent of coating requirements and, in fact, evermilling may substantially reduce final lamp efficiency.
Since it is essential that surface boric acid be minimized on the phosphor, additional strontium hydroxide aqueous washes are required after the initial mill washing. These are done by stirring a mixture of mill washed phosphor and a hot strontium hydroxide water solution in a container, without milling media, for preferably about 15 minutes. This procedure is done preferably a minimum of two times and is then followed by hot water rinses to remove excess strontium hydroxide and strontium hexaborate. It is preferable that no more than about 3 consecutive water washes be put on the strontium hydroxide washed phosphor to avoid degradation of the phosphor.
The final wash solution is then removed from the first washed phosphor by any standard technique such as filtration.
At this point the first washed phosphor can be dried to remove water. It can also be screened to remove any out of size material.
The strontium hydroxide washing reduces phosphor hydrolysis by the elimination of excess boric acid and by increasing the ratio of Sr to B on the phosphor surface.
To illustrate the importance of washing with strontium hydroxide the following brightness data is presented for lamps having the europium activated strontium borate phosphor. The data show that strontium hydroxide washed phosphers have a high brightness as opposed to phosphors washed with only water.
______________________________________ Relative UV Emission UnitsWash 0 hour 100 hour______________________________________None Lamps with the unwashed phosphor turn grey to brown and no brightness readings are obtained.Water only 2318 2252Strontium Hydroxide 3409 3315______________________________________
The first washed phosphor is then washed with a wash solution which results in a second washed phosphor. The wash solution can be a solution of ammonium fluoride in alcohol or ammonium bifluoride in alcohol to subsequently produce a strontium fluoride coating, or a solution of a strontium salt dissolved in ammonium hydroxide to subsequently produce a strontium peroxide coating.
To produce the strontium fluoride coating, the first washed phosphor is washed with a solution of ammonium fluoride and an alcohol or ammonium bifluoride in alcohol. The alcohol is chosen for its ability to dissolve the quantity of ammonium fluoride and/or ammonium bifluoride used in the process, and for its ability to be removed completely on heating. The preferred alcohol is denatured ethyl alcohol because of convenience. A preferred washing technique with strontium fluoride will be apparent in the example.
The resulting second washed phosphor is then separated from the resulting wash solution by any standard technique such as filtration.
The second washed phosphor is then heated to form the coated phosphor. The temperature is critical in formation of the strontium fluoride coating. The temperature range necessary to drive off excess organics is from about 450° C. to about 550° C. The preferred temperature is about 500° C.±10° C.
If the coating is to be strontium peroxide, the first washed phosphor is contacted with a solution of a strontium salt dissolved in ammonium hydroxide. The preferred strontium salt is strontium nitrate. The strontium nitrate is dissolved in ammonium hydroxide in a weight ratio of preferably about 1 to 1. The strontium nitrate-ammonium hydroxide solution is preferably heated to about 55° C. A temperature of about 55° C. is required because some heat is necessary for the strontium nitrate and ammonium hydroxide to react to form strontium peroxide which will eventually be the coating on the phosphor. However, it is important that the solution not be heated much above about 55° C. because excessive heat causes the strontium peroxide to decompose. The first washed phosphor is then contacted with this solution.
The heating of the second washed phosphor is done in essentially the same manner as described for the strontium fluoride phosphor. Upon heating, the strontium peroxide is deposited as a coating on the resulting second washed phosphor particles.
The strontium peroxide coating is used to subsequently prevent the interaction between the final phosphor and binder during the lehring process and to augment the lehring process by adding oxygen to the system.
To more fully illustrate this invention, the following non-limiting example is presented.
EXAMPLE 1
Washing the Phosphor with Strontium Hydroxide
About 10 kg of europium activated stronium borate phosphor is placed in a 12 gallon ceramic ball mill with 100 lbs. of alumina cylinders of 3/4 inch diameter. About 16 liters of hot (60°-80° C.) deionizd water and about 0.4 kg of Sr(OH) 2 .8H 2 O are added to the mill and the material is milled for about 15 minutes at about 27 rpm. The mill contents are then separated by pouring through a 60 mesh screen. About 30 kg of the above milled and screened phosphor slurry is placed in a 50 gallon ceramic tank. The phosphor is allowed to settle from the ball mill solution for about 20-30 minutes and the liquor is drawn eff. Hot (60°-80° C.) deionized water is added to the tank to bring the volume up to about 40 gallons. About 1 kg of strontium hydroxide is then added. The mixture is stirred with heating to maintain the water temperature for about 20 minutes. The mixture is then allowed to settle for about 20-30 minutes and the liquid portion is drawn off. The washing with strontium hydroxide is repeated a second time. Hot (about 60°-80° C.) deionized water is added to the tank to bring the volume to about 40 gallons. Rinsing with water is carried out in essentially the same manner as described for the strontium hydroxide washing. The rinsing is done a total of three times. The rinsed phosphor is then suction filtered as dry as possible. The filtered phosphor is then oven dried at about 115° C. for about 16 hours. The dried material is sifted through a 200 mesh screen. The resulting material can be processed further to coat it with the desired coating.
EXAMPLE 2
Applying Strontium Fluoride as a Coating on the Phosphor About 300 g of europium activated strontium borate which has been prewashed with strontium hydroxide is washed in about 600 ml of water in a 1 gallon ball mill for about 30 minutes. The washed phosphor is filtered and dried in a drying oven at about 110° C. The dried phosphor is washed in an alcoholic solution of ammonium fluoride or ammonium bifluoride. Preparation of this solution is as follows: about 6.05 g of NH 4 F is dissolved in about 600 ml of ethanol. The phosphor is then added and blended for about 30 minutes. The resulting mixture is filtered and the phosphor is rinsed with alcohol. The phosphor is then dried at about 500° C. in air for about 1 hour or until dry.
EXAMPLE 3
Applying Strontium Peroxide Coating on the Phosphor
A solution of strontium nitrate and ammonium hydroxide is prepared by adding about 250 g of strontium nitrate to about 600 ml of ammonium hydroxide. The resulting solution is heated at about 55° C. About 300 g of europium activated strontium borate which has been prewashed in strontium hydroxide is then slowly blended into this solution. The solution is allowed to cool, and is then filtered and dried in a drying oven at about 110° C.
While there has been shown and described what are at present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention as defined by the appended claims.
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A process is disclosed for producing a europium activated strontium borate phosphor having a strontium containing coating. The process involves washing a europium activated strontium borate phosphor with a solution of strontium hydroxide to produce a first washed phosphor followed by removing the first washed phosphor from the resulting wash solution. The first washed phosphor is washed with a wash solution selected from the group consisting of ammonium fluoride in alcohol, ammonium bifluoride in alcohol, and a strontium salt in ammonium hydroxide, followed by removing the resulting second washed phosphor from the resulting wash solution. The second washed phosphor is then heated to produce the coated phosphor.
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BACKGROUND OF THE PRESENT INVENTION
The present invention relates to exercise equipment and more particularly to a variable resistance exercise apparatus which is specifically adapted to provide an improved method of aerobic and anaerobic exercising of the upper extremity and upper body portions of a user.
It is now generally recognized in the medical profession that routine exercise programs are beneficial, if not necessary, to improved cardiovascular, pulmonary, and neuro-muscular health. The recognition of these benefits associated with routine exercise has resulted in a substantial number of the general public as well as professional athletes participating in various exercise programs such as jogging, weightlifting, aerobic dancing, and/or cycling. Although all of these exercise programs have proven beneficial in their general application, they each possess certain deficiencies which have detracted from their overall effectiveness.
With specific relation to weightlifting and weight apparatus, the resultant exercise has primarily been limited to the development of specific isolated muscles in the body with such exercise failing to provide any significant interaction between related muscle groups of the body. With reference to aerobic dancing and jogging, the exercise programs have usually been impaired by their inability to apply a significant enough resistance load to the exercise to permit full muscle development. Similarly, jogging and aerobic dancing as well as the cycling apparatus programs have typically been deficient in that only the lower extremities of the users have been exercised.
As such, there exists a substantial need in the art for an improved exercise apparatus and method of exercising which provides an interaction between related muscle groups of the body, permits the application of a variable exercise load into the exercise program, and effectively exercises the upper extremities and upper body portions of the user.
SUMMARY OF THE PRESENT INVENTION
The present invention specifically addresses and alleviates the above-referenced deficiencies associated in the art. More particularly, the present invention comprises a variable resistance exercise apparatus specifically adapted to provide an improved method of aerobic and anaerobic exercising of the upper extremities and body portions of a user. The particular exercise apparatus of the present invention when utilized in conjunction with other conventional exercise programs such as cycling or jogging has been found to insure a complete exercise program for the individual user.
The apparatus of the present invention is characterized by a support platform adapted to be stood upon by a user including a vertically extending column having a hand crank assembly mounted thereon. The column may be adjusted to a height dependent upon the size of the user to cause a full extension of the upper extremities (i.e., stretching) when the crank assembly is grasped in the hands of the user. Upon manual movement of the cranks, the user's body is additionally required to rotate (i.e., twist) about the waist and hips. This particular reaching and twisting motion utilized in the method of the present invention has been found to provide significant exercise to the arms, shoulders, neck, chest, abdomen, and waist of a user.
To augment the benefits of the particular reaching and twisting motion, the present invention incorporates a hydraulic pump which applies a variable exercise or resistance load to the hand crank assembly. As such, the apparatus permits purposeful stressing of the user which enables the device to be effective in residential fitness as well as professional athletic training applications.
The exercise apparatus of the present invention additionally includes a speed sensor adapted to yield a visual display of the revolutions of the hand crank during the exercise program and a timing device which advantageously indicates the desired overall exercise time and elasped exercise time.
The present invention further includes means for adjusting the length of the crank assembly to allow the apparatus to precisely suit differing extremity lengths of users and further includes a pair of rollers integrated into the platform to permit rapid transport of the apparatus.
DESCRIPTION OF THE DRAWINGS
These as well as other features of the present invention will become more apparent upon reference to the drawings wherein;
FIG. 1 is a perspective view of the exercise apparatus of the present invention;
FIG. 2 is an elevational view of the exercise apparatus of the present invention illustrating the vertical adjustment of a hand crank assembly mounted thereon;
FIG. 3 is a front elevational view of the exercise apparatus of the present invention;
FIG. 4 is an enlarged perspective view of the crank assembly of the present invention;
FIG. 5 is a schematic view of the twisting motion of the user during exercise upon the exercise apparatus of the present invention; and
FIG. 6 is a schematic view of the reaching motion of a user during exercise upon the exercise apparatus of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown the variable resistance exercise apparatus of the present invention designated generally by the numeral 10. The apparatus 10 is composed of a platform 12, one end of which is adapted to be stood upon by a user and a generally A-shaped column 14 extending vertically upward from the platform 12. In the preferred embodiment, the platform 12 and column 14 are fabricated from square metal tubing sufficient to provide a rugged structure; however, other tubing configurations and material may additionally be utilized. The column 14 is advantageously supported by a pair of angularly extending struts 16 which are mounted to the column 14 and base 12 as by way of a fillet weld to rigidify the structure of the apparatus 10.
As best shown in FIG. 4, the uppermost end of the column 14 mounts a generally Y-shaped yoke 18 which is pivotally connected at one end to the column 14 as by way of a shaft 20. The opposite end of the yoke 18 carries a gear 22 which is rotatably mounted for movement about a shaft 24 extending through the yoke 18. Opposite ends of the shaft 24 mount a hand crank assembly 26 composed of a pair of juxtoposed elongate members which extend angularly outward from the axis of the shaft 24. The outboard elongate members 27 of the crank assembly 26 include a plurality of apertures 30 positioned axially along their length each sized to receive a wing nut bolt fastener 32. The distal end of each of the outboard members 27 is provided with a handle 34 mounted for rotational movement and adapted to be grasped in the hand of a user. As will be recognized, by this particular arrangement, the effective length of the crank assembly 26 may be adjusted by positioning of the wing nut bolt 32 in a desired aperture 30 of the outboard elongate members 27.
The shaft 20 carries a pair of preferably dissimilar sized gears or sprockets 40 and 42 which rotate in unison upon the shaft 20. As best shown in FIGS. 2 and 4, the gear 40 communicates with the gear 22 of the crank assembly 26 via a chain drive 44, which chain drive is preferably covered by a protective shroud or housing 46. The outboard end of the yoke 18 is pivotally attached to a telescoping sleeve arrangement 48 which is mounted on its lowermost end to one of the angular support struts 16. A wind nut 50 is provided on the telescoping sleeve assembly 48 to lock the sleeve assembly 48 at a desired axial length. As will be recognized, due to the yoke 18 being pivotally mounted to the shaft 20, the vertical elevation of the crank assembly 26 relative the support platform 12 may be easily adjusted merely by loosening of the wing nut 50 rotating or pivoting the yoke 18 either in a clockwise or counterclockwise direction (as indicated by the phantom lines in FIG. 2) and subsequently locking the yoke 18 in a desired position by retightening of the wing nut fastener 50 on the telescoping sleeve assembly 48.
The gear or sprocket 42 mounted upon the shaft 20 communicates via a chain drive 60 with a gear or sprocket 62 disposed adjacent the platform 12. The gear 62 is rigidly connected to the output shaft 64 of an exercise load regulating means designated generally by the numeral 66. In the preferred embodiment, the load regulating means 66 comprises a hydraulic pump 67 having a pressure regulator valve 69 adapted to vary the pressure and thus vary the output torque of the pump 67 applied to the gear 62. As will be recognized, the direction of the rotational load applied by the load regulating means 66 to the gear 62 is in opposition to the rotational force applied by the hand crank assembly 26 to cause greater exertion to be applied by the user during the exercise program. A manually actuated lever and linkage 68 is connected to the pressure regulator valve of the load regulator means 66 to permit the magnitude of the counter rotational torque to be rapidly varied by a user. To reduce minor speed variations in the rotational speed of the gear 62, a high mass fly wheel 70 is preferably disposed upon the output shaft 64 of the load regulating means 66.
A display panel 80 is attached to the uppermost end of the column 14 and preferably includes gauge and display devices for communicating information related to the exercise operation to the user. In the preferred embodiment, the display 80 includes a conventional timing mechanism having a pair of digital displays 82 and 84 adapted to provide an overall exercise time and elasped exercise time display, respectively, to the user. In addition, a gauge 86 may be provided to indicate the number of revolutions per minute of the fly wheel 70 which gauge is responsive to signals obtained from a speed sensor 88 positioned adjacent the fly wheel 70. A percentage load indicator 90 may further be utilized to indicate the magnitude of the counter rotational torque being applied during the exercise program by the load regulating means 66.
A pair of wheels 92 is positioned upon the platform 12 to permit the apparatus 10 to be rapidly transported to a desired location. Advantageously, the wheels 92 are positioned such that their periphery is raised slightly above the lower planar surface of the platform 12 so as not to contact the floor when the apparatus 10 is being utilized. However, when it is desired to transport the apparatus, the apparatus 10 may be pivoted about the wheels 90 such that the wheels support the entire weight of the apparatus 10 during transport.
With the structure defined, the operation of the apparatus 10 of the present invention may be described. Initially, the vertical position and length of the hand crank assembly 26 must be adjusted for the particular user. This initial adjustment is effectuated by loosening of the wing nut 50 and rotating the yoke 18 either in a clockwise direction to increase the height of the crank assembly 26 from the support platform 12, or in a counterclockwise direction to decrease the height from the platform 12. When properly positioned, the wing nut 50 may be manually tightened to lock the yoke 18 in its desired position. In addition, the length of the hand crank assembly 26 may be adjusted to the particular user by selectively positioning the wing nut bolt assemblies 32 into one of the desired apertures 39 of the hand crank assembly 26.
It is an important feature of the present invention that the initial adjustment of the apparatus 10 is effectuated to require a full extension of the upper extremities of the user when the handle 34 of the crank assembly 26 are positioned at their uppermost vertical orientation. This extended position is indicated in FIG. 6 whereby the left side of the user's body is placed in a stretching motion as indicated by the arrow in FIG. 6 causing the abdomen, chest, and left arm to be fully extended.
Positioned in such a manner and by grasping both of the handles 34 of the crank assembly 26, the user subsequently rotates the hand crank assembly 26 in a cycling motion as in the direction indicated by the arrows in FIG. 6.
Upon rotation from the maximum extension position indicated in FIG. 6 to a position wherein both of the handles 34 of the crank assembly 26 are disposed in a horizontal plane, the user's body will twist or rotate about the hips and waist as indicated by the arrows in FIG. 5 thereby providing exercise of the waist and muscles of the abdomen, chest, back and shoulders. As will be recognized, by continued rotational movement of the hand crank assemblies, this reaching and twisting motion is repeated causing a full interactive exercise or the upper extremeties and upper body portions of the user.
To improve the quality of the exercise program, a user simply adjusts the counter-rotational force being applied to the hand crank assembly 26 by manual adjustment of the lever 68 which causes a corresponding throttling of the load regulating means 66. The particular exercise program may, of course, be continued for any desired length of time, however preferably, is continued only for the predetermined exercise time entered into the overall time display 82 and indicated on the elasped time display 84. In addition, during the exercise program, the user can continuously monitor the rotational speed of the hand cranks by the visual rotational speed display 86.
Thus, in summary, the present invention provides a significantly improved exercise apparatus which enables both aerobic and anaerobic exercise of the upper extremities and upper body portion of a user. Although in the preferred embodiment certain material sizes and configurations have been illustrated, those skilled in the art will recognized that various modifications can be made to the same without departing from the spirit of the present invention and that such modifications are anticipated within the scope of the present invention.
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A variable resistance exercise apparatus is disclosed specifically adapted to provide an improved method or aerobic and anaerobic exercising of the upper extremities and upper body portion of a user. The apparatus is characterized by the use of a hand crank assembly adjustably positioned at a vertical height above a support platform to cause a user to reach and twist during exercise upon the apparatus. The length of the hand crank assembly may be adjusted to accommodate differing extremity lengths of the particular user and the exercise resistance load applied to the hand crank may be varied to accommodate both professional athletic training as well as residential fitness programs.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to the synthetic methods and manufacture procedures for (methyl-d 3 )amine and salts thereof.
2. Description of Related Art
(Methyl-d 3 )amine and the hydrochloride thereof, the important intermediates for chemical synthesis, can be used to make medicinal compounds.
For example, the ω-diphenylurea derivatives are known as the compounds with c-RAF kinase inhibition activity. Initially, ω-diphenylurea compounds, such as Sorafenib, were firstly found as the inhibitors of c-RAF kinase. The other studies had shown that they could also inhibit the MEK and ERK signal transduction pathways and activities of tyrosine kinases including vascular endothelial growth factor receptor-2 (VEGFR-2), vascular endothelial growth factor receptor-3 (VEGFR-3), and platelet-derived growth factor receptor-β (PDGFR-β) (Curr Pharm Des 2002, 8, 2255-2257). Therefore, it is called multi-kinase inhibitor which possesses dual anti-tumor effects.
Sorafenib (trade name Nexavar), a novel oral multi-kinase inhibitor, was developed by Bayer and Onyx. In December 2005, based on its outstanding performance in phase III clinical trials for treating advanced renal cell carcinoma, Sorafenib was approved by FDA for treating advanced renal cell carcinoma. It was marketed in China in November 2006. However, Sorafenib has various side-effects, such as hypertension, weight loss, rash and so on.
(Methyl-d3)amine is used during the preparation of sorafenib derivatives. However, the synthetic steps or the current preparation processes are relatively complex, or the cost is high. Therefore, development of some simple, highly efficient, and/or low cost methods for preparing (methyl-d3)amine and salts thereof is needed.
BRIEF SUMMARY OF THE INVENTION
The subject of the invention is to provide a simple, highly efficient and/or low cost method for preparing (methyl-d 3 )amine and salts thereof.
In the first aspect, the invention provides a method for preparing (methyl-d 3 )amine or salts thereof, comprising:
(i) in the presence of a base and a phase transfer catalyst, reacting nitromethane with deuterated water to form deuterated nitromethane;
(ii-a) in an inert solvent, reducing deuterated nitromethane to form (methyl-d 3 )amine; then optionally reacting (methyl-d 3 )amine with an acid to form the salt of (methyl-d 3 )amine; or
(ii-b) in an inert solvent and in the presence of an acid, reducing deuterated nitromethane to form the salt of (methyl-d 3 )amine directly.
In one embodiment, said base is selected from sodium hydride, potassium hydride, deuterated sodium hydroxide, deuterated potassium hydroxide, potassium carbonate or the combination thereof.
In one embodiment, in step (ii-a) or (ii-b), zinc powder, magnesium powder, iron, or nickel is used as a catalyst.
In one embodiment, said acid is selected from hydrochloric acid, sulfuric acid, formic acid, acetic acid, or the combination thereof.
In one embodiment, in step (ii-a) or (ii-b), said inert solvent is selected from methanol, ethanol, water, tetrahydrofuran, isopropanol, or the combination thereof.
In the second aspect, the invention provides a method for preparing (methyl-d 3 )amine or salts thereof, comprising:
(a1) in an inert solvent and in the presence of a catalyst, reacting phthalimide with deuterated methanol to form N-(methyl-d 3 )phthalimide;
or (a2) in an inert solvent, reacting an alkali metal salt of phthalimide with compound A,
wherein, Z is CH 3 , O—CD 3 or
wherein R is methyl, nitro or halogen (F, Cl or Br), to form N-(methyl-d 3 )phthalimide;
(b) reacting N-(methyl-d 3 )phthalimide with an acid to form the salt of (methyl-d 3 )amine; and
optional (c): reacting the salt of (methyl-d 3 )amine with a base to form (methyl-d 3 )amine.
In one embodiment, in step (a1), said inert solvent is tetrahydrofuran.
In one embodiment, said acid is selected from hydrochloric acid, sulfuric acid, formic acid, acetic acid, or combination thereof.
In one embodiment, in step (a1), said catalyst is selected from diethyl azodicarboxylate (DEAD), diisopropyl azodicarboxylate (DIAD), triphenylphosphine, tributylphosphine, or the combination thereof.
In one embodiment, in step (a2), said inert solvent is selected from N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), or the combination thereof.
In one embodiment, in step (a2), the reaction temperature is −10° C. to reflux temperature, preferably, −4° C. to 100° C., and more preferably, 20˜80° C.
In one embodiment, the reaction time is 0.1-24 hours, preferably, 0.3˜5 hours, and more preferably, 0.5˜2 hours.
In one embodiment, in step (a2), said alkali metal salt of phthalimide includes potassium phthalimide, sodium phthalimide, lithium phthalimide, or the combination thereof.
In one embodiment, in step (a2), said compound A includes (methyl-d 3 ) 4-methylbenzenesulfonate, (methyl-d 3 ) 3-nitrobenzenesulfonate, or (methyl-d 3 ) 4-nitrobenzenesulfonate.
In one embodiment, there is another step prior to step (a2) of the said method: under a basic condition and in an inert solvent, reacting deuterated methanol with tosyl chloride to form (methyl-d 3 ) 4-methylbenzenesulfonate. Preferably, said inert solvents in such step include water, tetrahydrofuran, or the combination thereof.
In the third aspect, the invention provides a method for preparing a salt of (methyl-d 3 )amine, comprising:
In an aqueous solvent, reacting N-(methyl-d 3 )phthalimide with an acid to form a salt of (methyl-d 3 )amine, wherein said acid includes hydrochloric acid, sulfuric acid, hydrobromic acid, trifluoroacetic acid, or the combination thereof.
In one embodiment, the reaction temperature is 30° C. to reflux temperature (such as 120° C.), and preferably, 40˜110° C.
In one embodiment, the reaction time is 0.5˜48 hours, preferably, 1˜36 hours, and more preferably, 2˜24 hours.
In one embodiment, said method includes:
In the fourth aspect, the invention provides a method for preparing N-(4-chloro-3-(trifluoromethyl)phenyl)-N-(4-(2-(N-(methyl-d 3 )aminoformyl)-4-pyridyloxy)phenyl)urea using (methyl-d 3 )amine or salts thereof prepared according to the invention:
It should be understood that in the present invention, any of the technical features specifically described above and below (such as in the Examples) can be combined with each other, thereby constituting new or preferred technical solutions that are not described one by one in the specification.
DETAILED DESCRIPTION OF THE INVENTION
The inventors developed a simple, highly efficient and low cost method and procedure for producing (methyl-d 3 )amine and salts thereof. Based on this discovery, the inventors completed the present invention.
Furthermore, the inventors synthesized deuterated ω-diphenylurea compounds which could be used as the efficient kinase inhibitors. Taking the most preferred deuterated ω-diphenylurea compound N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-(methyl-d 3 )aminoformyl)-4-pyridyloxy)phenyl)urea (CM4307) and un-deuterated compound N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-methyl aminoformyl)-4-pyridyloxy)phenyl)urea (CM4306) as an example,
the results of pharmacokinetic test showed that the half life (T 1/2 ) of CM4307 was longer, the AUC 0-∞ of CM4307 increased significantly and the apparent clearance of CM4307 decreased compared to CM4306.
The results of pharmacodynamic test performed in the nude mouse model inoculated with human liver cancer cell SMMC-7721 showed that, after intragastric administration at 100 mg/kg per day for two weeks, the relative tumor increment rate T/C (%) as an evaluation index of CM4306 anti-tumor activity was 32.2%, while that of CM4307 was 19.6%. Therefore, the absolute value of anti-tumor activity increased over 10%, the relative value increased about 60% (32.2%/19.6%−1=64%), and CM4307 showed more significant tumor inhibition effect.
DEFINITIONS
As used herein, the team “halogen” refers to F, Cl, Br and I. Preferably, halogen is selected from F, Cl, and Br.
As used herein, the term “alkyl” refers to straight-chain or branched chain alkyl.
Preferable alkyl is C1-C4 alkyl, such as methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, etc.
As used herein, the term “deuterated” means that one or more hydrogens of compounds or groups are substituted by deuterium or deuteriums. “Deuterated” can be mono-substituted, hi-substituted, multi-substituted or total-substituted. The terms “one or more deuterium-substituted” and “substituted by deuterium once or more times” can be used interchangeably.
In one embodiment, the deuterium content in a deuterium-substituted position is at least greater than the natural abundance of deuterium (0.015%), preferably >50%, more preferably >75%, more preferably >95%, more preferably >97%, more preferably >99%, more preferably >99.5%.
As used herein, the term “compound CM4306” is 4-(4-(3-(4-chloro-3-(trifluoromethyl)phenyl)ureido)-phenoxy)-2-(N-methyl)picolinamide.
As used herein, the term “compound CM4307” is 4-(4-(3-(4-chloro-3-(trifluoromethyl)phenyl)ureido)-phenoxy)-N-(methyl-d 3 )picolinamide.
As used herein, the term “TsOH” represents p-toluenesulfonic acid. Therefore, CM4307.TsOH represents the p-toluenesulfonate of CM4307. CM4309.TsOH represents the p-toluenesulfonate of CM4309.
A key intermediate of the invention is N-(methyl-d 3 )phthalimide;
This intermediate can be called “deuterated methyl phthalimide”. Except for H, all or almost all (>99 wt %) of the elements (such as N, C, O, etc.) in the above compounds are naturally existed elements with highest abundance, such as 14 N, 12 C and 16 O.
Preparation
The preparation methods for the compound of the invention are described in detail as below. However, these specific methods are not provided for the limitation of the invention. The compounds of the invention can be readily prepared by optionally combining any of the various methods described in the specification or with various methods known in the art, and such combination can easily be carried out by the skilled in the art.
In general, during the preparation, each reaction is conducted in an inert solvent, at a temperature between room temperature to reflux temperature (such as 0˜80° C. preferably 0˜50° C.). Generally, the reaction time is 0.1˜60 hours, preferably, 0.5˜48 hours.
Taking CM4307 as an example, an optimized preparation route is shown as follows:
As shown in Scheme 1, in the presence of N,N′-carbonyldiimidazole, phosgene or triphosgene, 4-aminophenol (Compound I) reacts with 3-trifluoromethyl-4-chloro-aniline (Compound II) to give 1-(4-chloro-3-(trifluoromethyl)phenyl)-3-(4-hydroxyphenyl)urea (Compound III). 2-(N-(methyl-d 3 ))carbamoyl pyridine (Compound V) is obtained by reacting methyl picolinate (Compound IV) with (methyl-d 3 )amine or (methyl-d 3 )amine hydrochloride directly or in the presence of the base such as sodium carbonate, potassium carbonate, sodium hydroxide, triethylamine, pyridine and the like. In the presence of base (such as potassium tert-butoxide, sodium hydride, potassium hydride, potassium carbonate, cesium carbonate, potassium phosphate, potassium hydroxide, sodium hydroxide) and an optional catalyst (such as cuprous iodide and proline, or cuprous iodide and picolinic acid), Compound III reacts with Compound V to form compound CM-4307. The above reactions are conducted in an inert solvent, such as dichloromethane, dichloroethane, acetonitrile, n-hexane, toluene, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide and so on, and at a temperature of 0-200° C.
Another particularly preferred process for preparing CM4307 is shown as below:
wherein, the deuterium can be introduced by using deuterated methylamine. Deuterated methylamine can be prepared using a method known in the art as below, for example, hydrogenation of deuterated nitromethane shown as follows:
wherein r.t. means room temperature.
Alternatively, deuterated methylamine or the hydrochloride thereof can be prepared through the following reactions. Deuterated nitromethane is obtained by reacting nitromethane with deuterium water in the presence of base (such as sodium hydride, potassium hydride, deuterated sodium hydroxide, deuterated potassium hydroxide, potassium carbonate and the like) or phase-transfer catalyst. The above experiment can be repeated if necessary, to produce deuterated nitromethane in high purity. Deuterated nitromethane is reduced in the presence of zinc powder, magnesium powder, iron, or nickel and the like to form deuterated methylamine or the hydrochloride thereof.
Furthermore, deuterated methylamine or the hydrochloride thereof can be obtained through the following reactions.
The key intermediate 3 can be synthesized from deuterium methanol (CD 3 OD) through the following reactions.
The detailed preparation procedure is described in Example 1.
The main advantages of the method for preparing (methyl-d 3 )amine or salts thereof of the invention include:
(1) The method is simple, highly efficient and low cost.
(2) The purity of the product is high.
(3) The method can be used in various applications.
The present invention will be further illustrated below with references to the specific examples. It should be understood that these examples are only to illustrate the invention but not to limit the scope of the invention. The experimental methods with no specific conditions described in the following examples are generally performed under the conventional conditions, or according to the manufacture's instructions. Unless indicated otherwise, parts and percentage are calculated by weight.
Example 1
Preparation of N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-(methyl-d 3 )aminoformyl)-4-pyridyloxy)phenyl)urea (Compound CM4307)
1. Preparation of 4-chloropyridine-2-(N-(methyl-d 3 ))carboxamide (3)
To a 250 mL single-neck round-bottom flask equipped with waste gas treatment equipments, thionyl chloride (60 MO was added. Anhydrous DMF (2 mL) was dropwise added slowly while keeping the temperature at 40-50° C. After addition, the mixture was stirred for 10 min, and then nicotinic acid (20 g, 162.6 mmol) was added in portions in 20 min. The color of the solution gradually changed from green into light purple. The reaction mixture was heated to 72° C., and refluxed for 16 hours with agitation. A great amount of solid precipitated. The mixture was cooled to room temperature, diluted with toluene (100 mL) and concentrated to almost dry. The residue was diluted with toluene again and concentrated to dry. The residue was filtered and washed with toluene to give 4-chloro-pyridine-2-carbonyl chloride as a light yellow solid. The solid was slowly added into a saturated solution of (methyl-d 3 )amine in tetrahydrofuran in an ice-bath. The mixture was kept below 5° C. and stirred for 5 hours. Then, the mixture was concentrated and ethyl acetate was added to give a white solid precipitate. The mixture was filtered, and the filtrate was washed with saturated brine, dried over sodium sulfate and concentrated to give 4-chloropyridine-2-(N-(methyl-d 3 ))carboxamide (3) (20.68 g, 73% yield) as a light yellow solid.
1 H NMR (CDCl 3 , 300 MHz): 8.37 (d, 1H), 8.13 (s, 1H), 7.96 (br, 1H), 7.37 (d, 1H).
2. Preparation of 4-(4-aminophenoxy)-2-pyridine-(N-(methyl-d 3 ))carboxamide (5)
To dry DMF (100 mL), 4-aminophenol (9.54 g, 0.087 mol) and potassium tert-butoxide (10.3 g, 0.092 mol) was added in turn. The color of the solution turned into deep brown. After stirring at room temperature for 2 hours, to the reaction mixture was added 4-chloro-(N-methyl-d 3 )pyridine-2-carboxamide (3) (13.68 g, 0.079 mol) and anhydrous potassium carbonate (6.5 g, 0.0467 mol), then warmed up to 80° C. and stirred overnight. TLC detection showed the reaction was complete. The reaction mixture was cooled to room temperature, and poured into a mixed solution of ethyl acetate (150 mL) and saturated brine (150 mL). The mixture was stirred and then stood for separation. The aqueous phase was extracted with ethyl acetate (3×100 mL). The extracted layers were combined, washed with saturated brine (3×100 mL) prior to drying over anhydrous sodium sulfate, and concentrated to afford 4-(4-aminophenoxy)-2-pyridine-(N-(methyl-d 3 ))carboxamide (18.00 g, 92% yield) as a light yellow solid.
1 H NMR (CDCl 3 , 300 MHz): 8.32 (d, 1H), 7.99 (br, 1H), 7.66 (s, 1H), 6.91-6.85 (m, 3H), 6.69 (m, 2H), 3.70 (br, s, 2H).
3. Preparation of N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-(methyl-d 3 )aminoformyl)-4-pyridyloxy)phenyl)urea (CM4307)
To methylene chloride (120 mL), 4-chloro-3-trifluoromethyl-phenylamine (15.39 g, 78.69 mmol) and N,N′-carbonyldiimidazole (13.55 g, 83.6 mmol) was added. After stirring at room temperature for 16 hours, a solution of 4-(4-aminophenoxy)-2-pyridine-(N-(methyl-d 3 ))-carboxamide (18 g, 73 mmol) in methylene chloride (180 mL) was slowly added dropwise. The mixture was stirred at room temperature for another 18 hours. TLC detection showed the reaction was complete. The mixture was concentrated to about 100 mL by removing methylene chloride through a rotary evaporator and stood for several hours at room temperature. A great amount of white solid precipitated. The solid was filtered and washed with abundant methylene chloride. The filtrate was concentrated by removing some solvent, and some solid precipitated again. Two parts of solid were combined and washed with abundant methylene chloride to afford N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-(methyl-d 3 )aminoformyl)-4-pyridyloxy)phenyl)urea (CM4307, 20.04 g, 58% yield) as a white powder (pure product).
1 H NMR (CD 3 OD, 300 MHz): 8.48 (d, 1H), 8.00 (d, 1H), 7.55 (m, 5H), 7.12 (d, 1H), 7.08 (s, 2H), ESI-HRMS m/z: C 21 H 13 D 3 ClF 3 N 4 O 3 , Calcd. 467.11. Found 490.07 (M+Na) + .
Furthermore, Compound CM4307 was dissolved in methylene chloride and reacted with benzoperoxoic acid to afford the oxidized derivative: 4-(4-(3-(4-chloro-3-(trifluoromethyl)phenyl)ureido)phenoxy)-2-(N-(methyl-d 3 )aminoformyl)pyridine-1-oxide,
Example 2
Preparation of 4-chloropyridyl-(N-(methyl-d 3 ))-2-carboxamide (3)
a) To a solution of phthalimide (14.7 g, 0.1 mol), deuterated methanol (3.78 g, 0.105 mol, 1.05 eq) and triphenylphosphine (28.8 g, 0.11 mol, 1.1 eq) in anhydrous tetrahydrofuran was dropwise added a solution of DEAD (1.1 eq) in tetrahydrofuran under ice-bath. After addition, the mixture was stirred for 1 hour at room temperature. The mixture was purified by chromatography column, or the solvent in the mixture was removed, and then to the residue was added an appropriate amount of DCM and cooled in the refrigerator to precipitate the solid. The mixture was filtered and the filtrate was concentrated by a rotary evaporator, and then the residue was purified by flash chromatography column to afford the pure product of 2-(N-(methyl-d 3 ))-isoindole-1,3-dione, (14.8 g, 90% yield).
b) 2-(N-(methyl-d 3 ))-isoindole-1,3-dione (12.5 g, 0.077 mol) was dissolved hydrochloric acid (6 N, 50 mL) and the mixture was refluxed for 24-30 hours in a sealed tube. The reaction mixture was cooled to room temperature and then cooled below 0° C. in the refrigerator to precipitate the solid. The solid was filtrated and washed with cold deionized water. The filtrate was collected and concentrated by rotary evaporator to remove water. The residue was dried to afford (methyl-d 3 )amine hydrochloride salt. Anhydrous DCM (100 mL) was added in (methyl-d 3 )amine hydrochloride salt and 4-chloro-pyridine-2-carboxylic acid methyl ester hydrochloride salt (6.52 g, 0.038 mol, 0.5 eq) and sodium carbonate (12.2 g, 0.12 mol, 1.5 eq) were added. The reaction flask was sealed and placed in the refrigerator for one day. After the reaction was complete by TLC detection, the reaction mixture was washed with water, dried, concentrated and purified by chromatography column to afford 4-chloro-pyridine-2-(N-(methyl-d 3 ))formamide (compound (3), 5.67 g, 86% yield). The structural feature was the same as Example 1.
Example 3
Preparation of (methyl-d 3 )amine hydrochloride
1. Nitromethane-d 3
Nitromethane (0.61 g, 10 mmol, 1.0 eq) was dissolved in heavy water (5.0 g, 250 mmol, 25.0 eq). After Nitrogen replacement was conducted for three times, the mixture was refluxed for 16 hours. The reaction mixture was cooled to room temperature, and extracted with anhydrous ethyl ether (20 mL×2). The organic phase was dried over anhydrous sodium sulfate and filtered. The solvent in the filtrate was removed under reduced pressure to afford the title compound (0.1 g) as a yellow liquid. The result of NMR indicated that partially-deuterated nitromethane and totally-deuterated nitromethane was obtained.
2. (Methyl-d 3 )amine hydrochloride
Deuterated nitromethane (0.64 g, 10.0 mmol) was dissolved in methanol (25.0 mL). Pd/C (10%, 0.1 g) was added. H 2 replacement was conducted for three times through balloon. At the room temperature, the mixture was stirred for 16 hours. The mixture was acidified by dropping hydrochloric acid, and filtered. The solvent in the filtrate was removed under reduced pressure to afford the title compound (0.60 g) as a light yellow product. The result of NMR indicated that (methyl-d 3 )amine hydrochloride was obtained.
1 H NMR (DMSO-d 6 , 400 MHz): δ 8.05 (br, 2H)
Example 4
Preparation of (methyl-d 3 )amine hydrochloride
1. Preparation of (methyl-d 3 ) p-toluenesulfonate
To water (288 mL), sodium hydroxide (180 g, 4.5 mol, 5.0 eq) was added. At 0° C., methanol-d 3 (32.4 g, 900 mmol, 1.0 eq) was added, and the solution of tosyl chloride (206 g, 1.1 mmol, 1.2 eq) in tetrahydrofuran (288 mL) was dropwise added slowly. The mixture was warmed to room temperature and stirred overnight. The mixture was neutralized to neutral by dropwise adding acetic acid (206 g) at 25° C., filtered and partitioned. The aqueous phase was extracted with ethyl acetate (100 mL). The filter cake was dissolved in water (300 mL) and extracted with ethyl acetate (200 mL). The organic phases were combined and washed with saturated sodium carbonate (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate and filtered. The solvent in the filtrate was removed under reduced pressure to afford the title compound (160.5 g, purity 99%, yield 94%) as a pale yellow liquid.
1 H NMR(CDCl 3 , 400 MHz): δ3.20 (s, 3H), 7.71-7.75 (m, 2H), 7.84-7.88 (m, 2H).
2. Preparation of N-(methyl-d 3 )phthalimide
To N,N-dimethylformamide (DMF, 225 mL), potassium phthalimide (166.7 g, 0.9 mol, 2.0 eq) was added, and then methyl-d 3 p-toluenesulfonate (85.2 g, 0.45 mmol, 1.0 eq) was added dropwise at room temperature. The mixture was stirred at 60° C. for 0.5 hour, and filtered immediately. The solid was washed with DMF (250 mL and 100 mL) for two times. The DMF solutions were combined and water (1150 mL) was added dropwise at 0° C. to precipitate a white solid. The solid was filtered and washed with water (100 mL×2). The obtained solid was dried in vacuum to give the title compound (64 g, purity 99.6%, yield 85%) as a white solid.
1 H NMR (CDCl 3 , 400 MHz): δ7.71-7.77 (m, 2H), 7.84-7.88 (m, 2H).
3. Preparation of (methyl-d 3 )amine hydrochloride
To a solution of distilled water (625 mL) and concentrated hydrochloric acid (625 mL, 7.5 mol, 15 eq), N-(methyl-d 3 )phthalimide (82 g, 0.5 mol, 1 eq) was added at room temperature, and the mixture was heated to 105° C. and refluxed overnight. The mixture was cooled to room temperature, filtered, and washed with distilled water (50 mL×2). Hydrochloric acid was removed under reduced pressure to afford a light yellow solid. To the solid was added anhydrous ethanol (140 mL). The mixture was refluxed for 1 hour, cooled to room temperature, and filtered. The solid was washed with ethanol (30 mL) and dried in vacuum to give the title compound (28 g, yield 80%) as a white solid.
1 H NMR (DMSO-d 6 , 400 MHz): δ8.05 (br, 2H).
Example 5
Pharmacokinetic Evaluation in Rats
8 male Sprague-Dawley rats, (7-8 weeks old and body weight about 210 g), were divided into two groups, 4 in each group (rat No.: control group was 13-16; experimental group was 9-12), and orally administrated at a single dose at 3 mg/kg of either compound: (a) the undeuterated compound N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-methyl-aminoformyl)-4-pyridyloxy)phenyl)urea (control compound CM4306) or (b) N-(4-chloro-3-(trifluoromethyl)phenyl)-N′-(4-(2-(N-(methyl-d 3 )-aminoformyl)-4-pyridyloxy)phenyl)urea (Compound CM4307 of the invention) prepared in Example 1. The pharmacokinetics differences of CM4306 and CM4307 were compared.
The rats were fed with the standard feed, given water and chlordiazepoxide. Chlordiazepoxide was stopped at the last night before experiment, and given again two hours after the administration of the compound. The rats were fasted for 16 hours before the test. The compound was dissolved in 30% PEG400. The time for collecting orbital blood was 0.083, 0.25, 0.5, 1, 2, 4, 6, 8 and 24 hours after administrating the compounds.
The rats were anaesthetized briefly by inhaling ether. A 300 μL orbital blood sample was collected into the tubes containing a 30 μL 1% heparin saline solution. The tubes were dried overnight at 60° C. before being used. After the blood samples were sequentially collected, the rats were anaesthetized by ether and sacrificed.
After the blood samples were collected, the tubes were gently reversed at least five times immediately to mix the contents sufficiently, and placed on the ice. The blood samples were centrifuged at 4° C. at 5000 rpm for 5 minutes to separate the serum and red blood cells. 100 μL, serum was removed to a clean plastic centrifugal tube by pipettor, and the name of the compound and time point were labeled on the tube. Serum was stored at −80° C. before LC-MS analysis.
The results showed that, compared with CM4306, the half-life (T 1/2 ) of CM4307 was longer [11.3±2.1 hours for CM4307 and 8.6±1.4 hours for CM4306, respectively], area under the curve (AUC 0-∞ ) of CM4307 was significantly increased [11255±2472 ng·h/mL for CM4307 and 7328±336 ng·h/mL for CM4306, respectively], and apparent clearance of CM4307 was reduced [275±52 mL/h/kg for CM4307 and 410±18.7 mL/h/kg for CM4306, respectively].
The above results showed that, the compound of the present invention had better pharmacokinetics properties in the animal, and thus had better pharmacodynamics and therapeutic effects.
Example 6
The Pharmacodynamic Evaluation of CM4307 for Inhibiting Tumor Growth of Human Hepatocellular Carcinoma SMMC-7721 in Nude Mice Xenograft Model
70 Balb/c nu/nu nude mice, 6 weeks old, female, were bought from Shanghai Experimental Animal Resource Center (Shanghai B&K Universal Group Limited).
SMMC-7721 cells were commercially available from Shanghai Institutes for Biological Science, CAS (Shanghai, China).
The establishment of tumor nude mice xenograft model: SMMC-7721 cells in logarithmic growth period were cultured. After cell number was counted, the cells were suspended in 1×PBS, and the concentration of the cell suspension was adjusted to 1.5×10 7 /ml. The tumor cells were inoculated under the skin of right armpit of nude mice with a 1 ml syringe, 3×10 6 /0.2 ml/mice. 70 nude mice were inoculated in total.
When the tumor size reached 30-130 mm 3 , 58 mice were divided randomly into the different groups. The difference of the mean value of tumor volume in each group was less than 10% and drugs were started to be administrated.
The test doses for each group were listed in the following table.
Ani-
Com-
Adminis-
Group
mal
pounds
tration
Dose (mg/kg)
Method
1
10
control
Po
0.1 ml/
qd × 2 weeks
(solvent)
10 g BW
2
8
CM4306
Po
10
mg/kg
qd × 2 weeks
3
8
CM4306
Po
30
mg/kg
qd × 2 weeks
4
8
CM4306
Po
100
mg/kg
qd × 2 weeks
5
8
CM4307
Po
10
mg/kg
qd × 2 weeks
6
8
CM4307
Po
30
mg/kg
qd × 2 weeks
7
8
CM4307
Po
100
mg/kg
qd × 2 weeks
Animal body weight and tumor size were tested twice a week during the experiment. Clinical symptoms were recorded every day. At the end of the administration, the tumor size was recorded by taking pictures. One mouse was sacrificed in each group and tumor tissue was taken and fixed in 4% paraformaldehyde. Observation was continued after the administration, and when the mean size of tumor was larger than 2000 mm 3 , or the dying status appeared, the animals were sacrificed, gross anatomy was conducted, and the tumor tissue was taken and fixed in 4% paraformaldehyde.
The formula for calculating the tumor volume (TV) is: TV=a×b 2 /2, wherein a, b independently represent the length and the breadth of the tumor. The formula for calculating the relative tumor volume (RTV) is: RTV=Vt/V 0 , wherein V 0 is the tumor volume at the beginning of the administration, and Vt is the tumor weight when measured. The index for evaluating the antitumor activity is relative tumor increment rate T/C (%), and the formula is: T/C (%)=(T RTV /C RTV )×100%, wherein, T RTV is the RTV of the treatment group, and C RTV is the RTV of the negative control group.
Evaluation standard for efficacy: it is effective if the relative tumor increment rate T/C (%) is ≦40% and p<0.05 by statistics analysis.
The results showed that CM4306 and CM4307 were intragastric administrated every day for 2 weeks at doses of 10, 30, 100 mg/kg respectively, and both compounds showed the dose-dependent effect of the inhibition of tumor growth. At the end of administration, T/C % of CM4306 was 56.9%, 40.6% and 32.2%, respectively. T/C % of CM4307 was 53.6%, 40.8% and 19.6%. T/C % for 100 mg/kg dose groups was <40%, and tumor volume was significantly different (p<0.01) from the control group, indicating the significant effect in inhibiting tumor growth.
Compared with CM4306, the inhibitory efficacy of tumor growth at dosing 100 mg/kg of CM4307 was stronger (the T/C % for CM4307 and CM4306 is 19.6% and 32.2%, respectively, at day 15), there was significant difference in tumor volume between groups (p<0.01). Compared with CM4306, the absolute value of tumor inhibition rate for CM4307 increased more than 10%, the relative value increased about 60% (32.2%/19.6%−1=64%), and CM4307 showed more significant effect for inhibiting tumor growth.
In addition, during the experiment, no other drug-relevant toxic effects were observed.
All literatures mentioned in the present application are incorporated by reference herein, as though individually incorporated by reference. Additionally, it should be understood that after reading the above teaching, many variations and modifications may be made by the skilled in the art, and these equivalents also fall within the scope as defined by the appended claims.
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Preparation methods of methyl-d 3 -amine and salts thereof are provided, which contain the following steps: (i) nitromethane is subjected to react with deuterium oxide in the present of bases and phase-transfer catalysts to form nitromethane-d 3 , which is subsequently subjected to reduction in an inert solvent to form methyl-d 3 -amine, and optionally, methyl-d 3 -amine reacts subsequently with acids to form salts of methyl-d 3 -amine; or (ii) N-(1,1,1-trideuteriomethyl)phthalimide is subjected to react with acids to form salts of methyl-d 3 -amine. The present methods are easy, high efficient, and low cost.
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CROSS-REFERENCE TO RELATED APPLICATION(S)
This application claims priority from Provisional Application No. 60/194,813 filed Apr. 5, 2000, for “Double Sided Trench Fill For Electrical Isolation Of MEMS Structures” by W. Bonin, Z. Boutaghou, R. Hipwell, B. Wissman, L. Walter, and B. Ihlow-Mahrer.
BACKGROUND OF THE INVENTION
The present invention relates generally to microelectromechanical system (MEMS) devices, and more particularly to a method of electrically isolating MEMS device structures utilizing isolation trenches filled from both sides of a silicon product wafer.
Many MEMS devices require the fabrication of electrically isolated, mechanically connected structures. One approach to realizing these structures is through the use of insulator-filled isolation trenches. Under this approach, trenches separating high-aspect ratio MEMS structures are deep-trench reactive-ion etched through the wafer being employed for fabricating the-MEMS device. After the trenches are etched, they are filled with an insulating material such as silicon nitride. This electrically isolates the MEMS structures from one another while maintaining a mechanical connection.
However, conventional methods of filling isolation trenches have significant problems with the mechanical integrity of the fill. For example, as isolation trenches are filled according to these conventional methods, insulating material accumulates at the trench openings faster than at the trench bottoms. This results in a small void near the bottom of the isolation trenches, jeopardizing the mechanical integrity of the final device. These small voids form because conventional methods of trench filling permit insulating material to be deposited from only one side of the product wafer. Accordingly, there is a need for a method to ensure uniform filling of high-aspect ratio isolation trenches.
BRIEF SUMMARY OF THE INVENTION
The present invention is a method for filling a trench extending through a microelectromechanical system (MEMS) device patterned on a wafer. The method involves simultaneously depositing a trench-fill layer of insulating material over a first side of the wafer, over a second side of the wafer, and into the trench extending from the first side to the second side. Further, the width of the trench at the first side of the wafer and/or the second side of the wafer is variable to adjust the rate at which the trench fills.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of electrically isolated MEMS device structures fabricated on a wafer using a silicon-on-insulator (SOI) wafer process according to a first prior art method.
FIG. 2 a is a cross-section view showing a first step of fabricating electrically isolated MEMS device structures on a wafer using a SOI wafer process according to a first prior art method.
FIG. 2 b is a cross-section view showing a second step of fabricating electrically isolated MEMS device structures on a wafer using a SOI wafer process according to a first prior art method.
FIG. 2 c is a cross-section view showing a third step of fabricating electrically isolated MEMS device structures on a wafer using a SOI wafer process according to a first prior art method.
FIG. 2 d is a cross-section view showing a fourth step of fabricating electrically isolated MEMS device structures on a wafer using a SOI wafer process according to a first prior art method.
FIG. 3 is a perspective view of a second prior art method of fabricating electrically isolated MEMS device structures on a wafer using a fusion bonded cavity wafer process.
FIG. 4 a is a cross-section view showing a first step of fabricating electrically isolated MEMS device structures on a wafer using a fusion bonded cavity wafer process according to a second prior art method.
FIG. 4 b is across-section view showing a second step of fabricating electrically isolated MEMS device structures on a wafer using a fusion bonded cavity wafer process according to a second prior art method.
FIG. 4 c is a cross-section view showing a third step of fabricating electrically isolated MEMS device structures on a wafer using a fusion bonded cavity wafer process according to a second prior art method.
FIG. 4 d is a cross-section view showing a fourth step of fabricating electrically isolated MEMS device structures on a wafer using a fusion bonded cavity wafer process according to a second prior art method.
FIG. 5 is a perspective view of a product wafer including electrically isolated MEMS devices fabricated on the wafer according to a first embodiment of the present invention.
FIG. 6 a is a cross-section view showing the first step of fabricating electrically isolated MEMS device structures according to a first embodiment of the present invention.
FIG. 6 b is a cross-section view showing the second step of fabricating electrically isolated MEMS device structures according to a first embodiment of the present invention.
FIG. 6 c is a cross-section view showing the third step of fabricating electrically isolated MEMS device structures according to a first embodiment of the present invention.
FIG. 6 d is a cross-section view showing the fourth step of fabricating electrically isolated MEMS device structures according to a first embodiment of the present invention.
FIG. 7 a is a cross-section view showing the first step of fabricating electrically isolated MEMS device structures according to a second embodiment of the present invention.
FIG. 7 b is a cross-section view showing the second step of fabricating electrically isolated MEMS device structures according to a second embodiment of the present invention.
FIG. 7 c is a cross-section view showing the third step of fabricating electrically isolated MEMS device structures according to a second embodiment of the present invention.
FIG. 7 d is a cross-section view showing the fourth step of fabricating electrically isolated MEMS device structures according to a second embodiment of the present invention.
FIG. 8 a is a cross-section view showing the first step of fabricating electrically isolated MEMS device structures according to a third embodiment of the present invention.
FIG. 8 b is a cross-section view showing the second step of fabricating electrically isolated MEMS device structures according to a third embodiment of the present invention.
FIG. 8 c is a cross-section view showing the third step of fabricating electrically isolated MEMS device structures according to a third embodiment of the present invention.
FIG. 8 d is a cross-section view showing the fourth step of fabricating electrically isolated MEMS device structures according to a third embodiment of the present invention.
FIG. 8 e is a cross-section view showing the fifth step of fabricating electrically isolated MEMS device structures according to a third embodiment of the present invention.
FIG. 8 f is a cross-section view showing the sixth step of fabricating electrically isolated MEMS device structures according to a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In order to fully understand the significance of the present invention, several figures disclosing the context and prior art of the present invention-are first introduced. FIGS. 1, 2 a , 2 b , 2 c , and 2 d present a method for filling electrical isolation trenches according to a first prior art method wherein silicon-on-insulator (SOI) wafer handling technology is used. FIGS. 3, 4 a , 4 b , 4 c , and 4 d disclose a method for filling electrical isolation trenches according to a second prior art method wherein fusion bonded wafer handling technology is used. The remaining figures, FIGS. 5, 6 a , 6 b , 6 c , 6 d , 7 a , 7 b , 7 c , 7 d , 8 a , 8 b , 8 c , 8 d , 8 e , and 8 f , disclose three methods of filling electrical isolation trenches according to the present invention.
FIG. 1 is a perspective illustration of SOI wafer handling technology, wherein a thin product wafer 20 of the final device thickness is bonded to handle wafer 22 by continuous oxide layer 24 .
FIGS. 2 a - 2 d are cross-section views of the wafer configuration of FIG. 1, showing the steps for fabricating electrically isolated MEMS device structures using a SOI process. As a first step, shown in FIG. 2 a , isolation trenches 30 are reactive-ion etched through product wafer 20 to continuous oxide layer 24 . Oxide layer 24 acts as an etch stop, such that the accelerated ions of the reactive-ion etch stop at the interface between product wafer 20 and oxide layer 24 . However, this approach has significant disadvantages. For example, footing 32 is typically observed at the interface between insulating layer 24 and product wafer 20 . This effect is the result of charged ions from the reactive-ion etch gas becoming embedded in insulating layer 24 . As the ions build up in insulating layer 24 , a charge builds up. As etching ions flow through isolation trenches 30 toward insulating layer 24 , the charge in insulating layer 24 repels the etching ions laterally.
The lateral spread of footing 32 becomes significant after the trenches are filled with insulating material 34 , as shown in FIG. 2 b . As insulating material 34 is spread over product wafer 20 and into isolation trenches 30 , insulating material 34 builds up at the opening of isolation trenches 30 faster than at the bottom of the trenches. This manifests small voids (“keyholes” 36 ) near the bottom of isolation trenches 30 , resulting in a very thin and weak mechanical connection at the bottom of the trench. Keyholes 36 are manifested even if the walls of isolation trenches 30 are uniformly straight. However, keyholes 36 become even more significant when footing 32 spreads laterally along continuous oxide layer 24 , since the area to be covered by insulating material 34 is larger when footing 32 exists at the bottom of the trench. Thus, as the tops of isolation trenches 30 fill with insulating material 34 , even larger keyholes 36 remain, resulting in poor mechanical integrity. One proposed solution to this problem (not shown) is to fabricate isolation trenches that are wider at the trench openings than at the trench bottom. However, this introduces another problem. After subsequent process steps, slivers of silicon remain near the bottom of the trench, as the wider trench top shadows the silicon near the bottom of the trench, preventing etching. This is problematic in that these slivers cause short circuits in the final device.
A second potential problem associated with using SOI technology for handling product wafer 20 is shown in FIG. 2 c . As footing 32 spreads laterally along oxide layer 24 , it potentially infringes upon areas reserved for trenches 38 , which define high-aspect ratio MEMS structures such as a stator electrode on a disc drive microactuator. This is problematic for two reasons. First, as trenches 38 are fabricated, additional etching is required to etch through the infringing insulating material. This is because silicon nitride, a material typically used for filling isolation trenches 30 , is highly resistant to the gases used for etching the trenches in the silicon. It should be noted that although there is a potential for a footing effect to occur as trenches 38 are etched, its effect is less serious than that for isolation trenches 30 and is not shown here for clarity. After the device is released, a second problem is introduced. Because insulating material 34 that was coating footing 32 has been removed, no mechanical connection remains at the bottom of isolation trenches 30 . This not only jeopardizes the mechanical integrity of the MEMS device, but also leaves an opening at the bottom of isolation trenches 30 . On the other hand, if the infringing insulating material is not removed, there will be a weak mechanical connection at the bottom of trenches 38 . However, the movement of the MEMS device will be restricted by the insulating material protruding into trenches 38 .
A third problem associated with SOI wafer handling is shown in FIG. 2 d . After etching trenches 38 , a “release step” is required to remove oxide layer 24 (FIG. 2 c ) from product wafer 20 , thus freeing the completed devices. Oxide layer 24 is typically removed by etching with hydrogen fluoride (HF) or other similar reactive gas or aqueous solution. However, the release step is often extremely undesirable or incompatible with MEMS devices in that added etching can render the devices nonfunctional.
One proposed solution to these problems is to use a fusion bonded wafer handling process, as opposed to SOI wafer handling. FIG. 3 is a perspective illustration of a typical fusion bonded wafer handling process. Silicon fusion bonding involves bonding two silicon wafers to each other to form one structural element. In this prior art example, shallow cavities 50 are etched into a first side of handle wafer 52 . Next, product wafer 54 is fusion bonded to the first side of handle wafer 52 at the outer edge of cavities 50 . Once handle wafer 52 is bonded to product wafer 54 , cavities 50 provide non-bonded support for devices 56 after being released from product wafer 54 .
FIGS. 4 a - 4 d are cross-section views of the wafer configuration of FIG. 3, showing the steps for fabricating electrically isolated MEMS device structures using a fusion bonded wafer handling process. In the first step, shown in FIG. 4 a , isolation trenches 60 are reactive-ion etched through product wafer 54 down to cavity 50 . This method has an advantage over the previous prior art example (FIGS. 2 a - 2 d ) in that no footing occurs as isolation trenches 60 permeate product wafer 56 . However, this trench-fill method also has disadvantages.
FIG. 4 b shows the result of the step shown in FIG. 4 a after insulating material 62 has been spread over product wafer 54 and into isolation trenches 60 . It should be noted that as insulating material 62 is applied to product wafer 54 , it not only coats the walls of isolation trenches 60 , but also coats the bottom of product wafer 54 and the top of handle wafer 52 (thus coating cavity 50 ). This becomes significant in subsequent process steps. Furthermore, as was seen in the previous prior art example (FIGS. 2 a - 2 d ), isolation trenches 60 fill with insulating material 62 faster at the opening of isolation trenches 60 than at the bottom of the trenches. This again manifests keyholes 64 near the bottom of isolation trenches 60 , resulting in a mechanical connection only at the top of the trenches. A solution similar to that in the previous prior art example has been proposed, wherein isolation trenches 60 are fabricated wider at the trench openings than at the trench bottoms. However, this also results in slivers of silicon remaining near the bottom of the trenches after subsequent process steps, as the wider trench top shadows the silicon near the bottom of the trench. This prevents etching of these slivers and is problematic because these slivers cause short circuits in the final device.
FIG. 4 c shows the results of the step shown in FIG. 4 b after trenches 66 defining high-aspect ratio MEMS structures are etched down to insulating material 62 that is coating cavity 50 . An exemplary high-aspect ratio MEMS structure is a stator electrode on a disc drive microactuator. Because silicon nitride, a material typically used to fill isolation trenches 60 , is less chemically reactive than silicon, etching through insulating material 62 at the bottom of trenches 66 requires additional time.
FIG. 4 d shows the results of the step shown in FIG. 4 c after insulating material 62 has been etched from the.bottom of trenches 66 The added time necessary to etch through insulating material 62 is another disadvantage of using fusion bonded handle wafer 52 with cavity 50 . Not only does the added etch time impair the efficiency of MEMS device fabrication, but also it jeopardizes the etching uniformity of trenches 66 , and may result in a large undercut due to the footing effect described previously for the SOI wafer process.
FIG. 5 is a perspective view of product wafer 70 including electrically isolated MEMS device structures 72 fabricated thereon according to a first embodiment of the present invention. Product wafer 70 has been thinned at each device location prior to fabrication of MEMS devices 72 using either anisotropic potassium hydroxide thinning (product wafer 82 in FIGS. 6 a - 6 d and 7 a - 7 d ) or planar wafer thinning (product wafer 112 in FIGS. 8 a - 8 f ), for example, processes well known to the art. With these processes, product wafer 70 is left exposed at the back side (that is, the side opposite MEMS devices 72 ). This eliminates the problems (i.e., footing, added etch time, etc.) seen in the prior art examples when a wafer is bonded to the back side of product wafer 70 , as will be described in further detail below.
FIGS. 6 a - 6 d show in cross-section the steps for fabricating electrically isolated MEMS device structures according to the first embodiment of the present invention. As a first step, shown in FIG. 6 a , isolation trenches 80 are reactive-ion etched through product wafer 82 . It should be noted that fabrication of uniformly straight-walled trenches 80 is readily achievable when a handle wafer is not bonded to the back side of product wafer 82 , thereby eliminating the footing effect that was seen in the first prior art example (FIGS. 2 a - 2 d ).
FIG. 6 b shows the result of the step shown in FIG. 6 a after isolation trenches 80 of product wafer 82 are filled with insulating material 86 . Because product wafer 82 is left exposed on both sides, insulating material 86 is deposited from both sides of product wafer 82 and isolation trenches 80 . As insulating material 86 is deposited, it builds up near the openings of isolation trenches 80 >faster than in the middle of the trenches. Similar to the situation in the prior art examples, keyholes 88 form as isolation trenches 80 fill near the trench openings. However, because there is still a mechanical connection at both the top and bottom of isolation trenches 80 , keyholes 88 are acceptably small. This added mechanical integrity is important to the functionality of the final MEMS device.
FIG. 6 c shows the result of the step shown in FIG. 6 b after etching insulating material 86 from the back side of product wafer 82 . This process leaves the back side of product wafer 82 exposed. Etching the back side of product wafer 82 is readily achievable because no wafer is bonded to the back side of product wafer 82 , thus allowing processing on both sides of the wafer. By etching insulating material 86 down to the back side of product wafer 82 ,devices fabricated on product wafer 82 will release immediately upon etching through product wafer 82 . This is beneficial because silicon nitride, a material typically used for insulating material 86 , requires a longer etch time than silicon. Furthermore, removing insulating material 86 from the back side of product wafer 82 eliminates potential adverse footing effects seen in the first prior art example (FIGS. 2 a-d ). However, this back side blanket etch of insulating material 86 removes some of the material from the bottom of isolation trenches 80 . Although the removed insulating material is desired for mechanical strength, the impact on the mechanical integrity of the final device is acceptably small.
FIG. 6 d shows the result of the step shown in FIG. 6 c after etching trenches 90 defining high-aspect ratio MEMS structures through product wafer 82 . As trenches 90 are etched through product wafer 82 they are released without any additional etching. This not only increases the efficiency of the MEMS device manufacturing process, but also maintains the straight-walled uniformity of both trenches 90 and isolation trenches 80 .
To eliminate keyholes 88 of the first embodiment of the present invention (FIGS. 6 a - 6 d ), a second embodiment is set forth in FIGS. 7 a - 7 d . In this embodiment, isolation trenches 100 are tapered from one side of product wafer 82 to the other (FIG. 7 a ). This solution is similar to that proposed to eliminate the keyholes of the prior art examples. However, since insulating material 104 deposits from both sides of product wafer 82 , isolation trenches 100 do not have to be wider at the top. Rather, isolation trenches 100 can be wider at the bottom (FIG. 7 b ). This avoids the situation that occurs when isolation trenches 100 are wider at the top wherein etching on the portion of wafer 82 around the narrower trench bottom is prevented by the wider trench top. Consequently, this prevents slivers of silicon from being left unetched near the bottom of isolation trenches 100 after subsequent process steps, thus preventing short circuits in the final device. Next, insulating material 104 is removed from the back side of product wafer 82 . As was seen in the first embodiment of the present invention (FIGS. 6 a - 6 d ); the blanket etch on the back side of product wafer 82 removes some of insulating material 104 from isolation trenches 100 (FIG. 7 c ). However, with the elimination of the keyhole in this embodiment, the strength loss from the back side blanket etch is insignificant. Finally, trenches 108 defining high-aspect MEMS device structures are etched through product wafer 82 (FIG. 7 d ). Because there is no handle wafer bonded to the back side of product wafer 82 and no insulation material 104 on the back side of product wafer 82 , this last step releases the completed MEMS devices from product wafer 82 .
FIGS. 8 a - 8 f show a third embodiment of the present invention wherein planar thinned wafers are used for product wafer 112 , rather than potassium hydroxide thinned wafers. Planar thinning, a process well known to the art, involves the use of an abrasive material (e.g., aluminum oxide) rather than reactive ions (e.g., potassium hydroxide) to remove a portion of the wafer prior to fabrication of high-aspect ratio MEMS devices. An advantage of using planar thinned wafers over potassium hydroxide thinned wafers is that planar thinned wafers allow processing such as photopatterning and lapping on the back side as well as the front, etching side of product wafer 112 . As a first step, to this embodiment, shown in FIG. 8 a , isolation trenches 110 are reactive-ion etched through product wafer 112 . Isolation trenches 10 are tapered from bottom to top so as to prevent formation of keyholes.
Next, a thin layer of insulating material 114 is deposited over wafer 112 and into isolation trenches 110 (FIG. 8 b ). It should be noted that, in this third embodiment, insulating material 114 does not fill isolation-trenches 110 , but rather coats the inner walls of the trenches. This is because insulating material 114 is not used as the trench-fill material in this embodiment. However, insulating material 114 still serves to electrically isolate the final MEMS structures.
A trench-fill material 116 , such as polysilicon, is then spread over insulating material 114 , as shown in FIG. 8 c . It is advantageous to use polysilicon to fill at least a portion of isolation trenches 110 because polysilicon deposits faster than silicon nitride (a material typically used for insulating material 114 ). Furthermore, the double deposition of insulating material 114 and polysilicon 116 is also well suited to use chemical mechanical polish (CMP) or normal lapping to planarize product wafer 112 .
FIG. 8 d shows the result of the step shown in FIG. 8 c after lapping polysilicon 116 down to insulating layer 114 , thus planarizing the top and bottom of product wafer 112 while leaving polysilicon 116 in isolation trenches 110 . Using aluminum oxide as the abrasive material for lapping, with a Knoop hardness of 2100, the silicon, at a Knoop hardness of 850, will be readily removed. At the same time, the silicon nitride, at a Knoop hardness of 3490, will not be significantly attacked by the abrasive and will act as a stop.
Taking advantage of the photopatterning possible on the back side of product wafer 112 , insulating material 114 on the bottom of product wafer 112 can be selectively removed, as shown in FIG. 8 e . This method of removing insulating layer 114 is advantageous over the blanket etch method shown in FIG. 7 c , in that it will increase the mechanical strength of trenches 118 defining high-aspect ratio MEMS device structures, especially when isolation trenches 110 are not tapered and a keyhole is present.
FIG. 8 f shows the result of the step shown in FIG. 8 e after trenches 118 have been reactive-ion etched through product wafer 112 . Because insulating material 114 was selectively removed from the back side of product wafer 112 in the previous step, the etching of trenches 118 releases the completed MEMS devices from product wafer 112 . This is advantageous over the prior art examples because no additional release step or etching is required to release the completed devices.
The present invention provides a method by which trenches that electrically isolate MEMS device structures are filled with insulating material in a novel fashion. Conventional methods of filling isolation trenches involve bonding a handle wafer to the back side of the product wafer. This not only requires added processing to release the handle wafer from the product wafer, but also only allows the isolation trenches to be filled from one side of the product wafer. Further, conventional methods of trench filling result in nonuniform filling,jeopardizing the mechanical integrity of the device. To remedy this, the present method provides means for filling isolation trenches from both sides of the product wafer by eliminating the use of a bonded handle wafer. In a first embodiment of the present invention, straight-walled isolation trenches are etched into a potassium hydroxide thinned wafer and are filled with insulating material from both sides of the wafer. This results in a keyhole that is acceptably small compared to the keyhole that is manifested using conventional filling methods. A second embodiment of the present invention also involves the use of a potassium hydroxide thinned wafer, but the trenches are tapered from one side of the wafer to the other. This eliminates the small keyhole that exists in the first embodiment ,further increasing the mechanical integrity of the final device. In a third embodiment of the present invention, the product wafer is initially thinned using planar wafer thinning. After isolation trenches are etched through the wafer, they are first coated with a thin layer of insulating material. The trenches are then filled with a material such as polysilicon. This double deposition is more efficient than conventional single deposition techniques because the trench-fill material generally deposits faster than the insulating material. Furthermore, double deposition is well suited to use CMP or normal lapping to planarize the product wafer down to the insulating layer.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.
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A method for filling a trench extending through a microelectromechanical system (MEMS) device patterned on a wafer is disclosed. The method involves simultaneously depositing a trench-fill layer of insulating material over a first side of the wafer, over a second side of the wafer, and into the trench extending from the first side to the second side. Further, the width of the trench at the first side of the wafer and/or the second side of the wafer is variable to adjust the rate at which the trench fills.
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The present application is a divisional of Ser. No. 09/847,462 filed 2 May 2001, issued as U.S. Pat. No. 6,616,074 on 9 Sep. 2003.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a broadcast spreader and more particularly to a broadcast spreader having a simple and reliable movable deflector.
2. Description of the Related Art
Rotary broadcast spreaders are well known in the art. For example, reference is made to U.S. Pat. Nos. 1,769,302; 1,998,966; 2,287,080; 2,474,064; 2,537,916; 2,687,892; 2,955,828; 2,958,530; 2,989,314; 3,085,807; 3,094,333; 3,109,657; 3,157,402; 3,226,461; 3,411,719; 3,478,970; 3,576,262; 3,682,395; 4,272,028; 4,367,848; 4,492,341; 4,511,090; 4,580,730; 4,597,531; 5,123,598; and 5,203,510. U.S. Pat. Nos. 4,580,730 and 4,597,531, in particular, are incorporated herein by reference. An impeller broadcast spreader includes a hopper which receives material to be dispensed, such as particulate or granular materials like fertilizer, pesticides and seeds. The hopper is mounted to a pair of wheels, and a gearset is mounted to an axle between the wheels. The gearset rotates when the wheels are rotated. This causes the impeller to rotate which in turn causes the dispensing particulate matter to be distributed. Generally the dispensed material is spread about five feet to the left and to the right of the centerline of the hopper. Controls are provided to meter the dispensed material and a deflector may be present with its own control, such as shown in U.S. Pat. No. 4,511,090.
A problem that has been bothering the industry is the handling of dispensed material when there is a sharp divide between different areas of a yard. For example, grass may be immediately adjacent a flowerbed or a driveway. In these situations when there is a need to seed or fertilize the lawn area, but not have the seed land on the driveway where it will do no good or in the flowerbed where it is not wanted, adjusting the pattern of distribution is difficult. Another problem relates to the dispensing of certain material. It is desired that control products, such as herbicides and pesticides, be restricted only to the area intended and not where it may do damage.
BRIEF SUMMARY OF THE INVENTION
The difficulties encountered have been overcome by the present invention. What is described here is a spreader for broadcasting particulate material in a controlled distribution pattern comprising a container for holding material to be dispensed, a pair of wheels connected to the container for facilitating movement of the container in a direction of travel, a rotatable plate mounted to the container for receiving dispensed material from the container and for distributing the material, a mechanism for rotating the plate, a deflector connected to the container for controlling the distribution of the material, the deflector being movable about the plate, a track attached to the container for supporting the deflector, a port disposed between the container and the plate for passing dispensed material and a port closure element connected to and movable with the deflector for selectively blocking the port.
There are a number of advantages, features and objects achieved with the present invention which are believed not to be available in earlier related devices. For example, one advantage is that the present invention provides a control of the pattern of dispensing material from a yard spreader. Another object of the present invention is to provide a broadcast spreader having a dispensing control mechanism which is simple, reliable and economical. A further advantage of the present invention is that the dispensing control mechanism is easy to operate. Another feature of the present invention is that undesirable dispensed material is blocked from striking a user pushing the spreader from behind.
A more complete understanding of the present invention and other objects, advantages and features thereof will be gained from a consideration of the following description of the preferred embodiment read in conjunction with the accompanying drawing provided herein.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a front isometric view of the broadcast spreader of the present invention.
FIG. 2 is a rear isometric view of the broadcast spreader of FIG. 1 .
FIG. 3 is a plan view of the container of the spreader shown in FIGS. 1 and 2 .
FIG. 4 is an upward looking isometric view of a mounting track of the present invention.
FIG. 5 is a downward looking rear isometric view of the mounting track of FIG. 4 .
FIG. 6 is a front elevation view of the mounting track shown in FIGS. 4 and 5 .
FIG. 7 is an enlarged sectional view taken along line 7 - 7 of FIG. 5 .
FIG. 8 is a front isometric view of a deflector of the present invention.
FIG. 9 is a downward looking rear isometric view of the deflector shown in FIG. 8 .
FIG. 10 is a sectional view taken along line 10 - 10 of FIG. 9 .
FIG. 11 is an upward looking isometric view of the deflector and track attached to the bottom of the container and showing the deflector in a retracted position.
FIG. 12 is an upward looking isometric view of the deflector and track mounted to the bottom of the container and showing the deflector in an extended position.
FIG. 13 is a diagrammatic plan view illustrating a spread pattern with the deflector retracted.
FIG. 14 is a diagrammatic plan view illustrating a spread pattern with the deflector extended.
DETAILED DESCRIPTION OF THE INVENTION
While the present invention is open to various modifications and alternative constructions, the preferred embodiment shown in the drawing will be described herein in detail. It is understood, however, that there is no intention to limit the invention to the particular form disclosed. On the contrary, the intention is to cover all modifications, equivalent structures and methods, and alternative constructions falling within the spirit and scope of the invention as expressed in the appended claims.
The simplicity of the new spreader may be seen by referring first to FIGS. 1 and 2 . Front and rear isometric views of a broadcast spreader 10 are illustrated. The spreader includes a container or hopper 12 into which particulate or granular material such as fertilizer, pesticides, herbicides, seed and the like are placed by a user. The hopper 12 is mounted to a pair of wheels 14 , 16 which are connected by an axle 18 . Connecting the hopper to the wheels and the axle are opposing tubular legs 20 , 22 which are also connected to a tubular handle 24 and a tubular rest stand 26 .
Located beneath the hopper 12 is a rotatable plate, rotor plate or impeller 30 which is driven by a set of gears within a gearbox 32 . The upper portion of the tubular handle may include a foam grip 34 , and the spreader may be foldable at a junction 36 to allow storage and shipping in a compact configuration. A hopper closure assembly including a closure lever 40 , an adjustment micrometer 42 , a control wire 44 and a slidable closure plate 46 are provided to allow an operator to meter the amount of material which leaves the hopper. The hopper has an opening 45 , FIG. 3 , at its lowest elevation through which the dispensing material leaves the hopper. The closure plate 46 is mounted to the hopper to block or unblock the opening 45 depending upon whether the spreader is in use. When in use, an operator may manipulate the micrometer to adjust the degree to which the opening is unblocked. If larger particulate matter is being dispensed, the closure plate may block less of the opening. If fine material is being dispensed, more of the opening may be blocked. The position of the closure plate is controlled by the lever 40 and the micrometer 42 and the decisions of the user are transmitted by the wire 44 to the closure plate. Disposed just upstream of the impeller 30 are a deflector 50 and a track 52 to which the deflector is mounted in a rotatable relationship.
The deflector and track are simple, reliable and economical as reference to FIGS. 4-7 and then 8 - 10 will show. In FIGS. 4-7 , there is illustrated the integral one piece molded mounting track 52 having two attachment tabs 62 , 64 . Each tab has a hole for receiving a fastener for connection to the hopper 12 . The mounting track has an arcuate shape extending approximately one hundred and fifty five degrees and a smooth inner surface 66 . An outer surface 68 is reinforced by several ribs such as the rib 70 . The mounting track has a generally smoothly curved upsidedown L-shaped cross section as illustrated in FIG. 7 . A flange 72 extends from a lower edge. Depending fingers 73 , 74 , 75 are provided at spaced intervals along the flange 72 to receive and support a mating flange on the deflector as will be explained hereinbelow. A similar series of fingers 76 , 77 , 78 are located at the upper edge of the mounting track for the purpose of receiving and supporting another flange of the deflector as will also be explained hereinbelow. A channel shaped passage 79 is formed in the upper portion of the mounting track for accommodating a deflector operating link or cable 80 , FIGS. 1 and 2 .
Referring now to FIGS. 8-10 , the deflector 50 is illustrated in detail. The deflector has two portions, an arcuate shaped portion 102 and a radially extending arm portion 104 . The arcuate shaped portion 102 extends for approximately one hundred and twenty five degrees and includes a generally smoothly curved, upsidedown L-shaped cross section as shown in FIGS. 8 and 10 . The deflector has a smooth interior surface 106 and a similarly smooth exterior surface 108 which is to nest adjacent the inner surface 66 of the track 52 . A lower flange 110 is integral with the arcuate portion. An upper region 111 of the arcuate portion adjacent an upper edge 112 is formed like a flange to be received by the upper fingers 76 , 77 , 78 of the mounting track, FIG. 4 . The lower flange 110 of the deflector is adapted to be received by the lower fingers 73 , 74 , 75 on the mounting track. In this way the deflector may be engaged with the mounting track and supported thereby.
The deflector may be rotated between a retracted position as shown in FIG. 11 and a fully extended position as shown in FIG. 12 . The shape of the deflector matches that of the mounting track although the deflector extends for about one hundred and twenty five degrees. One can now appreciate that whether the deflector is in the retracted position or in the fully extended position or in any position in between, some dispensing material flowing from the hopper unto the rotating plate will impact the deflector. When the deflector is retracted, it and the track protect a user pushing the spreader from the dispensing material. When the deflector is fully extended, the mounting track is mostly exposed to block any particulate matter being distributed from hitting the user of the spreader. When the deflector is fully extended particulate material is also prevented from being distributed to the right of the spreader as will be explained. When retracted the combined track and deflector extend about one hundred and fifty-five degrees. When the deflector is extended the combined track and deflector extend about two hundred and twenty degrees.
The radially extending arm portion 104 extends from the leading end of the arcuate shaped portion 106 and includes a circular rim 114 and a bearing ring 116 that mates with a center post of the rotatable plate 30 . Extending beyond the circular rim is a projecting closure panel 118 . This panel acts as a valve for partially blocking a port through which the dispensing material flows when the spreader is operating and the closure plate 46 unblocks the hopper opening 45 . When the deflector is rotated relative to the mounting track, the blocking panel 118 also rotates and moves relative to the port for partially blocking the port to reduce the flow of dispensing material.
It should be noted that while the deflector rotated about the axis of rotation of the rotor plate in a generally horizontal plane, the deflector is offset slightly, about 0.030 inches, so that a lesser movement of a control lever is able to set the deflector's disposition. Also, forming the deflector as a molded, integral piece, means that only one operating lever is needed since the arcuate portion of the deflector and the arm portion with the closure panel move as one element. To facilitate movement of the deflector a hole 120 is formed in the radially extending arm portion 104 . The cable 80 leading to a control lever 122 , FIGS. 1 and 2 , may be connected to the arm portion through the hole.
Referring now to FIGS. 11 and 12 , the deflector is shown mounted to the underside of the hopper. There is also shown a port 126 which is disposed just downstream of the opening 45 in the hopper. In FIG. 11 , the deflector 50 is shown attached to the mounting track 52 . The upper region 111 of the deflector is engaged by the fingers 76 , 77 , 78 of the mounting track, and the flange 110 is engaged with the fingers 73 , 74 , 75 . There is a substantial arcuate overlap of the deflector with the mounting track. In this position, the port 126 is fully open or fully unblocked by the closure panel 118 . During operation, a full spread will be dispensed with only the rearward distribution of material being blocked by the deflector and to a smaller extent by that portion of the mounting track not covered by the deflector. It is noted that when the spreader is in operation, the deflector will always be impacted by the dispensing material whether in the retracted or in the extended position. A feature of the spreader is now apparent. None of the dispensed material will hit the user who will be located rearward of the spreader. This keeps the user clean and prevents undesirable material from landing on the user's clothes or shoes.
Referring to FIG. 12 , the deflector 50 is shown in its fully extended position. Much more of the mounting track is now exposed and the region to the right side of the rotor plate is blocked. This prevents rightward distribution. If there is a driveway or flowerbed to the right of a lawn, the lawn may be provided with a distributed material but not the flowerbed or the driveway. While the deflector is illustrated fully extended in FIG. 12 , a user may limit the extension of the deflector to any one of an infinite number of positions between the retracted position of FIG. 11 and the extended position of FIG. 12 . This provides for close control of the distribution pattern of the material.
It is again noted that regardless of the position of the deflector, it will be impacted by dispensed material when the spreader is operating. Also the user will always be protected from rearward projecting dispensed material. Both of these features are advantages of the present invention. It is further noted that because of the slight offset of the deflector, it will still rotate in a generally horizontal plane but it will move slightly outwardly and forwardly. Essentially, there is no vertical movement which may expose the region to the rear of the rotor plate to dispensing material as is the case with some older spreaders.
Again referring to FIGS. 11 and 12 , it is noted that when the deflector is in a retracted position ( FIG. 11 ), the closure panel 118 is in an unblocked position so that the full quantity of material will be dispensed through the port 126 . However, when the deflector is deployed by rotation in a clockwise direction toward the extended position ( FIG. 12 ), the closure panel also rotates clockwise to partially cover the port. (The view to determine rotational direction is made from under the hopper, looking upwardly.) The closure panel 118 will progressively block more and more of the port 126 as the deflector is extended resulting in a progressive reduction of the flow of material from the hopper. With the deflector extended, less ground is covered by the dispensed material. Hence, it is highly desirable to reduce the total amount of material dispensed so as to avoid “ridging” or the over-concentration of dispensed material.
The linkage mechanism for controlling the deflector includes the cable 80 attached to the deflector arm portion 104 after passing through the passage 79 in the track. The cable leads to the control lever 122 , mounted to the handle 24 . The lever may be operated by a user's thumb to extend or retract the cable and thereby to rotate the deflector one way or the other. It is noted that the same control lever operates both the deflector and the closure panel.
In operation, a user 140 , FIGS. 13 , 14 , fills the hopper 12 and sets the micrometer. The user sets the location of the deflector, pushes on the closure lever 40 and moves forward (in the direction of the arrow 142 ) by pushing on the handle 24 . When the deflector is fully retracted, the spread of material is fan shaped 144 , FIG. 13 , extending about one hundred and thirty degrees. When the deflector is fully extended, the distribution is a partial fan shape 146 as shown in FIG. 14 and extending about eighty degrees. By adjusting the lever 122 , the “fan shape” distribution may be contracted as desired. Hence, if a driveway edge 148 is to the right of the user (when facing in the direction of travel) he/she can move the deflector to cause the distribution pattern to cease at the driveway edge in a line nearly identical to the line traversed by the right wheel of the spreader. Not only is the distribution pattern closely controlled but concentrations of the material to be spread are also controlled, automatically, because the placement of the deflector 50 also determines the degree to which the port 126 is blocked by the closure panel 118 . The greater the spread pattern, the more material is dispensed; with a smaller pattern, less material is dispensed.
The full spread pattern shown in FIG. 13 is an elongated strip extending as far as the user walks and having a width identical to the width of the fan 144 , in practice, about ten feet. The head of the strip will be almost a semicircle. The partial spread shown in FIG. 14 is also a strip, but a narrow one having a width equal to the width of the partial fan 146 . The volume of material deposited in the wider strip will be greater than the volume of material deposited in the narrower strip because of the partial block of the port through which the material passes when flowing from the hopper to the rotor plate.
The specification describes in detail an embodiment of the present invention. Other modifications and variations will, under the doctrine of equivalents, come within the scope of the appended claims. For example, changing the dimensions of the hopper, the hopper opening, the port size, the deflector or any other element will still result in equivalent structures. Also changing the arcuate extent of the deflector and/or the mounting track are also considered equivalent structures. Still other alternatives will also be equivalent as will many new technologies. There is no desire or intention here to limit in any way the application of the doctrine of equivalents.
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A broadcast spreader with a movable deflector is disclosed. The spreader distributes particulate material by a rotating plate which when operating, always impacts material on the deflector. The deflector and a mounting track prevent dispensing material impacting on a user of the spreader, and when the deflector is extended, also prevent dispensing material distributing to the right side of the spreader. In this way, lawns which abut a driveway or a flowerbed may have material distributed on them without also depositing material on the driveway or flowerbed. Further, the deflector is integral with a port closure panel which automatically reduces, in a proportional manner, the flow of particulate material as the deflector is extended.
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THE FIELD OF THE INVENTION
This invention relates to adhesives. More precisely, the invention relates to improved reactive fluid adhesive compositions.
DESCRIPTION OF THE PRIOR ART
Reactive fluid adhesive compositions are known which are at least substantially solvent free, and cure by polymerization of monomeric components to provide strong adhesive bonds between surfaces of many different materials. These adhesive compositions may comprise two parts: one part comprising polymerizable acrylate or methacrylate ester monomers and a source of free radicals such as a peroxide or hydroperoxide and the other part comprising an activator for initiation of polymerization of the monomers at room temperature. The activator is conveniently one which can be used in nonstoichiometric quantities with respect to the monomers.
In one particularly convenient method of using reactive fluid adhesives, the part comprising the activator may be applied to the surfaces to be bonded in the manner of a primer prior to the application of the other or first part of the composition comprising the polymerizable monomers. This method allows the use of the adhesive composition without having to mix the two parts prior to application.
U.S. Pat. No. 3,890,407, describes and claims adhesive compositions comprising a solution of certain sulpur bearing compositions selected from chlorosulphonated polyethylene and a mixture of sulphonyl chloride with chlorinated polyethylene in at least one polymerizable vinyl monomer, for example methyl methacrylate monomer. According to U.S. Pat. No. 3,890,407, the sulfur bearing composition can contain between about 20 to about 70 weight percent chlorine.
Although adhesive compositions of this type have excellent bonding and performance characteristics, they do not generally provide an adhesive which sets sufficiently within 20 seconds of application to provide an acceptable handleable bond to a variety of surfaces. This disadvantage is particularly significant under production line conditions where it is highly desirable that adhesively bonded articles are bonded strongly enough for handling immediately after the parts to be bonded have been pressed together. This disadvantage is believed to result from the fact that polymerization of the monomers used in such a method begins at the surfaces of the layers of the two parts of the composition, where the monomers, peroxide and activators are in contact, and continued polymerization through the monomer containing layer is hindered by a number of factors. These hindering factors are considered to be related to the nature of the chemical ingredients used, their physical disposition to each other in the composition and the characteristics of the curing phenomenon.
A known method for increasing the speed of reaction of polymerizable compositions including acrylic monomers involves including minor proportions of polyunsaturated monomers in the composition to provide an increased quantity of potentially reactive sites. However, large quantities of such monomers tend to lead to cross-linked structures which in extreme cases tend to be hard and brittle and accordingly unsuitable for many adhesive applications. Moreover, polyunsaturated monomers such as diunsaturated monomers are generally so incompatible with chlorosulphonated polyethylenes as to preclude their use in large quantities in adhesives such as those described in U.S. Pat. No. 3,890,407 while tri- and higher polyunsaturated monomers are generally regarded as more incompatible.
SUMMARY OF THE INVENTION
The adhesive compositions of the present invention include first part compositions which are homogeneous solutions comprising selected sulfur-bearing compositions and substantial quantities of certain compatible polyunsaturated acrylic monomer materials in controlled proportions in vinyl monomer. The combination of a first part composition with an activator forms an adhesive composition which sets within as little as ten seconds to provide adhesive bonds of acceptable strength, and continues to cure to an acceptable bond strength over a period of several hours.
DESCRIPTION OF PREFERRED EMBODIMENTS
Homogeneous solution compositions providing a first part for adhesive compositions of the present invention comprise vinyl monomers polymerizable by a free radical mechanism. For the purpose of this invention "vinyl monomers" include acrylic monomers and mixtures of monomers, such as methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, butyl metahacrylate, cyclohexyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methacrylic acid, acrylic acid, glycidyl methacrylate itaconic acid, ethylene glycol and higher-glycol acrylates and methacrylates, acrylamide, and methacrylamide, halogenated monomers such as vinylidene chloride, chlorostyrene, 2,3-dichloro-1,3-butadiene, and 2-chlor-1,3-butadiene, and styrene and mono- and poly-alkylstyrenes, such as methylstyrene, dimethylstyrene, ethylstyrene, or tert-butylstyrene. Some of the aforementioned compounds are not, from a strictly chemical standpoint, "vinyl" monomers, but are regarded as such in the plastics art. The term "vinyl monomers" is used here in this broadened sense.
The preferred monomers are acrylate monomers, (i.e. esters of acrylic or methacrylic acid), especially c 1-8 alkyl acrylates and methacrylates.
A source of free radicals such as an organic peroxide (e.g. an organic hydroperoxide), a perester, or a peracid may also be included in the homogeneous solution. The preferred material is cumene hydroperoxide.
First part homogeneous solution compositions providing adhesive compositions of this invention also include sulfur-bearing compositions selected from chlorosulfonated polyethylene or a mixture of chlorinated polyethylene and sulfonyl chloride. The selected sulfur-bearing composition has a comparatively high chlorine content in order to achieve necessary compatability and reaction characteristics. Preferably, the chlorine content of the selected sulfur-bearing composition should be no less than about 35% by weight and the sulfur content should be greater than about 1.0% by weight. The selected sulfur-bearing composition is preferably used in amounts from about 20 to about 40% by weight of the first part composition. While larger amounts of the selected sulfur-bearing composition generally tend to lead to faster setting and higher tensile shear values, increasingly large amounts also tend to interfere with stability of the solutions. Smaller amounts of the selected sulfur-bearing composition tend to lead to first part compositions having viscosities which are too low for many adhesive purposes. A particularly preferred adhesive composition includes 30 to 35% by weight of the first part compositions of a chlorosulphonated polyethylene supplied by DuPont de Nemours Company under the Trade Name Hypalon 30, which is stated to have a chlorine content of 43% by weight, a sulphur content of 1.1% by weight and a Mooney viscosity of 30.
First part homogeneous solution compositions providing adhesive compositions of the present invention also include a compatible polyunsaturated monomeric material having three or more ethylenically unsaturated double bonds in its molecular chain. Additionally, the compatible monomeric material is one which can be mixed with the selected sulfur-bearing composition and vinyl monomer(s) to provide a homogeneous single liquid phase composition stable at temperatures between about 10° C. to about 30° C. over a period in excess of three months. Accordingly, for the purposes of this invention, "compatible polyunsaturated monomeric material" means a monomeric material having three or more ethylenically unsaturated double bonds in its molecular chain and which when mixed into a solution of Hypalon 30 in methyl methacrylate and acrylic acid to an extent that the solution comprises 20% by weight of the polyunsaturated monomeric material, does not separate when stored for three months in a sealed glass bottle at 20° C. Trimethylol propane tri-methacrylate is a particularly preferred compatible polyunsaturated monomeric material which meets this definition. An example of a polyunsaturated monomeric material which does not meet the defined compatibility criterion is pentraacrythritol tetracrylate.
First part compositions according to the invention also comprise 1.0 to 30% by weight of a compatible organic acid. Preferred acids are also vinyl compounds as above referred to, for example acrylic or methacrylic acid. The first part compositions may also include 0.01 to 10% by weight of stabilizers for example hydroquinone or 2,6-di-t-butyl-4-methylphenol.
The first part homogeneous solution compositions described above are combined with a second part composition comprising an activator to provide the adhesive compositions of this invention.
Activator compounds suitable for use in the second part may include for example a tertiary amine such as N,N-dimethylaniline, N,N-diethylaniline, N,N-diisopropyl (p-toluidine), or a condensation product of an aldehyde and a primary or secondary amine such as a condensation product of butyraldehyde with aniline or butylamine, or a condensation product of crotonaldehyde and aniline. Examples of suitable activators include DuPont accelerators 808 and 833, and Vulcazit 576 from Bayer AG.
Rapid setting of bonds to a finger-tight condition is achieved with second part compositions which include a promoter in combination with the activator. Suitable promotors capable of shortening the time required for curing of the adhesive composition include oxidizable organic compounds of transition metals such as cobalt, nickel, manganese. Other suitable promotors include iron naphthenates, copper octoate, iron hexoate, or iron propionate, or complexes of acetyl acetone with iron, copper, cobalt or vanadium.
Manners of making and using the invention as well as advantages derived from practicing the invention will be more fully appreciated from the following Examples presented to illustrate and not to limit the invention.
In the Examples, the adhesive composition was provided by combining a first part homogeneous solution composition with a second part composition including an activator. Each first part composition comprised ingredients in amounts by weight shown in Table 1 (First Part Compositions I-VI). These ingredients provided a homogeneous solution in vinyl monomer comprising methyl methacrylate as solvent, of 20 to 40% by weight of the solution of Hypalon 30, and 5 to 25% by weight of the solution of a compatible polyunsaturated monomeric material namely trimethylol propane trimethacrylate.
As will be seen from Table 1, for First Part Compositions I-VI, the ratio by weight of Hypalon 30 (H) to methyl methacrylate (M) lies in the range 1:0.9 to 1:1.5 the ratio by weight of Hypalon 30 to trimethylolpropane trimethacrylate (T) lies in the range 1:0.1 to 1:1, and the ratio by weight of methyl methacrylate (M) to trimethylol propane trimethacrylate (T) lies in the range 1:0.1 to 1:0.6. Further, the ratio by weight of (H) and (T) to vinyl monomer lies in the range 1:1.2 to 1:0.8.
EXAMPLE 1
Setting time and shear strength was examined of steel to steel bonds formed by combining First Part Compositions I-VI with a second part comprising a solution in acetone of 10% by weight DuPont Accelerator 808 and 0.1% vanadium acetonyl acetonate. It was observed that setting time was reduced when the higher quantities of Hypalon and trimethylol propane were present, and bond strength was increased when the higher quantities of Hypalon were present.
For these tests, sample bonds were formed from steel coupons 100 mm×25.4 mm overlapping by 12.7 mm with the adhesive between the overlapping portions. The steel coupons were prepared by sand blasting, rinsing with acetone and drying in air at room temperature. The second part was then painted onto the coupons and allowed to dry by evaporation of the solvent. The first part (Composition I-VI) was then applied as a thin coating on one of the coupons. The steel coupons were then pressed together firmly with the adhesive between them.
The setting time was determined by forming the bond and observing the period of time, in seconds, during which it remained possible for the observer to open the bond with his fingers by moderate hand power.
Shear strength of the sample bonds were determined at 20° C. (in Newtons per square mm) 24 hours after forming the sample bonds. An Instron machine set to peel the bonds apart at a rate of 1 mm per minute was used.
Results of these tests are shown in graph form in FIGS. 1, 2 and 3. FIG. 1 shows the setting time for adhesive compositions comprising Compositions I, II, III and IV as a first part and in which the contents of Hypalon 30 (H) and acrylic acid (A) are maintained at a constant level and the contents of methyl methacrylate (M) and trimethlol propane trimethacrylate (T) are varied. In this FIG. 1 the setting time is plotted against the amount of (T) present as a percentage by weight in the solution. It can be seen from FIG. I that the setting time is reduced with increasing content of trimethylolpropane trimethacrylate, and that amounts in excess of 15% by weight of the solution provide exceptionally fast setting adhesives with settng times of 20 seconds or less.
FIG. 2 shows the setting time for adhesive compositions comprising Compositions IV, V and VI, as a first part and in which the contents of trimethylolpropane trimethacrylate and acrylic acid are maintained at a constant level and the contents of Hypalon (H) and methyl methacrylate are varied. In this FIG. 2 the setting time is plotted against the amount of (H) present as a percentage by weight in the solution. It can be seen from FIG. 2 that the setting time is reduced with increasing content of Hypalon 30, and that amounts in excess of 25% by weight of the solution provide exceptionally fast setting adhesives with setting times of 15 seconds or less.
FIG. 3 shows the tensile shear strength of adhesive compositions comprising Compositions IV, V and VI as a first part. The tensile shear strength is plotted against the amount of (H) present as a percentage by weight of the solution. It can be seen from FIG. 3 that the bond strength is increased with increasing content of Hypalon 30.
EXAMPLE 2
Composition IV was used to prepare adhesive compositions as described in Example 1 using the same second part as in Example 1. The sample bonds were subjected to the tensile shear test five minutes after formation of the bond, and 60 minutes after formation of the bond. Results of 9.5 and 12.0 N/mm 2 respectively were recorded.
EXAMPLE 3
Composition IV was used to prepare adhesive compositions as described in Examples 1 and 2 but using as a second part, either a solution in acetone of 10% by weight Accelerator 808 and 0.1% Cu(II) acetylacetonate. Setting times of 5 to 10 seconds were observed in both cases.
TABLE I______________________________________Example Adhesives - Part A. I II III IV V VI______________________________________Chloro-sulphonated 35 35 35 35 25 30polyethylene(H)Methyl 50 45 40 35 45 40methacrylate(M)Trimethylol 5 10 15 20 20 20propanetri-methacrylate(T)Acrylic acid 10 10 10 10 10 10(A)Cumenehydro- 1 1 1 1 1 1peroxide2 . 6 . di-t-butyl-4- 0.5 0.5 0.5 0.5 0.5 0.5methylphenolRatio of:-H:M 1:1.43 1:1.28 1:1.14 1:1 1:1.8 1:1.3H:T 1:0.13 1:0.28 1:0.43 1:0.57 1:0.8 1:0.67M:T 1:0.1 1:0.22 1:0.38 1:0.57 1:0.22 1:0.5H+T: A+M 1:1.5 1:1.22 1:1 1:0.82 1:1.2 1:1______________________________________
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An adhesive composition formed by combining two parts capable of causing polymerization to form adhesive bonds rapidly. One part comprises polymerizable vinyl monomer, selected chloro-sulphonated polyethylenes or mixtures of sulphonyl chlorides and chlorinated polyethylenes, compatible monomeric material having three or more ethylenically unsaturated double bonds. The other part comprises an activator.
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FIELD OF THE INVENTION
The present invention relates generally to retail display devices and more particularly to a modular wallcovering display rack for providing a convenient and cost effective means of displaying wallpaper samples and the like to potential customers.
BACKGROUND OF THE INVENTION
As is well known, wallcoverings, such as wallpaper, are typically marketed to customers via sample books which comprise a collection of various samples of wallcoverings from a particular manufacturer. By manually paging through such sample books a customer/purchaser is given an opportunity to choose a particular wallcovering according to the customer's own tastes and desires. Although such sample books have proven generally suitable for their intended purpose, they possess inherent deficiencies which detract from their overall effectiveness in the marketplace.
In this regard, the use of such prior art sample books limits the number of wallcoverings that can be displayed at any given time to essentially the one wallcovering visible on the open page of the sample book. As such, the customer must view the samples essentially one at a time by manually turning pages within the prior art wallcovering sample book. This makes comparisons difficult and is an extreme inconvenience when attempting to decide between several different wallcoverings.
The use of such prior art wallcovering sample books also limits viewing of the samples essentially to a single customer. It is virtually impossible for several customers having different wallcovering needs to utilize a single sample book simultaneously.
Further, the prior art wallcovering sample books are typically heavy and awkward to manipulate. This is a problem since it is often desirable to carry one or more sample books to a different location in order to observe particular samples under specific lighting conditions or next to another sample or object. Also, the size and weight of the sample book makes moving the same extremely inconvenient and may require the aid of a sales person.
In addition, frequently the customer desires to take a sample of a wallcovering off premises so that the sample may be viewed in the environment in which it is to be used in order to judge the aesthetic compatibility of the sample to its environment. This entails transporting the sample book from the retail outlet to the location where a new wallcovering is desired. Removal of the sample book from the retail outlet reduces that outlet's marketing effectiveness and incurs the risk that the sample book may be damaged or not returned.
As such, although the prior art sample book has recognized to a limited extent the problem of providing customers with a means of viewing various wallcovering samples and the problem of providing a means of viewing a desired wallcovering sample in the environment in which it is to be used, the proposed solutions have to date been ineffective in providing a satisfactory remedy.
SUMMARY OF THE INVENTION
The present invention specifically addresses and alleviates the above-mentioned deficiencies associated in the prior art. More particularly, the present invention comprises a modular wallcovering display rack for providing a convenient and cost effective means of displaying wallcovering samples and the like to potential customers. The wallcovering display rack is fabricated in modular form so that it may be adapted to fit various store configurations and is also easily expandable.
The wallcovering display rack comprises a plurality of vertically stacked, inclined shelves upon which individual sheets of wallcovering samples may be placed for display. Vertical columns support the shelves and house fluorescent lights which provide a soft, even illumination of the wallcovering samples. An individual Wallcovering sample can be easily removed from the wallcovering rack for closer inspection. The ease of removal also facilitates rapid sample changes to reflect updates in inventory and changes in fashion and design taste.
Each vertical support column has an array of pockets positioned in alignment with and adjacent to the stack of shelves. Each pocket may contain a plurality of wallcovering samples of the type displayed in the adjacent shelf. A customer may thus remove and keep a sample from the pocket for use in deciding upon a particular wallcovering.
Use of the wallcovering display rack of the present invention facilitates segregation of wallcoverings according to both type and color, thereby making it easier for the customer to quickly find the desired wallcovering. For example, each individual vertical stack or module of sample wallcoverings may contain a separate type of wallcovering. One stack could contain floral patterns while another could contain striped patterns. Colors could then be distributed throughout each stack such that all reds, for instance, are at the upper-most end of the stack and all blues are at the lower-most end of each stack, with various other colors arranged similarly therebetween.
Thus, a customer approaching the wallcovering display rack may almost instantly recognize the desired type of wallpaper and may quickly scan down that column of shelves to locate the desired color.
These, as well as other advantages of the present invention will be more apparent from the following description and drawings. It is understood that changes in the specific structure shown and described may be made within the scope of the claims without departing from the spirit of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the wallcovering display rack of the present invention;
FIG. 2 is a perspective view of one side of the wallcovering display rack of FIG. 1 having shelves removed to show the important features of the rack;
FIG. 3 is a perspective view of the rear of the wallcovering displaY rack of FIG. 2;
FIG. 4 is an exploded view of two columns and a base of a single module of the wallcovering display rack of the present invention;
FIG. 5 is a plan side view of a vertical support column showing the relative positions and orientations of the shelves;
FIG. 6 is a perspective view of the upper surface of a single shelf;
FIG. 7 is an enlarged perspective view of a portion of a single module showing the shelf support posts and the sample pockets formed on each column;
FIG. 8 is an enlarged side view showing a single shelf resting upon two shelf support posts which extend from a vertical support column;
FIG. 9 is an enlarged sectional perspective view of a vertical support column showing a fluorescent light and fixture housed therein;
FIG. 10 is an enlarged sectional view taken along lines 10--10 of FIG. 3 of several shelves within a stack showing the attachment of the shelves to the vertical support member using attachment hooks and shelf posts;
FIG. 11 is an enlarged sectional view of a single shelf and a shelf support post showing the attachment hook by which the shelf is attached to the shelf posts; and
FIG. 11a is a rear perspective view of a single shelf showing the hooks by which the shelf is attached to the posts.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The wallcovering display rack of the present invention is illustrated in FIGS. 1-11a which depict a presently preferred embodiment of the invention.
Referring to FIG. 1, plural shelves 10 are stacked vertically and spaced sufficiently from one another to permit the easy insertion and viewing of a sheet of wallcovering samples. The shelves 10 are angularly inclined such that a person standing before them may easily view the outer-most edge of each wallcovering sample. The wallcovering display rack is comprised of a plurality of such modules or stacks of shelves 10 separated by intermediate support columns 16 and terminated on either end by first 12 and second 14 end support columns.
Two such arrays of shelves may be placed back to back as depicted in FIG. 1 to form a single display rack. Base trim 36 may be added to secure the individual modules together and to enhance the wallcovering display rack's aesthetic appeal. An optional semi-circular base member 46, shown in phantom, can also be added to help secure the front display rack to the rear display rack and to further enhance the aesthetic appeal of the display racks.
The wallcovering display rack of the preferred embodiment can be constructed using wood products, such as plywood, lumber, particle board, or the like. The use of wood products permits the simple and inexpensive manufacture and assembly of the wallcovering display rack of the present invention. Those skilled in the art will recognize, however, that other materials, such as plastics or glass, and conventional methods of manufacture are also suitable.
Referring now to FIGS. 2 and 3, light apertures 20 provide an opening through which a fluorescent lamp disposed within each of the support columns 12, 14, and 16, may illuminate the wallcovering samples disposed upon each shelf, thereby facilitating their proper display. A light filter/diffuser 22 disposed at the upper-most end of each light opening 20 diffuses the intensity of the light falling upon the upper-most shelf 10 and provides a pleasing aesthetic effect.
Pockets 24, formed upon each of the support columns 12, 14, and 16, allow small take-home samples of each of the wallcoverings to be disposed adjacent the shelf displaying that wallcovering. These small take-home samples of wallcovering may be removed by the customer and kept in order to help the customer decide upon which wallcovering to purchase.
Bases 18 space the lower-most shelf 10 a few inches off of the floor to permit better viewing and to provide easier access. Gussets 78 strengthen the corners of bases 18 and provide rigidity thereto. Fasteners, such as bolts 40, attach bases 18 to intermediate support columns 16 and end support columns 12 and 14. The base trim 36 is attached to the bases 18, thus concealing the bases 18 from view.
First 28 and second 30 long horizontal members rigidly connect first 12 and second 14 end support columns. Fasteners, such as screws 38, are used to attach first 28 and second 30 long horizontal members to the first 12 and second 14 end support columns.
First 32 and second 34 short horizontal members rigidly connect intermediate support columns 16. Fasteners, such as screws 38, may be used to attach first 32 and second 34 short horizontal members to the intermediate support columns 16. The desired number of modules or stacks of shelves 10 can thus be connected together to form a composite wallcovering display rack of the desired length.
Referring now to FIG. 4, an exploded view of an end support column 12, a base 18, and an intermediate support column 16 is presented. The end support column 12 is comprises of inside panel 48, outside panel 50, front vertical member 52, and spacer 76. The inside panel 48, outside panel 50, front vertical member 52, and spacer 76 are assembled using suitable fasteners, such as wood screws. End support column 14 is constructed in a similar manner. Spacers 76 add rigidity to end support columns 12 and 14 and maintain the proper spacing of panels 48 and 50.
A fluorescent lamp fixture 64 is disposed within each end support column 12 and 14. The fluorescent lamp illuminates the displayed wallcovering samples through light opening 20. Filter/diffuser 22 extends from the upper-most end of light opening 20 a distance downwards such that it terminates below the upper-most shelf 10 in each module. Filter/diffuser 22 diffuses the intensity of the light cast upon the upper-most shelf 10 and also provides a pleasing aesthetic effect. The intensity of the light cast upon the upper-most shelf 10 is reduced due to the larger surface area of the light opening 20 disposed above the top shelf 10.
Each intermediate support column 16 is comprises of first 56 and second 58 side panels, front vertical member 60, and rear vertical member 62. The first 56 and second 58 side panels, front vertical member 60, and rear vertical member 62 are attached using suitable fasteners, such as wood screws. A fluorescent light fixture 64 is disposed within each intermediate support column 16 in a like manner to that of each end support column 12 and 14. Each intermediate support column 16 also has a light opening 20 on either side and a filter 22 disposed in the upper-most portion of each light opening 20.
A quadrilateral base 18 is comprises of longitudinal members 80 and lateral members 82. The intersection of each longitudinal 80 and lateral 82 member is reinforced by a gusset 78. Bolt holes 41 accept bolts which attach the base 18 to end support columns 12 and 14 or to intermediate support columns 16.
Referring now to FIG. 5, a side view of an intermediate support column 16 showing the relative placements and orientations of the shelves 10 is illustrated. The shelves 10 disposed at the lower-most portion of the stack are inclined somewhat less than the shelves 10 disposed in the middle and upper-most portions of the stack. This facilitates the convenient viewing of the lower-most shelves 10 by customers. The outline of an end support column 12 or 14 is depicted in phantom to provide a comparison to the intermediate support columns 16.
Referring now to FIG. 6, a single shelf 10 is illustrated. Each shelf 10 is comprised of a planar member 74 and a stop 72 formed perpendicular to the planar member 74 and disposed along the front edge of the planar member 74. The stop 72 prevents a sample wall covering sheet from sliding downward off of the inclined shelf 10.
As best shown in FIG. 11, each shelf 10 further comprises a rear hook 42 and front hooks 43. Rear hook 42 engages posts 26 disposed upon end support columns 12 and 14 and intermediate support columns 16. Front hooks 43 secure the front of each shelf 10 to front posts 27. This prevents the front of the shelf 10 from being bumped upwards when a lower shelf is being removed or installed. The rear hook 42 and the front hooks 43 secure the shelf 10 in place within the wallcovering display rack and also permit the shelf 10 to be easily repositioned, cleaned, or replaced.
The positioning of the rear hook 42 and the front hooks 43 upon the lower surface of the shelves 10 is illustrated in FIG. 11a. The rear hook 42 extends across a substantial portion of the rear of each shelf 10 and provides structural support thereto. Two separate front hooks 43 are used. One front hook 43 is disposed upon either side of the front lower surface of the planar member 74.
A wallcovering sample 68 is shown disposed upon a shelf 10 of FIG. 6. Wallcovering samples 68, such as wallpaper, are cut to approximately the same dimensions as the planar member 74 and disposed upon the shelf 10 with their decorative side upper-most such that it can be viewed by customers.
The wallcovering sample 68 may be viewed under various lighting conditions, such as by viewing it near an open window or under incandescent lights. The wallcovering sample may also be compared to items brought into the retail outlet by the customer. It is not intended that the sample wallcovering 68 generally be removed from the retail outlet by the customer. Smaller precut take-home samples are provided for this purpose in each pocket 24 located adjacent shelves 10.
Referring to FIGS. 7 and 8, mounting of the shelves 10 upon the posts 26 and 27 attached to end support columns 12 and 14 and intermediate support column 16 is illustrated. Each shelf 10 rests upon two rear posts 26 and two front posts 27. One front post 27 and one rear post 26 is attached to a first support column 12, 14, or 16 on each side of the shelf 10. The hook 42 located at the rear of each shelf 10 upon its lower surface engages the rear posts 26 and the hooks 43 located at the front of each shelf 10 engage the front posts 27. The hooks 42 and 43 thereby prevent the shelf 10 from sliding off of the posts 26 and 27. Each shelf 10 is inclined sufficiently to permit the viewing of the front portion of each wallcovering sample.
Each shelf 10 may be removed from the wallcovering rack by sliding the shelf inward approximately one inch and then raising the shelf slightly to permit its withdrawal without re-engaging the hooks 42 and 43 with a post 26 or 27. Each shelf 10 is installed by simply sliding the shelf 10 in over the posts 26 and 27 upon which it will rest, while simultaneously raising the hooks 42 and 43. Raising the shelf 10 allows it to ride over the posts 26 and 27. The shelf 10 is then lowered and slid forward to permit the hooks 42 and 43 to engage the posts 26 and 27.
Referring now to FIG. 9, the fluorescent fixture 64 and fluorescent light 66 are depicted as they are disposed within an intermediate support column 16. The fluorescent light 66 extends to a distance slightly above the uppermost end of light opening 20. This assures even illumination of the light opening 20.
Referring now to FIG. 10, the attachment of the long horizontal member 28 to the end support column 12 is shown. Suitable fasteners, such as screws 38, are used to secure the long horizontal member 28 to the end support column 12. The long horizontal member 28 is disposed within a recess 49 formed in inside panel 48. This assures a more secure engagement of the long horizontal member 28 and the inside panel 48. Additional fasteners (not shown) may be used to secure the long horizontal member 28 to the outside panel 50.
Hook and looP fasteners may be used to conveniently attach sections of the wallcovering display rack together. For example, the first 12 and second 14 end support columns and the intermediate support columns 16 could be attached to the bases 18 with hook and loop fasteners.
A connecting member 44, shown in phantom in FIG. 10, may be used to connect two Wallcovering racks back-to-back, as shown in FIG. 1. Suitable fasteners, such as wood screws, secure the connecting member 44 to the end support columns 12 and 14. The semi-circular base 46 of FIG. 1 can also be used to further secure two wallcovering racks of the present invention together in a back-to-back fashion.
The wallcovering display rack of the present invention is best utilized by displaying wallcovering samples in a manner that facilitates the customer's rapid and simple location of the desired wallcovering. This can be accomplished by arranging the wallcovering samples in a logical order that is immediately apparent to the customer upon viewing the wallcovering display rack.
An example of such a logical order would be to arrange wallcovering samples such that each column or stack of shelves contains a particular type of wallcovering, e.g. floral, striped, or textured. Colors would then be arranged in order from top to bottom for each column. That is, reds could be disposed upper-most in each stack, followed by pinks, oranges, and yellows, and ending with blues and purples lower-most. Thus, a customer desiring a floral patterned wallcovering having a predominantly blue color would immediately recognize that floral wallcoverings are all disposed within a particular column and thus would visually search that column for the desired color. On noticing that the blue shades are disposed toward the lower-most portion of the column, the customer would then concentrate his efforts upon the lower-most portion of the column in which the floral wallcoverings are disposed.
Therefore, any wallcovering desired can be quickly and easily located by a customer with little or no assistance from sales personnel. The wallcovering storage rack of the present invention provides a convenient and space efficient means of storing and displaying wallcovering samples while reducing the amount of sales assistance required by the customer in selecting the desired wallcovering.
It is understood that the exemplary wallcovering display rack described herein and shown in the drawings represents only a preferred embodiment of the invention. Indeed, various modifications and additions may be made to such embodiment without departing from the spirit and scope of the invention. For example, other types of construction and materials may be used. Molded plastic, foam core, and sheet metal construction is contemplated. Also, light sources other than fluorescent lights may be utilized Thus, these and other modifications and additions may be obvious to those skilled in the art and may be implemented to adapt the present invention for use in a variety of different applications.
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A modular wallcovering display rack for providing a convenient and cost effective means of displaying wallpaper samples and the like to potential customers is disclosed. The wallcovering display rack is fabricated in modular form so that it may adapted to fit various store configurations and is also easily expandable. The wallcovering display rack comprises a plurality of vertically stacked, inclined shelves upon which individual sheets of wallcovering samples may be placed for display. Vertical columns support the shelves and house fluorescent lights which provide a soft, even illumination of the wallcovering samples. An individual wallcovering sample can be easily removed from the wallcovering rack for closer inspection. The ease of removal also facilitates rapid sample changes to reflect updates in inventory. Each vertical support column has an array of pockets positioned in alignment with and adjacent the stack of shelves. Each pocket may contain a plurality of wallcovering take-home samples of the type displayed in the adjacent shelf. A customer may remove and keep a take-home sample from the pocket for use in deciding upon a particular wallcovering.
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TECHNICAL FIELD
This invention relates to a process for fracturing a subterranean formation such as an oil and/or gas producing formation in order to increase the effective permeability in a portion of the formation surrounding a wellbore penetrating the formation and to enhance the productivity or injectivity of the well.
More particularly, the invention relates to an improved process for removing a gel filter pad which typically builds up on the surfaces of a wellbore and on fractures resulting from fracturing the formation using an aqueous gel material as a part of the fracturing fluid.
BACKGROUND AND SUMMARY OF THE INVENTION
Hydraulic fracturing of subterranean formations is an old and highly developed process, used primarily to increase the permeability of a portion of a formation surrounding a wellbore. The process may be applied to new wells to increase productivity, or to old wells to increase or restore productivity. The process is also applicable to injection wells used in secondary recovery or fluid disposal operations.
In a typical fracturing process, a thickened fluid such as an aqueous gel or an emulsion is utilized. The thickened fluid increases the fracturing effect and also supports proppant material which is deposited in the fractures created by the process. In many cases, a fluid loss additive material is included with the fracturing fluid to further enhance the results. A common fluid loss additive material is silica flour. Many other natural and synthetic solid materials have been utilized as fluid loss additives in fracturing processes.
A detailed description of the hydraulic fracturing process, including a recitation of suitable gelling agents useful therein, is found in U.S. Pat. No. 4,470,915 to Conway.
When solid fluid loss additives are included in the fracturing fluid, a gel filter pad comprising fluid loss additive and concentrated gel material forms on the surfaces of the wellbore and the fractures creates by the process. Ideally, this gel filter pad is subsequently removed by backflow of fluid from the formation (except in the case of injection wells), but in actual practice, it is usually necessary to follow the treatment with gel breaking and/or gel filter pad removal steps. These steps often only recover a small fraction of the potential productivity of the well.
A fracturing fluid comprised of an aqueous gel and a hydrolyzable organic ester which breaks the gel is described in U.S. Pat. No. 3,960,736 to Oree et al. That patent does not suggest that the organic ester is used in an amount or form to provide fluid loss properties to the treatment fluid.
U.S. Pat. Nos. 4,387,769 and 4,526,695 to Erbstoesser et al. describe use of a polyester polymer as a fluid loss additive material. The polymers degrade at formation conditions to facilitate removal from the treated well.
U.S. Pat. No. 3,868,998 to Lybarger et al. describes a process for placing a self-cleaning pack of particles in a formation utilizing a solution of a slowly reactive acid-yielding material.
U.S. Pat. No. 4,715,967 to Bellis et al. describes a condensation product of hydroxyacetic acid with itself or other compounds, the condensation product having the ability to provide fluid loss properties to a fluid and being degradable at formation conditions. The condensation products described in that patent are particularly useful in the process of this invention.
According to the present invention, condensation products of the type described in the aforementioned Bellis et al. patent are utilized in a fracturing fluid to provide fluid loss properties and to also provide gel breaking capabilities such that the gel filter pad comprised of condensation product and concentrated gel on the wellbore and fracture surfaces is essentially completely removed, thereby restoring full permeability to the well.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The process of this invention basically is a hydraulic fracturing procedure utilizing as the fracturing fluid an aqueous gel with a specific fluid loss additive in a specific amount.
The fluid loss additives in the present invention comprise inexpensive, low molecular weight condensation products of hydroxyacetic acid with itself or with compounds containing other hydroxy-, carboxylicacid- or hydroxycarboxylic-acid moieties. The condensation products are friable solids with a melting point of about 160° C. or higher and being substantially crystalline at both ambient and wellbore temperatures. They have a number average molecular weight of 200 to 4000 and preferably are oligomers having a number average molecular weight of about 200 to about 650. They are primarily trimers up through decamers. They are insoluble in both aqueous and hydrocarbon media but will degrade at specific rates in the presence of moisture and temperatures above about 50° C. to form oil- and/or water-soluble monomers and dimers. Rate of hydrolysis at a given temperature can be increased by incorporating small amounts of other molecules (usually less than 15% by weight) into the hydroxyacetic acid condensation reaction. These materials are usually flexible or more bulky molecules that partially disrupt crystallinity but leave the condensation product friable. Thus, the treatment agent can be tailored to adjust the rate of hydrolysis from a few hours to several days by controlling the amount and nature of the crystallinity.
As used herein, the term "hydroxyacetic acid condensation product" refers to a material within the description in the preceding paragraph.
The aqueous gels applicable to the present invention include those formed from the gelling agents recited in the aforementioned U.S. Pat. No. 4,470,915. The most commonly used gelling agent, and the preferred one for purposes of this invention, is crosslinked hydroxypropylguar.
The treatment fluid in accordance with the invention comprises an aqueous gel, preferably substantially completely hydrolyzed, and a fluid loss additive comprised at least in part of hydroxyacetic acid condensation product. The amount of condensation product in the treatment fluid is at least that amount which, upon degradation, results in substantial removal of the gel filter pad formed during the fracturing step. For normal fracturing treatments, at least 30 pounds of condensation product per 1,000 gallons of treatment fluid is necessary. Condensation product concentration in treatment fluid refers to the portion of the treatment fluid to which it is added. It is not unusual to use one or more slugs of treatment fluid during the procedure which do not contain the fluid loss additive.
To illustrate the unexpected results obtained by the process of this invention, simulated fracturing treatments using hydroxyacetic acid condensation products were carried out and the results compared to simulated treatments using other fluid loss additive materials. These simulated treatments and the results are described and set forth in the following examples.
FRACTURING TREATMENT SIMULATION PROCEDURES
The fracturing fluid reservoirs for this study were two 55-gallon polyethylene drums manifolded together. The base gel was batch mixed by adding gel and additives to the drum while circulating with a Moyno pump at 20 gal/min. The base gel consisted of 2% KCl+40 pounds per thousand gallons Hi-Tek polymer HP-8 (hydroxypropylguar) with 21/2 pounds per thousand gallons fumaric acid and 10 pounds per thousand gallons sodium bicarbonate.
During a fracturing fluid run, the base gel was fed to an open blending device by the Moyno pump where the fluid was stirred with a ribbon shaped stirring device while sodium persulfate and fluid loss additives were added. Delayed titanate crosslinker (0.8 gal Tyzor 101) was added with a syringe pump on the low pressure side of the intensifier system.
The fluid proceeded from the intensifier pumps to a length of 1/4 inch tubing where it was sheared at near 1000/sec for 5 minutes to simulate pumping down tubing at 12 barrels per minutes. The fluid then entered a length of 1 inch tubing surrounded by a heating jacket. The shear rate was 40-50/sec while undergoing heat-up to formation temperature. A temperature of 50° C. was selected to represent the average cool down temperature of a point within 50 feet of the wellbore in formations with a bottom hole temperature of 85° C. Residence time in the formation simulator was approximately 5 minutes. With a bottom hole temperature of 85° C., the formation simulator was set at 50° C. to model cooldown.
Once the fluid was heated at 40-50/sec it flowed through the test cell, again at a shear rate of 40-50/sec. Flow was between 23/8 inch slabs of core that had been saturated with 2% KCl. The leakoff rate through each core was monitored versus time. The fluid traveled to a series of high pressure knock-out pots where the sand-laden fluid was collected and dumped while maintaining a constant pressure of 1000 psi on the system.
A complexed gel pump time of 90 minutes was performed on all reported tests. The time was divided into the following stages:
______________________________________Stage Fluid Test______________________________________1 2% KCl 10 min2 Base Gel 10 min3 Complexed Gel Pad 90 min4 Slurry to pack cell to desired concentration______________________________________
The amount of proppant was selected to provide 2 pounds per square foot in the 1/3 inch slot. The final slurry was flowed into the cell and the cell shut in. The pipe-to-slot flow ends were removed and replaced with inserts containing a 1/8 inch hole with a filter screen to confine proppant to the cell during closure. The top piston setscrews and spacers were removed and closure was applied while heating to 85° C. and monitoring leakoff. A closure of 1000 psi was applied over the course of 30 minutes.
Fluid was leaked off until a net cell pressure of zero was obtained (closure-internal cell pressure=0). This amounted to 23 ml of static leakoff. At this point the cell was shut in at temperature and allowed to set static for 4 hours. After 4 hours, 2% KCl flow was initiated through the core and pack simulating flow back while closure was slowly increased to 4000 psi. Thereafter conductivity and permeability of the pack was monitored versus time for 50 hours.
Using the above procedure, the conductivity, conductivity coefficient Cw, permeability and retained permeability (compared to a control) were determined for treatment fluids containing various fluid loss additives. The results are summarized in Table 1 below. In each run, the base fluid was a 2% KCl plus 40 pounds per thousand gallons crosslinked hydroxypropylguar and test temperature was 185° F., except for the last run in which test temperature was 200° F.
TABLE 1______________________________________ Effective Conduc- Permea- RetainedAdditives Cw tivity bility Permeability(per mgal) (ft/min.sup.1/2) (md-ft) (darcies) (%)______________________________________50 pounds HAA*** .0017 7919 482 10050 pounds SilicaFlour .0028 48 3 0.650 pounds HAA +5% Diesel .0016 1873 114 2450 pounds SilicaFlour + 5%Diesel .0011 25 2 0.450 pounds HAA .0018 7853 478 100None .0029 67 4 0.8______________________________________ *Based on control of 472 dercies. **Hydroxyacetic acid condensation product, 8-10 micron particle size average, melting point 206° C.
The process of this invention can effectively control fluid loss in fracturing operations, and the degradation products (hydroxyacetic acid monomer and dimer) of the fluid loss additive which are produced as a result of the formation conditions break the gel in the gel filter pad and essentially completely remove the gel filter pad with no permanent formation damage.
The hydroxyacetic condensation products can be utilized as the sole fluid loss additive or in combination with other fluid loss additives such as silica flour or diesel fluid. It is only essential that the condensation products be degradable at formation conditions, and that they be used in an amount sufficient to substantially completely break the gel in the gel filter pad which is formed during the fracturing treatment. The condensation products, as shown in the aforementioned Bellis et al. application, can be tailored to suit the conditions in the formation to be fractured. The process eliminates the need for a separate gel breaker injection step. Often, a separately injected gel breaker only contacts a small fraction of the gel pad, resulting in less than full restoration of well productivity or injectivity after the fraction treatment.
Photomicrographs of proppant packs from the tests described above showed essentially complete removal of filter cake when hydroxyacetic acid condensation product was used as the sole fluid loss additive, whereas significant impairment was visible in the run using silica flour as the sole fluid loss additive. The presence of diesel fuel impedes the effectiveness of the degradation products to clean up the gel filter pad, but still a significant amount of gel damage was repaired. The ability of the hydroxyacetic acid condensation product, when used as the sole fluid loss additive, to return a proppant pack to 100% of its potential conductivity and permeability is indeed surprising.
The exact amount and type of additive for a particular fracturing treatment in accordance with the invention will depend on factors such as formation type and temperature, amount of fracturing desired, etc. It is essential in carrying out the invention that a condensed hydroxyacetic acid product in the form of finely divided particles be incorporated in a treatment fluid in an amount sufficient (when combined with other fluid loss additives where applicable) to provide effective fluid loss properties to the fracturing fluid and to provide sufficient degradation products in a reasonable time at formation conditions to restore formation conductivity and permeability by breaking the gel in the gel filter pad formed during the fracturing step.
Numerous modifications to and variations of the above described preferred embodiments will be apparent to those skilled in the art. Such modifications and variations are intended to be included within the scope of the invention as defined by the appended claims.
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Hydroxyacetic acid condensation product is used as a fluid loss material in a formation fracturing process in which a fracturing fluid comprising a hydrolyzable aqueous gel is used. The hydroxyacetic acid condensation product degrades at formation conditions to provide hydroxyacetic acid which breaks the aqueous gel, which provides restored formation permeability without the need for separate addition of gel breaker.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is in the field of metering devices and metering methods for controlling the flow of molten metal from a reservoir to a casting mold, and utilizing computer generated signals dependent upon the pressure conditions existing in the reservoir.
2. Description of the Prior Art
Pressure control means for casting devices, particularly for low pressure casting of aluminum have been developed but, for the most part, these have the disadvantage that they do not respond promptly and accurately to the variables such as the amount of metal in the reservoir, pressure and the speed of filling of the casting mold. Consequently, the casting may be non-uniform because the casting variables are not accurately reproduced so the castings may vary from each other as to shape and quality.
There is a regulating device known in which during the interval between two casting operations, a correction of the gas pressure in the reservoir is undertaken because of the decreased level of the molten bath in the reservoir. An exact regulation of greater volumes within small units of time is, however, not possible when using electrically regulated valves.
Such prior art devices frequently make use of two pressurizing steps, a higher pressure to bring the melt out of the reservoir into the casting mold, and a lower pressure in order to fill the mold (see, for example, German Laid Open Specificaton No. 2,435,734). In this type of system, prior art valves may be utilized as discussed in German Laid Open Specificaton No. 1,558,166 which cooperate with two control valves for the two different pressure steps.
SUMMARY OF THE INVENTION
The present invention provides a metering device in which an exact regulation of the casting operation may be attained with relatively simple means by responding directly to the quantity of melt removed from the reservoir per each casting piece, the filling speed of the mold, and the duration of time up to solidification of the first casting piece in the mold so that an exact, accurately reproducible casting results.
In accordance with the present invention, we provide a device in which a pilot valve cooperates with a control valve and the pilot valve is controllable by means of the control current of an analog computer which is fed with signals dependent upon the rate of metal flow up to solidification of the first casting in the mold, the change of flow on account of the decrease in the quantity of molten metal in the reservoir, and the speed of increase in the flow upon filling of the casting mold.
The regulation of the timewise variation of the control current takes place according to a pressure-time diagram of the analog computer with an integrated operation amplifier, whereby for controlling the casting sequence, the following three variables are introduced into the computer:
1. The rate of metal flow up to solidification of the first casting piece,
2. The necessary change of flow on account of the decrease in the quantity of melt during the casting procedure, and
3. The speed of increase in the flow upon filling of the mold.
In addition to these variables, there may be introduced into the computer or to the control valve or pilot valve through a time relay the length of solidification for the casting pieces.
It is particularly advantageous if the three or four mentioned variables are fed continuously to the computer individually in each case through a potentiometer which is actuated by each variable. Thus, a very precise control of the casting operated is possible with respect to the accuracy of the charge.
The pressure of the gas in the pressure conduit in front of the control valve and the stabilization of the pressure in the control gas before the pilot valve may be accomplished by means of a fines valve and a pressure reducing valve. It is also advantageous to incorporate a 3/2-way magnet valve and a safety valve in the feed conduit between the control valve and the reservoir. It is also advantageous to provide a return conduit parallel to the feed conduit of the pressure gas to the reservoir.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features and advantages of the invention will be readily apparent from the following certain of certan preferred embodiments thereof, taken in conjunction with the accompanying drawings, although variations and modifications may be effected without departing from the spirit and scope of the novel concepts of the disclosure, and in which:
FIG. 1 is a somewhat schematic view illustrating a pneumatic control for a low pressure casting device used with a mold fed by means of fluid pressure; and
FIG. 2 is a pressure-time diagram of two casting steps showing the dependence of the control current to the pilot valve from a time after commencement of the casting operation for the casting of two different pieces.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the system shown in FIG. 1, compressed air is introduced through a line P, and particles of dirt and water may be separated from the compressed air by means of a fines filter 1 equipped with a water separator. In a pressure reducing station 2, there is a further fines filter 2a and a pressure reducing valve 2b, where the compressed air is again cleaned as well as having its pressure reduced to about 1.3 atmospheres. Pressure is fed by means of a conduit 2c to the inlet side of an electrically controllable pilot valve 3 whose pressure on the outlet side is fed to a conduit 4 and is proportional to the current flowing in the coil of the electrically operated pilot valve 3. The pilot valve 3 is arranged to handle a small volume of air and cannot directly handle the substantial pressure in the conduit 1a.
The pressure in the conduit 4 is applied to a control valve such as a gate valve 6 in which there is a chamber closed by means of a diaphragm which is acted upon by the air in the conduit 4 under pressure. A pressure reducing valve 5 is connected between the filter 1 and the control valve 6 in order to exclude fluctuations in pressure in the conduit 1a. This pressure reducing valve 5 as well as the control valve 6 itself have sufficiently large cross-sectional areas to handle the required quantity of pressurized gas. The pressure is conveyed through an energized 3/2-way magnet valve 7 through a supply conduit 8 into a closed melt reservoir 9. The pressure in the reservoir 9 causes liquid metal in the reservoir to be forced though pg,6 a pipe 10 into a mold 11. There is also provided a parallel circuit consisting of a return conduit 12 which is disposed between the reservoir 9 and the control valve 6. In the supply conduit 8 there is installed a safety valve 13 which prevents the accumulation of undesired excess pressure. The pressure prevailing in the conduit 12 may be read on a manometer 14.
The pilot valve 3 is under the control of an analog computer R to which signals corresponding to the various variables are fed. The speed of filling of the mold is identified at (α), the variable (a) refers to the rate of metal flow up to solidification of the first casting piece, and the variable (b) refers to the change in pressure due to the decrease of the melt volume in the reservoir 9 at each casting operation. The introduction of the individual variables, (α), (a) and (b) takes place preferably continuously through potentiometers P.sub.α, P a and P b .
The computer R delivers the control signals to the magnet of the pilot valve 3.
In the pressure-time or control-current time diagrams I and II for two casting pieces illustrated in FIG. 2, the pressure p in the reservoir 9 and the control current i proportional to it fulfills the reqirements as to casting techniques for two differnt casting pieces as follows.
For a first casting piece identified at diagram I, the filling speed of the mold is related to the increase in the flow (α 1 ), while the variable (a) indicates the pressure and, therefore, the flow rate up to solidification of the first casting piece. The symbol b 1 represents the necessary rise in temperature and, therefore, the flow change between successive fillings F 1 , F 2 , F 3 , F 4 , and so on of the mold. The lines in the diagram extending horizontally indicate the solidification time of the casting pieces which may be introduced into the computer R or they may be passed to the pilot valve 3 or the control valve 6 by means of time relays.
The control flow-time diagram II is appropriate for a second casting piece with greater volume. The rise in flow (α 2 ) or the speed in the rise of pressure, respectively, is smaller and the filling time of the mold 11 is longer. It should also be recognized that the rate of metal flow (a 2 ) and the flow change (b 2 ) is greater between each individual casting operation.
The regulation of the duration of the electrical control signal for the pilot valve 3 occurs preferably through an analog integration step, an analog and digitally controlled multiplier as well as an analog adder and an impedance transformer as is well known to those skilled in the art. The magnitude of the three factors (α), (a) and (b) determining the pressure control are adjusted continuously by means of the potentiometers P.sub.α, P a and P b . The potentiometer shown in dotted lines to the left of computer R may serve for the control of the duration of rigidification of the casting pieces. Through the analog computer with integrated operation amplifier, the straight rise of the diagrams I and II in FIG. 2, that is, the constancy of the casting speed and the precision of the previously selected adjusted values is attained. This brings about a high accuracy, constant and reproducible casting operation and thereby provides a high grade uniform casting.
If desired, the rise in flow rate (α) shown in straight lines in the diagrams may also follow an irregular straight line, so that first a rapid filling of the conduit 10 takes place and subsequently a slower filling of the mold as is known to those skilled in the art.
As may be seen from diagrams I and II, the dimension (a), represents the pressure with which the melt for each casting is transmitted out of the reservoir 9 through the conduit 10 into the mold 11. As the level of the melt in the reservoir 9 drops during a casting operation, the melt column in the conduit 10 becomes higher and requires an increase in pressure up to the dimension (b) above the pressure with the previous casting, so that the rise in pressure (b), as indicated above, indicates a measure for the volume of the casting piece.
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A metering device and method for introducing molten metal from a reservoir into a mold, the metering device including a pilot valve, a control valve actuated by the pilot valve, and an analog computer controlling operation of the pilot valve, the computer receiving signals corresponding to the speed of filling of the mold, the magnitude of the pressure up to solidification of the first casting in the mold, and the change in pressure in the reservoir due to decrease in the metal level in the reservoir.
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RELATED APPLICATION
This application claims the benefit of priority, pursuant to 35 U.S.C. §119(e), from copending U.S. Provisional Patent application Ser. No. 60/202,587 filed May 9, 2000, incorporated by reference.
FIELD OF THE INVENTION
The present invention is directed to a control system for linear actuator devices, and more particularly to a control system for linear actuator devices utilized upon a floor maintenance machine.
BACKGROUND OF THE INVENTION
For purposes of convenience, the invention will be described in conjunction with a presently preferred implementation thereof embodied in an electric linear actuator. It will be understood, however, that the principles of the invention may apply equally as well to devices of analogous structure.
The design of automatic floor cleaning equipment often involves a considerable amount of rotary and/or linear motion actuation and control. Positioning of structures such as cleaning heads and squeegees must be accomplished quickly and transparently to the operator. The traditional method of controlling motion on cleaning equipment utilizes limit switches or other proximity switches that either directly control the power to one or more linear actuators, e.g., via relay switches, etc., or indirectly control linear actuators via a signal sent to a CPU indicating the position of the actuators. These switches introduce negative reliability and assembly issues into the design of the machine. For example, an actuator or linkage could be damaged if a jam occurs in mid stroke of the actuator as current would continue to be supplied to the actuator. Additionally, limit switches may become contaminated or damaged through the operation of the machine. The switches may also be mis-aligned during the assembly of the machine. Any of these situations can cause the actuator to stall, overheat, and/or damage the linkage or associated structure coupled thereto.
In mobile equipment systems that include a plurality of electric and or hydraulic devices, such as servo actuators, motors and pumps, it is conventional practice to couple all of such devices to a remote master controller for coordinating or orchestrating device operation to perform a desired task. Motors and actuators may be employed, for example, at several coordinated stages of a surface cleaning machine for automated control of fluids and surface working devices. In accordance with conventional practice, the master controller may comprise a programmable controller or the like coupled to the various remotely-positioned devices. Feedback from the remote devices may be provided via control signals therefrom. For closed-loop operation, a sensor may be coupled to each device for sensing operation thereof, and feeding a corresponding signal to the master controller through an analog-to-digital converter, etc.
Thus, in a system that embodies a plurality of electric and/or hydraulic devices, a substantial quantity of electrical conductors must be provided for feeding individual control signals to the various devices and returning sensor signals to the master controller. Such conductors interfere with system design and operation, and are subject to failure. The bank of D/A and A/D converters for feeding signals to and from the master controller add to the expense and complexity of the overall system. Perhaps most importantly, system performance is limited by capabilities of the master controller. For example, a programmable controller may require one hundred milliseconds to scan a device sensor signal, compute a new control signal and transmit such control signal to the remote device. An overburdened programmable controller may not perform acceptably in high performance applications that may require a ten millisecond response time, for example, at each of a plurality of remote devices.
SUMMARY OF THE PRESENT INVENTION
The present invention relates to a linear actuator control system exhibiting improved performance. To solve some of these limitations associated with the prior art devices, a control system has been implemented in which the speed and force from the actuator can be independently controlled from a control processing unit (CPU). In a system according to the present invention, the CPU can monitor the force being delivered to the actuator and that information can be used to deduce the force and/or position of the actuator. This information can also be used to determine that the actuator has reached the end of its stroke. A system according to the present invention has the ability to reduce or terminate the power being delivered to the load device in order to prevent damage to the device. The reaction time of this protection circuitry is short enough to prevent damage to the load and the energy control circuitry. Importantly, such a system can eliminate the position sensing devices normally used in this type of machine.
The present invention relates to a control system for one or more linear actuator devices, such as present on a surface maintenance machine. One aspect of the invention is to provide a linear actuator control system for use on a surface maintenance machine, such as a scrubber or sweeper, which utilizes a comparison circuit in which a signal representative of the load current in an linear actuator is modified by a signal representative of the desired load current to maintain applied load current at a desired level.
Another aspect of the present invention provides a control system which automatically limits the current load to a linear actuator in the event of an abnormal condition, e.g. linkage jamming, obstruction contact, etc.
Another aspect of the present invention provides a control system for automatically controlling one or more linear actuators of a surface maintenance machine which may be applied to various types of surface maintenance machines having different surface maintenance tools and providing for different surface maintenance functions.
A linear actuator control system in accordance with a further aspect of the invention includes a linear actuator having an electric motor component. The electric motor component is connected to drive circuitry that includes a solid state switch, preferably a FET, that is connected between one terminal of the electric motor, with the other terminal being connected to electrical ground. The control switch circuit receives a switch control signal from the microprocessor-based control electronics, and is connected to the control electrode (gate) of the FET for setting the switch circuit and controlling power to the electric motor of the linear actuator through the FET in response to the control signal. Feedback circuitry is responsive to the current through the electric motor for resetting the switch circuit and interrupting application of power to the electric motor. The feedback circuitry is responsive to a voltage drop across a shunt resistor.
It is therefore a general object of the present invention to provide a linear actuator control system that exhibits a fast response time necessary for high performance applications, while at the same time reducing cost and complexity that are inherent in prior art system of the character described above. In furtherance of the foregoing, a more specific object of the invention is to provide a system of the described character wherein each of the system linear actuators embodies microprocessor-based control adapted to communicate with a central or master controller and for thereby distributing, at least partial, control of the several linear actuators while maintaining overall coordination thereamong.
Another object of the present invention is to provide a linear actuator control structure in which all control components, including current level detectors and microprocessor-based control electronics, are fully integrated into compact inexpensive packages, and which may be readily employed in a wide variety of system applications.
Yet another object of the invention is to provide a linear actuator of the described character with enhanced robustness of hardware, including the elimination of limit switches or other position detection devices within or in association with the linear actuator.
Still another object of the present invention is to provide a system for controlling a linear actuator device, with control electronics that limit current overload as compared with prior art devices of a similar character, and that have enhanced capabilities for protecting the linear actuator against damage due to structure obstruction, contact, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention will be described in detail hereinafter with reference to the accompanying drawings, in which like reference numerals refer to like elements throughout, wherein:
FIG. 1 is a perspective of a typical walk-behind surface maintenance machine which may utilize the control system of the present invention;
FIG. 2 is a block diagram illustrating the control system for a linear actuator according to the present invention;
FIG. 3 is a simplified schematic circuit illustrating a preferred embodiment of the present invention; and
FIGS. 4A and 4B together illustrate a preferred embodiment of the control system of FIG. 1 .
DESCRIPTION OF PREFERRED EMBODIMENTS
For purposes of convenience, the invention will be described in conjunction with a presently preferred implementation thereof embodied in an electric linear actuator. It will be understood, however, that the principles of the invention may apply equally as well to devices of analogous structure.
In FIG. 1 , a vehicle such as a floor scrubbing machine 10 is indicated generally and may be of a type manufactured by Tennant Company of Minneapolis, Minn., assignee of the present invention. Such a device is disclosed in U.S. Pat. No. 4,757,566, the entire disclosure of which is incorporated by reference herein for all purposes. The scrubber 10 may include a housing 12 and a rear operating control 14 which is used by the operator to control vehicle 10 speed and direction. A control device 16 is used to control functions of the machine 10 . There may be a pair of rotating brushes or pads 18 . A linear actuator 20 may be utilized to control the position, and hence the downward force, of the brushes 18 . A squeegee 22 is normally positioned at the rear of the vehicle 10 and is effective, as is known in the art, to squeegee the floor and remove any standing water. Normally, there will be a vacuum device 24 attached to the squeegee 22 which will apply suction to remove standing water collected by the squeegee.
In one embodiment of the present invention, there may be one or more surface working tools such as sweeping brushes, scrubbing brushes or polishing pads, and there may be one or more electric actuators 20 controlling the position of said surface maintenance tools 18 . In other embodiments of the present invention, there may be one or more hopper or debris containers (not shown), and there may be one or more linear actuators 20 controlling the lifting of the hopper during a hopper dumping procedure. Linear actuators 20 may comprise an electric DC motor as the motive element. Those versed in the art are aware that in an electric DC motor the current which the motor draws is proportional to the load on the motor.
Although the invention will be described in connection with a scrubber 10 , it should be clear that the control structure according to the present invention has application to other types of vehicles using surface maintenance tools, such as a sweeper or a polishing or burnishing machine.
Referring to FIG. 2 , a block diagram is provided to explain functional interrelations between various elements of a control device 16 according to the present invention. The control device 16 is utilized to control the linear actuator 20 . Control device 16 includes a central processor unit 30 (CPU) which receives input from elements of the control system and provides output signals to elements of the control system. Control device 16 includes the additional elements: maximum current level converter 32 , high speed current limit 34 , power control device 36 , current measurement element 38 , current level converter 40 . Additional elements or components would be appreciated by those skilled in the relevant arts.
CPU 30 may be a dedicated controller or may be part of a larger controller for operating additional functions of a maintenance machine. CPU 30 may be a programmable logic controller (PLC). CPU 30 provides a speed request signal 42 to the high speed limit block 34 . The speed request signal 42 may be an analog or digital signal. In one embodiment, the speed request signal 42 is an analog signal comprising a voltage level representative of the speed request. CPU 30 also provides a maximum force request signal 44 which is converted by the maximum current level converter 32 , which may be D/A converter, into a maximum current level signal 46 . Maximum current level signal 46 is provided as another input signal to the high speed current limit block 34 .
CPU 10 receives a signal 48 from the high speed current limit block 34 indicating whether or not a maximum designated current of the linear actuator 20 has been exceeded. The CPU 10 utilizes this information to determine if the actuator 20 has reached the end of its stroke, or if it has come in contact with an obstacle. The CPU 10 can utilize internal timers to estimate the position of the actuator 20 during a move. It can use this information to adjust the speed and maximum force of the actuator 20 as the actuator movement progresses. For instance, the CPU 10 may request high speed and high current to start the actuator moving, high speed and medium current through the bulk of the movement, and low speed, low current to minimize the impact at the end of actuator stroke. The feedback signal 48 could be a current level, rather then the maximum force signal. In that case, the CPU 10 could also use the load information to make decisions as to actuator 20 speed, position, or stroke length. For example, this would be useful if a hopper lift height of a particular machine should be limited by load. This could also be used to estimate the speed and position of the actuator 20 using back EMF calculations or changes in mechanical advantage as the actuator 20 progresses through its stroke.
The maximum current level conversion block 32 converts the force request 44 from the CPU 10 to a maximum current level 46 that can be interpreted by the high speed current limit block 34 . The high speed current limit block 34 uses the maximum current level signal 46 from the maximum current level conversion block 32 , the speed request signal 42 from the CPU block 10 , and a current level signal 50 from the current level conversion block 40 to generate an energy level control signal 52 for the power control device 36 . In one embodiment, the energy level control signal 52 is a pulse width-modulated signal used to control the gate of a Field Effect Transistor (FET) within the power control device 36 .
The output of the high speed current limit block 34 will reflect the duty cycle of the speed request 42 unless the maximum current level is exceeded (current limit mode). When in current limit mode, block 34 will signal the power control device 36 to limit the current of the linear actuator 20 in order to prevent overheating of the device or other damage. Also when in current limited mode, the high speed current limit block 34 will send a maximum force exceeded signal 48 to the CPU 10 indicating that the maximum allowable current has been exceeded. The CPU 10 can then utilize this information to terminate operation of the load. Because the high-speed current limit 34 acts prior to CPU 10 direction to reduce the current to the load 20 , the time delay induced waiting for the CPU 10 to directly terminate operation of the load 20 is less critical.
The power control device 36 receives the control signal 52 from the high speed current limit block 34 , and uses it to control power flow from a battery 54 to the load. In one embodiment, the power control device 36 is a Field Effect Transistor (FET). The current measurement block 40 provides a voltage level 50 proportional to the level of current flowing to the load. In this design, the current measurement device 38 is a shunt resistor. The current level conversion block 40 receives the raw current level information from the current measurement block 38 , and transforms it into a format that can be received by the high speed current limit block 34 .
FIGS. 3 and 4 illustrate preferred embodiments of the present invention. A microprocessor controller (or CPU) 110 is utilized in the control structure. Those skilled in the relevant arts will recognize that the controller 110 can receive a variety of inputs and control a variety of outputs. Specific to illustrated embodiment of the present invention, the outputs of the controller 110 include a PWM (pulse-width-modulated) drive signal 112 and a “force request” signal 114 . An input to the microprocessor 110 includes a comparison signal 106 .
The force-request signal 114 is received by a D/A converter 122 which calculates a maximum current level corresponding to the force request signal 114 and outputs an analog signal representing the maximum current level 124 to a threshold comparator 160 . The output input 130 to the comparator 160 is received from a motor current signal circuit 142 , as described hereinafter. The comparator output 136 is provided both to a NAND device 162 and as a comparison signal 106 to the microprocessor 110 (as a feedback signal). The PWM drive signal 102 and comparator output 136 are received as input signals into the NAND device 162 , the output of which is used to control the power control device (FET) 138 . The linear actuator power control switch 138 is a FET having primary current-conducting source and drain electrodes connected in series with the linear actuator 120 and a current sensing shunt resistor 166 between ground. The motor current signal 130 (to the comparator) 160 is obtained via a motor current signal circuit 142 vis-a-vis an amplified shunt resistor voltage. The output 130 from an amplifier 143 is a voltage indicative of load current in the linear actuator 120 . The motor current sensor 142 utilizes a shunt resistor 166 , with the voltage drop across the shunt 166 used as an indicator of the current flow to the motor 120 . Alternative current sensors 142 maybe used, however. For example, a toroidal core or other non-contact type of sensor may be utilized.
In operation, the microprocessor 110 generates a PWM drive signal 102 and a force request signal 104 . In under-load current conditions (the comparison signal 106 not high), the PWM signal 102 is passed through the NAND device 162 to the FET switch 138 to control the duty cycle of the linear actuator 120 . Conversely, when under excessive current load condition (the comparison signal 106 is high), the NAND device 162 blocks the PWM signal 102 from activating the FET switch 138 .
After the PWM drive signal 102 is generated, the force request signal 114 is generated and passed from further processing by the D/A converter 122 . The threshold comparator 160 is used to detect over current conditions (the motor current signal 130 exceeds the D/A output signal) 124 . A comparison signal 136 is generated and fed back to the microprocessor 110 .
FIG. 3 includes additional aspects of the present invention, include a multiplexer and the FET-based bridge for implementing the control system for a pair of linear actuators.
Various modifications of the above-described embodiment of the invention will be apparent to those skilled in the relevant arts, and it is to be understood that such modifications can be made without departing from the scope of the invention.
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A control system for a linear actuator having an electric motor drawing a variable current level during operation. The control system includes a current level sensor for determining an operational current level of the linear actuator and a controller for generating a drive signal and a force request signal representative of a desired current level of the linear actuator. The drive signal remains constant during a predetermined time interval of the controller. The control system further includes a current limiting component for receiving the force request signal, the current level of the linear actuator and the drive signal. The current limiting component minimizes the current level of the electric motor in response to a comparison between the force request signal and the desired current level within a time interval substantially smaller than the predetermined time interval of the controller.
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BACKGROUND OF THE INVENTION
The invention relates to a height-adjustable support for semitrailers or the like, comprising a locally fixed external support tube, an internal support tube, which is fixed to a nut on a spindle, the spindle being driven by a change-over gear and a bevel gear assembly. The change-over gear has two gear wheel stages which can be alternately activated, a separate gear stage comprising bevel gear toothing being provided for the distribution of forces after each gear wheel stage.
Supports of this type are disposed, generally in paired arrangement, as a supporting apparatus in the front region of the semitrailer.
An apparatus of this type is known from EP 0 675 0029. Here the speed-change gear mechanism is accommodated in a housing attached to the front of the support outer tube. The transmission input shaft and the transmission output shaft, on which the gearwheels are seated in a rotationally secure manner, are mounted respectively in the housing and in that wall of the support outer tube which lies opposite the housing. The transmission input shaft is in this case disposed below the bevel gear set, and alongside the spindle. The transmission output shaft is located above the ring gear, in whose upwardly directed toothing the bevel pinion seated in a rotationally secure manner on the transmission output shaft engages. The transmission input shaft can be rotated by means of a crank handle. The large gearwheel fitted on the transmission input shaft is provided in engagement with the smaller gearwheel, seated on the transmission output shaft, for a rapid height adjustment of the support; and the transmission generated by the pinion on the transmission input shaft with the large gearwheel on the gearwheel set of the transmission output shaft serves for the height adjustment of the support under load. Both in low-speed gear and in the faster height adjustment of this apparatus, the further power flow is effected via the bevel gear set to the spindle drive, and this apparatus is very bulky.
A pair of supports of the generic type is also known from EP 1 104 369 B1. The speed-change gear mechanism of this so-called apparatus for supporting the semitrailer of a truck tractor is disposed almost fully within the support, the transmission input shaft and the spindle disposed, for this purpose, outside the middle of the support being mounted in a common pillow block. The transmission input shaft and the transmission output shaft are mounted in a large cover, which is attached in protruding arrangement on the front wall of the support outer tube and which is also necessary to enlarge the installation space for the speed-change gear mechanism. The transmission input shaft arranged pointing to the spindle has a pinion, which engages in a large-diameter gearwheel of a gear set integral with the transmission output shaft and effects the transmission for a height adjustment under load. A further large-diameter gearwheel, which is mounted concentrically to the transmission input shaft, can be coupled and driven, following axial displacement of the transmission input shaft, by means of the pinion thereof. This latter large-diameter gearwheel hereupon engages in the pinion which belongs to the gear set of the transmission output shaft and via which the transmission for a faster adjustment of the support without load is realized. Disposed in a rotationally secure manner on the upper end of the spindle is a ring gear, in whose upward-pointing toothing the bevel pinion of the above-situated transmission output shaft engages. Here too, the bevel gear set is the second transmission stage both for the low-speed gear and for the faster adjusting process for the support.
In these known supports, it is particularly disadvantageous that behind the speed-change gear mechanism the power flow is effected always, i.e. both in the adjustment under load, the lifting process, and in the fast adjustment, the load-free height adjustment process, via one and the same bevel gear stage. Based on its large step-down ratio, the bevel gear stage is actually only fit for the lifting process. The result is that, in the previous transmission design for such supports, the speed increase attained via the step-up gear stage of the speed-change gear mechanism is very largely cancelled out by the step-down of the bevel gear set. And that the following spindle drive extends or retracts the support inner tube only at relatively moderate speed, even though this unsatisfactory process is referred to throughout the industry, for time-saving purposes, as the high-speed gear.
The object of the invention is to provide a height-adjustable support for semitrailers, which support has a particularly high high-speed gear in order to achieve a significant time gain, and in which all transmission parts are accommodated in the support outer tube without the need for a structural expenditure which enlarges the installation space.
SUMMARY OF THE INVENTION
This object is achieved according to the invention by the support according to the invention wherein it is proposed to provide a separate power transmission for high-speed gear operation from the speed-change gear mechanism into the spindle drive. For load operation, a first bevel gear set, as previously the norm, with step-down can be provided, which, together with the likewise speed-reducing speed-change gear mechanism stage before it and the spindle drive arranged after it, is ergonomically optimally designed with respect to the hand drive power. Regardless of this, the bevel gear set for the high-speed gear, on the other hand, is according to the invention particularly advantageously designed in terms of its transmission, if it has a substantially more direct transmission than the first-named bevel gear set. Thus in practice, for example, a transmission ratio of 1:1 already yields more than a doubling of the adjustment speed, with corresponding time savings compared with the traditional supports.
This design affords the possibility, in a superb manner, that the ring gears can be disposed above the transmission output shaft.
The transmission output shaft therefore no longer has to be led over the spindle and the ring gear, as previously, which, as a result of its consequently adverse height arrangement and predefined attachment height in the case of traditional supports, helps constructively to reduce the lift.
In a refinement, the invention provides a mounting support part, in which the transmission output shaft, as well as the spindle and a pinion unit installed therein, are jointly mounted. The transmission region of the support is hence made very compact.
According to the invention, the pinion unit to be disposed in the mounting support part preferably consists, in one-piece construction, of the pinion of the high-speed gear stage and the associated bevel pinion, as well as a small shaft. It is also conceivable, however, purely to connect the said pinions in a rotationally secure manner and to use for this purpose a small axle.
A gear unit of this kind can advantageously be inserted as a part from above into the mounting support and favorably requires no installation opening on the front side of the support.
According to another refinement according to the invention, the ring gear for the high-speed gear can be fastened on the spindle jointly with the ring gear for the low-speed gear, or the ring gear for the high-speed gear is fastened to the ring gear for the low-speed gear, which latter ring gear is fixed on the spindle.
The ring gear for the low-speed gear can also be provided with a second bevel gear toothing, corresponding to the ring gear for the high-speed gear, so that the latter ring gear is advantageously no longer required as a part.
And economically, the bevel toothings for the high-speed gear, because they are placed under less load, can be dimensioned smaller than those for the low-speed gear.
The four gearwheels of the speed-change gear mechanism are arranged such that the gearwheel and the pinion of the high-speed gear stage are disposed in front of, and the gearwheel with the pinion of the low-speed gear stage are disposed behind the spindle.
Because of this design according to the invention, the spindle can be centrally positioned and the advantageously short-length transmission output shaft can be disposed behind the spindle, pointing away therefrom.
If, according to the invention, the transmission input shaft is provided with preferably two radially protruding dogs as coupling means, these, after being appropriately engaged, can transport the large gearwheel, loosely mounted on the transmission input shaft, of the high-speed gear stage, or, for the low-speed gear, can transmit the torque to the pinion provided for this, and can also, in an intermediate setting, effect a freewheel. In this way, a cost-effective gearshift is realized.
The pinion of the low-speed gear stage of the speed-change gear mechanism is advantageously provided with a hollow shaft, in which the transmission input shaft can be mounted in an axially displaceable manner. Favorably, according to the invention, the necessary engagement regions for the dogs of the transmission input shaft can also be shaped on the hollow shaft of this pinion.
In an advantageous refinement of the invention, the transmission output shaft is preferably a part with square cross section and a cylindrical bearing journal and can be inserted in a positive-locking manner into the gearwheel/bevel gear stage, thereby greatly simplifying the assembly.
As another refinement of the invention, it is proposed to attach a motor in such a way to that support of a support pair which has no speed-change gear mechanism and is connected by a connecting shaft to the transmission output shaft of the support with speed-change gear mechanism, which latter support is drivable with a crank handle, that said motor can drive the hollow-shaft pinion.
Advantageously, a motorized drive of the support pair, for example for an automated hitching and unhitching operation with respect to truck tractors, is thereby enabled and manual operation can become the alternative for the special or emergency case.
In a bearing flange sleeve, three radial grooves are provided for the selective engagement of a ball spring element, seated in the transmission input shaft, for the purpose of locking the gearshift settings of the transmission input shaft.
In the engaged middle setting, in the aforesaid motorized operation, it is thus advantageously ensured that the speed-change gear mechanism of the manual drive remains in freewheel.
As another embodiment of the invention, for the separate high-speed gear power flow to the spindle drive, an intermediate drive unit having a toothed pinion as well as a bevel pinion is proposed, which shall be provided axially in front of a gearwheel and bevel pinion arrangement for the low-speed gear. Into the gearwheel and bevel pinion arrangement, on the support rear side, a transmission output journal can favorably be inserted positively from outside, by which the second support of a support pair can be driven.
The spindle with mounted ring gears, the toothings of which point upward, can here be stored in a bearing plate.
Advantageously, the transmission input shaft must be installed such that, in parallel arrangement to the intermediate drive unit, it extends only so far into the support outer tube as corresponds to the width of the large gearwheel of the high-speed gear and as its mounting depth in the hollow shaft pinion demands.
The gearwheel and bevel pinion arrangement for the low-speed gear can advantageously be shaped in one piece and provided with a bearing journal on which the intermediate drive unit can be mounted.
The bearing journal for the intermediate drive unit can also be provided as an extension on the transmission output shaft placed from behind through the gearwheel and bevel pinion arrangement, thereby facilitating the assembly.
It is advantageous to configure the intermediate drive unit in one piece such that it at one end receives a bearing bore, which is mounted on the bearing journal of the gearwheel/bevel pinion unit or on an extended transmission output journal, and at the other end is stored in the front region of the support.
The intermediate drive unit can also be shaped such that, instead of a bearing bore, it has a bearing journal, which is mounted in the gearwheel and bevel pinion arrangement for the low-speed gear or on the power-take-off journal, the bevel gear being fitted in a positive-locking manner, which produces a favorable means of assembly.
For a further embodiment of the support according to the invention, it is proposed to provide a gearwheel drive unit, which is disposed parallel to the intermediate drive unit and the gearwheel/bevel pinion unit and alternately transmits the power flow for the high-speed gear to the intermediate drive unit or, in low-speed gear, to the gearwheel/bevel pinion unit.
In preferably one-piece construction, the gearwheel drive unit, on one end region, can be configured with a large-diameter gearwheel for the high-speed gear operation and, at the other end, with a pinion for the low-speed gear.
The gearwheel drive unit can be connected in a rotationally secure and axially fixed manner to the transmission input shaft, which, in a manner appropriate thereto, must extend into the support outer tube by a still small extent than in the previously described embodiment. Apart from this connection and the thereby effected mounting of the gearwheel drive unit, it is advantageous to store the other side of the gearwheel drive unit displaceably on a bearing journal to be provided on the inner side of the rear wall of the support outer tube.
Through axial displacement of the transmission input shaft, the gearwheel drive unit is also correspondingly displaced and brought either into the high-speed gear or the low-speed gear, or in-between into neutral setting. In this embodiment, the unused gearwheel or pinion is respectively disengaged.
The support can advantageously also be provided with a bearing plate for the spindle, which bearing plate is cup-like and is preferably shaped with a square edge. At variance from the cup shape, individual edge regions may also be arranged taller.
If, moreover, the nut of the spindle drive is disposed in the support inner tube instead of over the support inner tube, the support inner tube can beneficially be extended upward to the point where its upper end face, in retracted setting, reaches up to directly against the bottom side of the edge of the proposed cup-like bearing plate.
If edge regions of the bearing plate are made taller, the side walls of the support inner tube, if stepped on the end face or provided with recesses, can also be correspondingly extended further upward. This gives rise to the possibility of building, according to the invention, supports with extremely low overall height and relatively large lift. In practice, this is advantageous with regard to ground clearance, especially in supports for large-capacity semitrailer units with low-lying frames. And in longer supports for higher vehicles, according to this embodiment there is a greater overlap of the support outer tubes with the support inner tubes, due to upwardly extended support inner tubes in the extended state. The increase in overlap favorably increases the transverse rigidity, and hence the operating reliability of the supports.
Finally, it proves favorable with regard to the gearwheel design if the transmission input shaft disposed above the intermediate drive unit of the high-speed gear is installed laterally offset from the intermediate drive unit.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is next explained with reference to the drawings, in which:
FIG. 1 shows a front view of the support according to the invention,
FIG. 2 shows a side view of the support shown in FIG. 1 ,
FIG. 3 shows a longitudinal section of the support shown in FIG. 1 along the line A-A, with the speed-change gear mechanism in the high-speed gear setting,
FIG. 4 shows a second longitudinal section analogous to FIG. 2 , wherein the speed-change gear mechanism can be seen in the low-speed gear setting,
FIG. 5 shows a third longitudinal section analogous to FIG. 2 , wherein the speed-change gear mechanism can be seen in the high-speed gear setting,
FIG. 6 shows a fourth longitudinal section analogous to FIG. 2 , wherein the speed-change gear mechanism can be seen in the high-speed gear setting,
FIG. 7 shows a fifth longitudinal section analogous to FIG. 2 , wherein the speed-change gear mechanism can be seen in the high-speed gear setting,
FIG. 8 shows a sixth longitudinal section analogous to FIG. 2 , wherein the speed-change gear mechanism can be seen in the high-speed gear setting,
FIG. 9 shows a seventh longitudinal section analogous to FIG. 2 , wherein the speed-change gear mechanism can be seen in the high-speed gear setting,
FIG. 10 shows a front view of the upper support region.
DETAILED DESCRIPTION
The support 10 shown in FIGS. 1 to 9 is fastened in paired arrangement to the chassis of a semitrailer in the front region thereof. The supports 10 of a pair are mutually connected by means of a connecting shaft 11 on the transmission output shafts 12 and in the transport setting are retracted, i.e. are in shortened state. And before the semitrailer is uncoupled from the tractor truck, they are extended.
The support 10 has a support outer tube 13 , and a support inner tube 14 mounted in a longitudinally displaceable manner therein. The support outer tube 13 and the support inner tube 14 preferably have square cross sections. The support 10 is fastened to the semitrailer frame by a screw-on plate 15 seated on the support outer tube 13 . Fastened to the lower end of the support inner tube 14 is a foot 16 for placement onto the ground. In addition, the support 10 has a spindle 17 with a nut 18 .
As shown by FIGS. 1 to 4 , seated on the spindle shoulder is an axial bearing 19 , which is supported on a mounting support part 20 fastened in the support outer tube 13 . In the mounting support part 20 , the transmission output shaft 12 , the spindle 17 and a pinion unit 21 are jointly mounted. The pinion unit 21 consists, in one-piece construction, of a pinion 21 a , a bevel pinion 21 b and a small shaft 21 c . For the installation and mounting of the pinion unit 21 , the mounting support part 20 has pockets 22 , 23 and upwardly open bearing points 24 . Likewise, the mounting support part 20 has a larger pocket 25 for the installation of a gearwheel 26 and of a bevel pinion 27 of the low-speed gear stage of the speed-change gear mechanism. On the mounting support part 20 are located a large ring gear 28 for the low-speed gear and a small ring gear 29 for the high-speed gear. The ring gears 28 , 29 are jointly connected in a rotationally secure and axially non-displaceable manner to the journal of the spindle 17 . The toothings of the ring gears 28 , 29 point downward. The ring gear 28 meshes with the bevel pinion 27 seated below it on the transmission output shaft 12 . And the bevel pinion 21 b of the pinion unit 21 engages from below in the ring gear 29 .
The short-length transmission output shaft 12 has a square cross section with a cylindrical bearing journal, can be easily inserted in a positive-locking manner into the gearwheel 26 connected to the bevel pinion 27 and, for the purpose of axial fixing, is pinned to a collar bushing. Axially parallel to the transmission output shaft 12 and above the ring gears 28 , 29 there is disposed a hollow-shaft pinion 30 , which engages in the gearwheel 26 . The hollow-shaft pinion 30 is mounted on the rear side in the rear wall of the support outer tube, and supported coaxially in its hollow shaft is a longitudinally displaceable transmission input shaft 31 , which has its second mounting in a bearing flange sleeve 32 seated on the front side of the support outer tube 13 .
Located between the front end face of the hollow-shaft pinion 30 and a collar bushing 33 seated in the wall of the support outer tube 13 there is a gearwheel 34 , which is mounted loosely on the transmission input shaft 31 and belongs to the high-speed gear stage of the speed-change gear mechanism. In the bore of the gearwheel 34 there are two axial grooves 34 a , and the front region of the hollow-shaft pinion 30 has a cylindrical counterbore 30 a and a continuous transverse slot 30 b , corresponding to the width of the axial grooves 34 a.
The transmission input shaft 31 has two radially protruding dogs 31 a , which, following appropriate axial displacement of the transmission input shaft 31 , can engage either in the axial grooves 34 a or in the transverse slot 30 b so as to be able to transmit the torque generated via a hinged crank handle 35 selectively to the high-speed gear or the low-speed gear stage of the speed-change gear mechanism. And if the dogs 31 a are brought into the region of the counterbore 30 a as an intermediate setting, a freewheel exists.
An axial locking of the transmission input shaft 31 against unwanted displacement during the cranking and to ensure that the manual drive mechanism, in motorized operation of a support pair, remains securely switched off, in the bearing flange sleeve 32 three radial grooves 32 a are provided, into which a ball spring element 31 b placed in the transmission input shaft 31 selectively engages.
In order to illustrate the working of the speed-change gear mechanism, in FIG. 3 the power flow in high-speed gear is represented schematically in the form of arrowed lines. The dash-dot lines show the power take-off to the neighboring support. In the same way, the power flow in low-speed gear is shown in FIG. 4 .
The support 10 according to the invention which is shown in FIG. 5 , having a spindle 37 which is mounted in a bearing plate 36 and on which a ring gear 38 with two concentric toothings 38 a / 38 b is seated, has an intermediate drive unit 39 for the high-speed gear and a gearwheel/bevel pinion unit 40 for the low-speed gear. The gearwheel/bevel pinion unit 40 consists of a gearwheel 40 a and a bevel pinion 40 b and is provided with a bearing journal 40 c , on which the intermediate drive unit 39 is mounted rotatably in the bearing bore 39 c . In the gearwheel/bevel pinion unit 40 , axially opposite its bearing journal 40 c , a transmission output journal 41 is inserted in a positive-locking and axially fixed manner, which also serves for the storage of said unit in the rear wall of the support 10 .
The intermediate drive unit 39 consists of a hollow shaft, a bevel gear 39 a being seated on the open side thereof and a pinion 39 b being disposed on the oppositely adjoining region. The end piece of the intermediate drive unit 39 serves for the mounting 42 of the same in the front region of the support outer tube 13 . The mounting 42 of the intermediate drive unit 39 is shaped such that, located in a cap 43 , it projects into the outer tube 13 of the support 10 .
On the transmission input shaft 31 there is a rotationally movable, large-diameter gearwheel 44 for the high-speed gear. The gearwheel 44 has on the inside, apart from axial grooves 44 a for rotary transport by dogs 31 a of the transmission input shaft 31 , also a cylindrical counterbore 44 b for the freewheel setting of the dogs 31 a . The axial setting of the transmission input shaft 31 is represented in the high-speed gear setting. The force path in the high-speed gear setting is from the transmission input shaft 31 via the gearwheel 44 and the pinion 30 b to the intermediate drive unit 39 and, via the bevel gear 39 a thereof, to the toothing 38 b of the ring gear 38 to the spindle drive (see arrow line in FIG. 5 ).
At the same time, a part of the torque is transferred from the ring gear 38 via its toothing 38 a to the bevel pinion 40 b , and via the transmission power take-off journal 41 and the connecting shaft 11 (see FIG. 1 ) to the neighboring support (see dash-dot arrow line in FIG. 5 ). In this embodiment of the support 10 , the hollow-shaft pinion 30 is provided on the end face of the hollow shaft merely with transverse slots 30 b , in which, after the transmission input shaft 31 has been switched over, its dogs 31 a engage and the low-speed gear is realized in the manner described earlier.
In the support 10 shown in FIG. 6 , in contrast to that shown in FIG. 5 , the bevel gear 39 a of the intermediate drive unit 39 is located on the other end region of its hollow shaft. In functional terms, this embodiment therefore advantageously differs from the semitrailer supports presently on the market by virtue of an opposite drive rotational direction of the high-speed gear and the low-speed gear. The direction of rotation of the crank handle 35 can namely be formulated in high-speed gear, i.e. without load when the support inner tube 13 is extended (let out), such that cranking can perforce easily be carried out counterclockwise. By contrast, the retraction (drawing-in) of the support inner tube 13 , at perforce higher necessary cranking pressure in the clockwise direction, can be cranked more comfortably. On the other hand, in low-speed gear, the extension of the support inner tube 13 , i.e. the raising of the load, can continue to be well realized, as previously, rotating in the clockwise direction. The power flow in high-speed gear is represented with arrow lines or dash-dot lines in FIG. 6 .
In FIG. 7 , a support 10 is shown in which, unlike in FIG. 5 , the transmission output journal 41 is provided with a bearing journal 41 a , which is placed in a positive-locking manner partially in the gearwheel/bevel pinion unit 40 and on which, moreover, the intermediate drive unit 39 is rotatably mounted. The working is described as for FIG. 5 .
FIG. 8 shows a support 10 according to FIG. 5 , yet with an intermediate drive unit 39 which is fully cylindrical and has a second bearing journal 39 c , which is mounted rotatably in the gearwheel/bevel pinion unit 40 and the transmission output journal 41 . And the bevel gear 39 a is mounted in a rotationally secure manner. The working is described as for FIG. 5 .
The support 10 shown in FIG. 9 has a gearwheel drive unit 45 , which has a gearwheel 45 a and a pinion 45 b . The gearwheel drive unit 45 is on one side, seated on the transmission input shaft 31 , connected to this in a rotationally secure and axially coupled manner by pinning. And the other side of the gearwheel drive unit 45 is mounted in an axially displaceable manner on a bearing journal 46 , which is seated on the inner side of the rear wall of the support outer tube 13 . In high-speed gear of the support 10 , the gearwheel 45 a of the gearwheel drive unit 45 meshes with the pinion 39 b of the intermediate drive unit 39 and the power flow takes place according to the arrow lines included in FIG. 9 . If the transmission input shaft 31 , for the purpose of shifting to the low-speed gear, is pushed in as far as possible, the pinion 45 b of the intermediate drive unit 39 enters into engagement with the gearwheel 40 a of the gearwheel/bevel pinion unit 40 and the power flow can then be realized according to the previously described embodiments. In an axial intermediate setting of the gearwheel drive unit 45 , the gearwheel 45 a and the pinion 45 b are disengaged, which corresponds to the neutral gearshift.
FIG. 9 additionally shows the bearing plate 36 in a cup-like configuration, in an edge region a recess 36 a being provided, into which the gearwheel 40 a extends. The edge of the cup-like bearing plate 36 is welded to the support outer tube 13 . The support inner tube 14 extends, in its transport setting which is shown here, to right up to the lower region of the edge of the cup-shaped bearing plate 36 . The nut 18 is fixed in the support inner tube 14 in a manner which is not shown.
Finally, FIG. 10 shows an embodiment of the support, in which the transmission input shaft 31 disposed above the intermediate drive unit 39 of the high-speed gear is installed laterally offset from the intermediate drive unit 39 by, for example, a measure X.
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A height-adjustable support ( 10 ) for semi-trailers or similar, comprising a locally fixed external support tube ( 13 ), an internal support tube ( 14 ), which is fixed to a nut ( 18 ) on a spindle ( 17 ), the spindle being driven by a change-over gear and a bevel gear assembly. The change-over gear has two gear wheel stages which can be alternately activated, a separate gear stage comprising bevel gear toothing being provided for the distribution of forces after each gear wheel stage.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a novel DNA construct, segment or fragment containing a promoter obtained from yeast and to an application thereof in genetic engineering.
2. Prior Art
With widespread utilization of recombinant DNA techniques, it has now become possible to produce useful polypeptides using prokaryotes or eukaryotes. Escherichia coli has thus far been employed in the large scale production of polypeptides. However, the use of eukaryotes is desired for the production of polypeptides particularly important in pharmacology. Yeasts, a group of eukaryotic microorganisms, have a number of similarities with mammalian cells and, therefore, are advantageous for use in the expression of genes coding for mammalian proteins. Further, yeasts do not contain endotoxin in their cells. Yeasts are easily cultivated. Culture of yeasts has been made from the past on a large, industrial scale, and its safety is confirmed. Additionally, a number of studies have been made to clarify their genetic biological mechanism. All the above circumstances surrounding yeasts have led to the utilization thereof as host organisms in genetic engineering.
Several yeast vectors for gene cloning are known at present. There are, however, few known yeast promoters capable of effectively expressing foreign genes.
Two acid phosphatases and two alkaline phosphatases are known to exist in a lysate of a strain of yeast Saccharomyces cerevisiae. The acid phosphatases are found on the surface of cells. The production of one of the acid phosphatases is suppressed by an inorganic phosphate, while the other acid phosphatase is constitutively produced. One of the alkaline phosphatases is a repressible one whose production is repressed by an inorganic phosphate and which has a wide substrate specificity. The other alkaline phosphatase is a specific p-nitrophenylphosphatase whose substrate is only p-nitrophenylphosphate, and which is constitutively produced. The mutants, pho5, pho4, pho2 and pho81 which lack repressible acid phosphatase activity have been isolated. The PHO5 gene is a structural gene for the repressible acid phosphatase, whereas the PHO4, PHO2 and PHO81 genes are genes which produce proteins regulating the expression of the repressible acid phosphatase structural gene PHO5. Further, the PHO4 and PHO81 genes serve to regulate the expression of repressive alkaline phosphatase structural gene similar to PHO5.
Various yeast vectors for gene cloning are known and may be utilized at present. In order to express native or endogeneous genes and foreign or exogeneous genes effectively, it is necessary to select a potent yeast promoter suitable for the host organisms to be used.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a restriction map of a plasmid pAC4 having an insertion of a DNA fragment bearing the PHO81 gene;
FIG. 2 is a schematic representation of restriction map for a DNA fragment and derivatives thereof bearing the PHO81 gene and the PHO81 promoter cloned according to the present invention, and indicating their ability to complement the PHO81 mutation;
FIG. 3 is a representation showing the identification of the PHO81 transcription products;
FIG. 4 illustrates cleavage maps for the base sequence of a cloned DNA fragment bearing PHO81;
FIG. 5 shows the nucleotide sequence of the promoter region of the PHO81 gene;
FIG. 6 is a scheme for constructing the pAC430 plasmid;
FIG. 7 is a scheme for constructing a recombinant DNA for the expression of adr type hepatitis B virus surface antigen gene;
FIG. 8 is a a scheme for constructing a lacZ expression plasmid; and
FIGS. 9-1 to 9-5 show the DNA sequence containing the PHO81 gene.
SUMMARY OF THE INVENTION
The present invention relates to a promoter of the PHO81 gene (hereinafter referred to as the PHO81 promoter). The PHO81 gene is a regulatory gene for expression of the structural genes of the repressible acid and alkaline phosphatases of yeast. Thus, the present inventors have cloned the PHO81 gene, determined the restriction enzyme cleavage map for the cloned DNA and determined the nucleotide sequence of the promoter region thereof. As a result, it has been found that the promoter is a novel DNA which may be suitably used for efficiently expressing both foreign and native genes. The present invention has been made on the basis of the foregoing studies.
More particularly, the present invention provides a DNA fragment having the promoter activity of the PHO81 gene regulating the production of phosphatase and being obtainable from Saccharomyces cerevisiae; a DNA fragment of the above-mentioned type, said fragment being a recombinant DNA; a DNA fragment bearing a structural gene coding for a positive regulatory factor for production of repressible phosphatases or other structural gene at a position downstream from the PHO81promoter; a transformant containing a DNA fragment having a promoter activity of PHO81 gene regulating the production of phosphatase, and being obtainable from Saccharomyces cerevisiae; a transformant containing a DNA fragment bearing the above PHO81 promoter and a structural gene downstream from the PHO81 promoter; and a process for the production of a gene product including the steps of cultivating a transformant containing a DNA fragment having a promoter activity of PHO81 gene regulating the production of phosphatase, and being obtainable from Saccharomyces cerevisiae and a structural gene located downstream from said PHO81 promoter, so that the transformant grows with the accumulation of the gene product, and recovering the gene product from the culture. The above-described DNA fragment having a promoter activity of the PHO81 gene, the transcription of which is preferably regulated with phosphoric acid. The above-described DNA having a promoter activity of the PHO81 gene, is preferably, a DNA bearing a base sequence of between the position 1 and cleavage site with the restriction enzyme ##STR1## in FIG. 9
DETAILED DESCRIPTION OF THE INVENTION
A DNA fragment, segment or construct according to the present invention containing the PHO81 promoter and a structural gene coding for the positive regulatory factor for the repressible phosphatase production (the PHO81 structural gene) may be isolated and collected from yeast cells.
Any strain of Saccharomyces cerevisiae may be used for this purpose. An especially suitable yeast strain is a strain of microorganism belonging to the genus Saccharomyces, such as S. cerevisiae. Commercially available baker's yeasts and brewer's yeast are particular examples of suitable yeast.
The extraction of DNA from yeast may be effected, for example, in accordance with the method described in Methods in Cell Biology, 12, 13-44 (1975).
The extracted DNA is treated with a suitable restriction enzyme to otain a DNA fragment. The fragment is ligated with a plasmid or phage which has been digested with the same restriction enzyme as above or with a restriction enzyme capable of forming the same or compatible cohesive ends as those with the above enzyme, thereby to obtain a gene bank. The plasmid may be, for example, pBR322 or E. coli-yeast shuttle vector YEp13 [Gene, 8, 121 (1979)]. The phage may be, for example, charon phage [J. Virol., 29, 555 (1979)]. If necessary, sub-cloning may be further effected with the use of, for example, E. coli-yeast shuttle vector YEp6 [Gene, 8, 17 (1979)].
A host organism is then transformed with the vector bearing the thus cloned DNA. The host organism is preferably yeast, particularly a strain belonging to the genus Saccharomyces, preferably a strain belonging to the species Saccharomyces cerevisiae, more particularly a strain of Saccharomyces cerevisiae NA95-4B. It is preferred that the host organism be a pho81 mutant.
The strain NA95-4B may be obtained by customarily employed crossing methods [Handbook of Genetics, p366, Plenum Press, New York (1974)]. That is, the strain NA95-4B may be obtained by crossing the strain AL211-12B (MAT.sup.α, pho3-1, pho8, arg6) [Mol. Cell. Biol., 2, 127 (1982)], the strain AH22 (MATa, leu2, his4, canl) [Proc. Natl. Acad. Sci. USA, 80, 1 (1983)], the strain D13-1A (MATa, trpl, his3, ga12, SUC2) [Proc. Natl. Acad. Sci. USA, 76, 1035 (1979)], the strain YAT228 (MATa, leu2, lys10, cyh, karl-1) [J. Bacteriol., 145, 1421 (1981)] and the strain W755-1C (MATa, pho81, leu2, his3, his4).
The pho81 mutant is transformed with the DNA of the gene bank constructed as described above or sub-clone to obtain a plasmid containing the PHO81 structure gene bearing the PHO81 promoter and open reading frame coding for regulatory factor of the repressible phosphatase production.
The transformation may be performed in any known manner, for example, in accordance with one of the methods described in Proc. Natl. Acad. Sci. USA, 75, 1929 (1978), Nature, 275, 104 (1978), Cold Spring Harbor Symp., Quant. Biol., 43, 1305 (1979), and Proc. Natl. Acad. Sci. USA, 76 1035 (1979), or with the similar methods.
Whether or not the transformant contains the PHO81 promoter and the coding region of the PHO81 gene producing the regulatory factor for the repressible phosphatases can be determined in the following manner:
The transformant is cultured in Rubin's modified medium (C. M. Rubin, low phosphoric acid complete medium) [Eur. J. Biochem., 41, 197 (1974)] to allow for the formation of colonies. Then, the medium is overlaid with an agar layer containing α-naphthyl phosphate and fast blue salt B.
If the DNA containing the PHO81 promoter and the coding region of PHO81 protein, the regulatory factor for the repressible phosphatases, is cloned, the colonies will turn red, indicating the presence of the PHO81 gene. The plasmid is extracted from the transformant harboring the PHO81 gene and then digested with, for example, a restriction enzyme. The digest is then subjected to agarose gel electrophoresis or acrylamide gel electrophoresis to fractionate a DNA fragment having the inserted gene. A series of these operations is well known in the art and described in detail in, for example, Molecular Cloning (1982), Cold Spring Harbor Laboratory.
The nucleotide sequence of the DNA containing the PHO81 gene may be determined by, for example, the dideoxynucleotide synthetic chain termination method [Proc. Natl. Acad. Sci. USA, 74, 5463 (1977)], Maxam-Gilbert method [Proc. Natl. Acad. Sci. USA, 74, 560 (1970)] and so on.
The position of the protein-coding region of the PHO81 gene may be deduced by examining the relationship between deleted plasmids and their complementation ability of the pho81 mutation (FIG. 2). Using the plasmid bearing the suspected PHO81 gene (shown by white box in FIG. 2) as a probe, a PHO81 transcript is detected. From the size of the transcript and the base sequence of the PHO81 gene the position of the PHO81 promoter is estimated (FIGS. 3, 5 and 9).
The base sequence of a region which is considered to contain the PHO81 promoter is then determined (FIG. 5). Determination of the nucleotide sequence indicates the presence of an open reading frame. The promoter is thus expected to locate upstream from the open reading frame. The portion of the DNA upstream from the open reading frame and having PHO81 promoter activity [ability to produce the regulatory factor for the repressible phosphatases production (See Table 1)] is prepared (FIG. 7). An expression vector is then prepared by inserting the portion having the PHO81 promoter activity and, if necessary, a desired structural gene downstream thereof into a vector (FIG. 8). The expression vector is inserted into a suitable host microbe which, upon culturing, produces the desired gene product.
The DNA bearing the PHO81 promoter activity may be entirely or partially synthesized by chemical processes and the synthetic or semisynthetic DNA may be used for the purpose of the present invention.
The vector into which the PHO81 promoter is inserted may be, for example, previously described shuttle vector YEp6 or YEp13 or plasmid pSH19 [Mol. Cell. Biol., 4, 771 (1984)] or pJDB219 [Nature, 275, 104 (1978)].
Illustrative of suitable structural genes to be inserted downstream from the PHO81 promoter are the regulating gene encoding the repressible acid phosphatase expression regulating factor (PHO81), the adw-type or adr-type hepatitis B virus surface antigen gene (HBsAg), human α-interferon gene, human β-interferon gene, human γ-interferon gene, human lisozyme gene, human interleukin-2 gene.
The host organism to be transformed with the PHO81 promoter-harboring DNA is preferably yeast, particularly a strain belonging to the genus Saccharomyces, preferably a strain belonging to the species S. cerevisiae, more particularly strains such as S. cerevisiae AH22R - [Proc. Natl. Acad. Sci. USA, 80, 1 (1983)] or S. cerevisiae NA95-4B vide supra).
The transformants thus obtained may be cultured in any known medium such as Burkholder minimum medium [Proc. Natl. Acad. Sci. USA, 77, 4505 (1980)].
The culture conditions such as temperature and time may be varied so as to obtain the maximum yield of the desired gene product. Generally, a temperature of about 15°-40 °C., preferably about 24°-37° C. and a time of about 10-96 hours, preferably 24-72 hours are used. Aeration and agitation may be adopted, as necessary.
The gene product accumulated in the culture may be extracted in any known manner, such as by lyzing or disrupting the cells with the use of lysozyme such as Zymolyase (Seikagaku Kogyo, Ltd. Japan) or by mechanical disrupting method using glass beads. A detergent such as Triton-X100 and a protein denaturating agent such as guanidine hydrochloride may be used to facilitate the extraction of the product. The extract is then subjected to isolation and purification treatments conducted in conventional manner such as by precipitation using a precipitating agent, dialysis, electrophoresis, chromatography using ion exchange resins, gel filtration or a method using an antibody column.
In accordance with the present invention, there is provided a novel and potent promoter obtained from yeasts which are eukaryotic microorganisms. The promoter is very useful for the effective expression of pharmacologically important protein genes.
The following examples will further illustrate the present invention.
Saccharomyces cerevisiae P-28-24C used as a starting material in Example 1 is deposited at the Institute for Fermentation, Osaka, Japan under the accession number of IFO-10153, and deposited at the American Type Culture Collection (ATCC), U.S.A., under the accession number of ATCC 60202. The transformant S. cerevisiae P-28-24C. is deposited at IFO and ATCC under permanent deposition and is freely available to any requester.
The transformant, Escherichia coli DHl/pAC430 shown in Example 8 is deposited at the Institute for Fermentation, Osaka, Japan under the accession number of IFO-14456 and has also been deposited at Fermentation Research Institute, Agency of Industrial Science and Technology, Ministry of International Trade and Industry, Japan (FRI) under the accession number of FERM P-8411 since Aug. 9, 1985 and changed to the deposit under the accession number of FERM BP-1089 according to the Budapest Treaty.
The transformant, Saccharomyces cerevisiae AH22R - /pACZ403 shown in Example 12 is deposited at the Institute for Fermentation, Osaka, Japan under the accession number of IFO-10207 since May 28, 1986 and also deposited at FRI under the accession number of FERM BP-1090 according to the Budapest Treaty since June 25, 1986.
EXAMPLE 1
Cloning of the PHO81 gene (See FIG. 1)
Chromosomal DNA obtained in a conventional manner from S. cerevisiae P-28-24C (MATa pho3-1) (IFO 10153, ATCC 60202) was partially digested with Sau3AI. The Sau3AI restriction fragments were inserted into the BamHI site of yeast-E. coli shuttle vector YEp13 [J. R. Broach et al., Gene, 8, 121 (1979)] according to the method of Nasmyth and Reed [K. A. Nasmyth & S. I. Reed, Proc. Natl. Acad. Sci. USA, 77, 2119 (1980)] to prepare a yeast gene bank consisting of about 2000 clones of E. coli showing the ampicillin resistant (Amp r ) and tetracycline sensitive (Tc s ) phenotype. The plasmid DNA of the yeast gene bank was introduced into the strain S. cerevisiae NA95-4B (MATα pho81 leu2 his3 trpl canl) for transformation. Transformants showing repressible acid phosphatase producing activity (rACp + ) were screened by the colony staining method [modified method of G. Dorn, Genet. Res., 6, (1965)] using a 1% agar solution containing 0.5 mg/ml of α-naphthylphosphate, 5 mg/ml of fast blue salt B and 0.05M acetate buffer. Five rACp + transformants were obtained from about 8×10 3 transformants which are prototrophic for leucine (Leu + ). One of the five rACp + transformants was used to prepare a plasmid DNA according to the method of Cameron et al [J. R. Cameron et al., Nucleic Acids Res., 4, 1429 (1977)] and the plasmid DNA was transformed into E. coli JA221. All of the 35 Amp r transformants were Tc s and had a plasmid of the same molecular weight. This plasmid was named pAC4 and was again introduced into S. cerevisiae NA95-4B for transformation. Eighteen of the thus obtained Leu + transformants were tested for their repressible acid phosphatase production activity to reveal that all of them were rACp + . This suggests that pAC4 has an insertion of a DNA fragment bearing the PHO81 gene. If PHO81 is included, then pAC4 is expected to be able to be integrated into the pho81 locus of chromosome by virtue of its homology. A stable transformant of S. cerevisiae YAT408 (leu2, lys10, canl, cir 0 ) containing pAC4 was subjected to genetic analysis for the determination of the integration site of pAC4. Thus, the transformant containing pAC4 was crossed with S. cerevisiae YAT637 (MATa pho81 leu2) and was subjected to a tetrad analysis. As a result, the segregation of Leu 30 Acp + and Leu - Acp - phenotypes in tetrad showed 4:0, 3:1 and 2:2. The numbers of tetrads showing 4:0, 3:1 and 2:2 segregations were 0, 2 and 21, respectively. A second cross was carried out with the pAC4-containing transformant and S. cerevisiae YAT61 (MATa PHO81 LEU2). The tetrad analysis of the resultant diploid revealed that a ratio of the tetrads showing 4+:0-, 3+:1- and 2+:2- segregations of Leu phenotype was 2:33:4. The foregoing genetic data permit one to conclude that pAC4 is inserted on the PHO81 gene site or its vicinity, i.e., the PHO81 gene is cloned into pAC4.
EXAMPLE 2
Preparation of Restriction Enzyme Map for DNA Fragment Bearing the PHO81 Gene
The pAC4 DNA (1-5 μg) was digested in TA buffer [P. H. O'Farrell et al., Molec. Gen. Genet., 179, 421 (1980)] with 4-6 units of single or a combination of restriction enzymes selected from BamHI, EcoRI, HindIII, PstI, SalI and XhoI at 37° C. for 1 hour. The digestion products were electrophoresed on a 1% agarose gel or 7.5% polyacrylamide gel and the gels were examined for the restriction patterns to estimate molecular weights of the restriction fragments. Then, a restriction enzyme cleavage map was prepared as shown in FIG. 1, in which restriction sites are designated by letters as follows:
______________________________________E: EcoRI H: HindIIISa: SalI X: XhoIP: PstI B: BamHI______________________________________
EXAMPLE 3
Estimation of the Position of PHO81 Gene on Cloned DNA Fragment (See FIG. 2)
In order to estimate the position of the PHO81 gene in the cloned DNA fragment, various deletion derivatives of pAC4 were prepared. Thus, pAC4 (5 μg) was digested in 50 μl of TA buffer containing 6 units of BamHI at 37°C. for 1 min and then at 65° C. for 10 min to obtain a partially digested product. A 25 μl -portion of the digestion mixture was mixed with 50 μl of T4 ligase solution containing 5 mM MgCl 2 , 10 mM dithiothreitol, 0.05 mM ATP and 3 units of T4 ligase and the mixture was allowed to stand at 4° C. for 18 hours to religate the partially digested product described above. E. coli JA221 was transformed with the use of the T4 ligase reaction solution (10 μl). From the Amp r transformants thus obtained, a plasmid DNA was isolated in accordance with the method of Birnboim and Doly [H. C. Birnboim & J. Doly, Nucleic Acids Res., 7, 1513 (1979)], to afford the deleted plasmid pAC4-LB3. The above procedures were repeated in the same manner using SalI and XhoI in place of BamHI to obtain pAC4-LS1 and pAC4-LX1, respectively. Further, pAC4-LB3 was treated in the same manner using HindIII to obtain the deleted plasmid pAC4-LB3H. Each of the resultant deleted plasmid DNA was used for transformation of S. cerevisiae NA95-4B and Leu + transformants were selected. Ten selected transformant strains were tested for their phenotype with respect to repressible acid phosphatase (rACp + 1). The positive or negative result of complementation tests of the pho81 mutation with the deletion plasmids is shown in FIG. 2 in terms of + and -.
S. cerevisiae NA95-4B was transformed with pAC4-LX1. The rACp producing activity of the resultant Leu + transformants is lower than that of the wild type strain (the activity is shown as + in FIG. 2). The foregoing results indicate that the PHO81 gene is located at a region (about 3.0 kb) shown by the white box in FIG. 2.
EXAMPLE 4
Acid Phosphatase Producing Activity of Transformant Containing pAC4-LB3
The pAC4-LB3-containing transformant S. cerevisiae NA95-4B/pAC4-LB3 obtained in Example 3 was cultivated in 5 ml of Berkholder's modified high phosphoric acid medium and low phosphoric acid medium [A. Toh-e et al, J. Bacteriol., 113, 727 (1973)] for 20 hours with shaking. The cells were collected for measuring the acid phosphatase activity in accordance with the modified method of Torriani [A. Torriani, Biochim. Biophys. Acta, 38, 460 (1960)]. The results were as shown in Table 1.
As will be understood from Table 1, the production of the acid phosphatase by pAC4-LB3 is repressed by inorganic phosphate. Thus, the cloned PHO81 gene is considered to include both a region coding for the protein (PHO81 gene product) which regulates the expression of PHO5 and a promoter region.
TABLE 1______________________________________Acid Phosphatase Production Activityof Transformants Containing pAC4-LB3 Acid Phosphatase Activity*Strain of High Phosphoric Low PhosphoricS. cerevisiae Genotype a Acid b Acid c______________________________________P-28-24C Wild type 0.003 0.099NA95-4B/ pho81[pAC4- 0.003 0.102pAC4-LB3 LB3]NA95-4B pho81 0.004 0.005______________________________________ a Indicated with respect to phosphatase only *Units/ml/OD.sub.660 b KH.sub.2 PO.sub.4 concentration of 1.5 mg/ml c KH.sub.2 PO.sub.4 concentration of 0.03 mg/ml
EXAMPLE 5
Identification of PHO81 Gene Transcript
The transcription product of PHO81 was identified according to the Northern hybridization method. Total RNA was prepared from S. cerevisiae P-28-24C cultured in a complete medium (+P) and a low phosphoric acid medium (-P) in accordance with the method of Jensen [R. Jensen et al., Proc. Natl. Acad. Sci. USA, 80, 3035 (1983)], followed by purification by affinity column chromatography on oligo dT-cellulose in accordance with the method of Schleif and Wensink [R. F. Schleif & P. C. Wensink, Practical Methods in Molecular Biology, (1981), Springer-Verlag] to obtain poly(A) + RNA. The poly(A) + RNA sample thus obtained was subjected to formaldehyde gel electrophoresis as described in the article [Molecular Cloning, (1982), Cold Spring Harbor Laboratory], followed by blotting and hybridization according to the method of Thomas [P. S. Thomas, Proc. Natl. Acad. Sci. USA, 77, 5201 (1980)]. Autoradiography was performed at -80° C. employing a Kodak X-O-mat RP film and a Kodak intensifying screen. The probe DNA used for the identification of the transcript was prepared by nick translation [P. W. J. Rigby et al., J. Mol. Biol., 113, 237 (1977)] of a plasmid pAC450 obtained by subcloning a BamHI-SalI restriction fragment of about 3.2 kb, which was located between the BamHI restriction cleavage site in the vicinity of 9.2 kb of the cloned yeast chromosomal DNA (FIG. 1) and the SalI restriction cleavage site of YEp13, into pBR322 double-digested with BamHI and SalI.
The results are shown in FIG. 3. The size of the PHO81 transcript is 2.8 kb. The fact that the amount of the PHO81 transcript is much greater than that of the URA3 gene which codes for orotidine-5'-phosphate-decarboxylase [The Molecular Biology of the Yeast Saccharomyces, life cycle and inheritance, Cold Spring Harbor Lab., 731 (1981)] suggests the strong activity of the PHO81 promoter. Since the transcription of PHO81 is repressed in the high phosphate environment (+P), the PHO81 promoter is considered to be repressed by phosphoric acid.
EXAMPLE 6
Preparation of Restriction Enzyme Map for 3.0 kb DNA Fragment Bearing the PHO81 Gene
The restriction enzyme map for the restriction fragment between the BamHI site and the Sau3AI/BamHI site including the PHO81 gene (the region shown by white box in FIG. 2) was prepared with the use of 14 different restriction enzymes (AluI, BanII, BstNI, DdeI, EcoRI, HaeIII, HindIII, HpaI, HpaII, RsaI, SalI, Sau3AI, Sau96I and XhoI) and is shown in FIG. 4. The fragment was digested with one or a combination of two of the enzymes. The digestion mixtures were electrophoresed on 7.5% or 12% polyacrylamide gels. Restriction enzyme cleavage sites were estimated from the cleavage patterns. A HaeIII or AluI digest of pBR322 was used as a molecular weight marker. Only the restriction enzyme cleavage sites whose positions are confirmed are shown in FIG. 4.
EXAMPLE 7 Determination of the Base Sequence of DNA Bearing the PHO81 Gene
The base sequence of the DNA fragment of 3.0 kb located between BamHI and BamHI/Sau3A sites (See FIG. 2) and considered to bear the PHO81 gene was determined according to the method of Maxam and Gilbert (vide supra) and is shown in FIG. 5. In the nucleotide sequence, there exists a translatable region of about 2.5 kb. From this frame, the direction of transcription is expected to be from the BamHI site to the BamHI/Sau3A site. A translational initiation codon "ATG" is present at about 520 bases downstream from the BamHI cleavage site. At 67 bp (base pairs) upstream from the "ATG", there is present a sequence TATTA which is considered to function as a TATA box. A sequence TCATCA, which is similar to capping site, exists at 57 bp upstream from the "ATG". Further, there is a sequence CCAAT at 109 bp upstream from the "ATG". This sequence is identical with that of CCAAT box [Nucleic Acids Res., 10, 2625-2637 (1982); ibid 12, 857-872 (1984); ibid 12, 1137-1148 (1984)]. FIG. 5 shows the base sequence of a region of 700 bases downstream from the BamHI cleavage site. A non-translational region of 5'-upstream side of the PHO81 gene and a 5'-terminal region of the PHO81 gene are considered to be included within the illustrated region.
EXAMPLE 8
Construction of Plasmid pAC430 and Preparation of Transformant Using Same
The plasmid pAC4-LB3 (5 μg) was digested with 5 units of BamHI and 5 units of SalI in the manner described in Example 2. The digestion mixture was subjected to electrophoresis on a 1% low melting agarose gel to recover a DNA fragment of 3.2 kb. This fragment was mixed with pBR322 (5 μg) digested with 5 units of BamHI and 5 units of SalI, and the mixture was ligated by T4 ligase in the same manner as described in Example 2 to obtain a plasmid pAC430 (See FIG. 6). The plasmid pAC430 was introduced into E. coli DH1 for transformation to obtain a transformant Escherichia coli DH1/pAC430(IFO 14456, FERM BP-1089).
EXAMPLE 9
Construction of adw-Type Hepatitis B Virus Surface Antigen P25 Gene Expression Plasmid Using the PHO81 Promoter and Transformation of Yeast with the Plasmid
The plasmid pAC430 (0.5 μg) is digested with 1 unit of restriction enzyme AccII (manufactured by Nippon Gene Inc.) in 20 μl of a reaction medium [6 mM Tris-HCl (pH7.5), 60 mM NaCl, 6 mM MgCl 2 , 6 mM 2-mercaptoethanol] at 37° C. for 2 hours, followed by elimination of protein with phenol and the DNAs were precipitated by addition of cold ethanol. The precipitated DNA is mixed with 50 ng of a SalI linker having a phosphorylated 5'-terminal [5'-P-d(GGTCGACC)] (manufactured by New England Biolabs Inc.) and the mixture was reacted in 20 μl of a reaction liquid containing 66 mM Tris-HCl (pH7.6), 6.6 mM MgCl 2 , 10 mM dithiothreitol, 1 mM ATP and 2 units of T4 DNA ligase (manufactured by New England Biolabs. Inc.) at 14° C. overnight to ligate the DNA. E. coli DH1 [T. Maniatis et al., Molecular Cloning, Cold Spring Harbor Laboratory, 254-255 (1982)] is transformed with the use of the above ligation liquid, and ampicillin resistant transformants were selected. From the selected transformants, plasmid pAC430-1 having a SalI site substituted for the AccII site of the plasmid pAC430 is obtained (See FIG. 7). The plasmid pAC430-1 (10 μg) is digested with 10 units of restriction enzyme BamHI and 10 units of restriction enzyme SalI (manufactured by Nippon Gene Inc.) in 50 μl of a reaction medium [10 mM Tris-HCl (pH7.5), 7 mM MgCl 2 , 100 mM NaCl, 7 mM 2-mercaptoethanol] at 37° C. for 2 hours. The digest is then applied to a 1.2% agarose-slab gel and electrophoresed in a buffer [100 mM Tris-HCl, 100 mM boric acid, 2 mM EDTA (pH 8.3)] at 140 V for 2 hours. After the electrophoresis, the region of the gel containing 0.5 kb DNA fragment is placed in a dialysis tube and immersed in the above electrophoresis buffer. The DNA fragment is extracted from the gel by electrical elution [M. W. McDonell et al., J. Mol. Biol., 110, 119 (1977)]. The liquid within the dialysis tube is extracted with phenol and then with ether. Following extraction,.the aqueous phase is adjusted to 0.2M with NaCl. The DNA fragment containing the PHO81 promoter is precipitated by the addition of 2 volumes of cold ethanol.
The adw-type hepatitis B virus surface antigen (HBsAg P25) gene expression plasmid pPHO17-58 (50 μg) disclosed in the Example of the specification of Japanese-Patent Application No. 59-193765 filed Sept. 13, 1984 (which corresponds to European Patent Publication No. 175283 and corresponds pending U.S. patent Appln. Ser. No. 774,333 filed September 10, 1985) is partially digested with 50 units of restriction enzyme XhoI (manufactured by Nippon Gene Inc.) in 100 μl of a reaction medium [10 mM Tris-HCl (pH 7.5), 7 mM MgCl 2 , 100 mM NaCl, 7 mM 2-mercapto- ethanol] at 37° C. for 20 min. From the digest mixture is separated a DNA fragment of 9.1 kb, which is cleaved at only one of the two XhoI restriction enzyme cleavage sites of the plasmid, by means of the agarose-slab gel under the same condition as described previously.
The DNA fragment of 9.1 kb (4 μg) thus recovered is then digested with 4 units of restriction enzyme BamHI in 20 μl of a reaction medium [6 mM Tris-HCl (pH 7.9), 150 mM NaCl, 6 mM MgCl 2 ] at 37° C. for 2 hours, followed by electrophoresis conducted under the same conditions as above, thereby to isolate 8.55 Kb DNA.
The 8.55 kb DNA (200 ng) is ligated with the 0.5 kb DNA (20 ng) containing the PHO81 promoter using T4 DNA ligase. With the use of the resultant mixture, E. coli DH1 is transformed. From the ampicillin resistant transformants, transformant DH1/pPHO81-P25 containing the plasmid pPHO81-P25 in which the PHO81 promoter is inserted in the same direction as the HBsAgP25 gene is selected. Plasmid pPHO81-P25 is then isolated from the transformant (See FIG. 7) and introduced into a yeast strain of Saccharomyces cerevisiae AH22R - , thereby to obtain transformant AH22R - /pPHO81-P25.
EXAMPLE 10
Construction of an Expression plasmid for the production of adr-type Hepatitis B Virus Surface Antigen P31 Using PHO81 Promoter and Transformation of Yeast with the Plasmid
The adr-type hepatitis B Virus surface antigen (HBsAg P31) gene expression plasmid pPHO P31-R (50 μg) disclosed in Example 3 of International Patent Application No. PCT/JP84/423 (International Filing Date: September 4, 1984) (which corresponds to European Patent Publication No.171908 and corresponds to pending U.S. patent application Ser. No. 753,540 filed Jul. 10, 1985) is digested with 50 units of restriction enzyme SalI in 100 μl of a reaction medium [6 mM Tris-HCl (pH 7.9), 150 mM NaCl, 6 mM MgCl 2 , 6 mM 2-mercaptoethanol] at 37°C. for 20 min. From the digest is separated a DNA fragment of 9.7 kb, which is cleaved at only one of the two SalI restriction enzyme cleavage sites of the plasmid, by means of the agarose-slab gel in the same manner as above.
The DNA fragment of 9.7 kb (4 μg) thus recovered is then digested with 4 units of restriction enzyme BamHI, followed by electrophoresis under the same conditions as above, thereby to isolate a 9.2 kb DNA. The 9.2 kb DNA (200 ng) is ligated with the 0.5 kb DNA (20 ng) containing the PHO81 promoter with the employment of T4 DNA ligase. Using the resultant mixture, E. coli DH1 is tansformed. From the ampicillin resistant transformants, transformant DH1/pPHO81-P31 containing the plasmid pPHO81-P31 in which the PHO81 promoter is inserted in the right direction as the HBsAg P31 gene is selected. Plasmid pPHO81-P31 is then isolated from the transformant (See FIG. 7) and introduced into yeast host Saccharomyces cerevisiae AH22R - to obtain transformant AH22R - /pPHO81-P31.
EXAMPLE 11
Expression of the HBsAg Gene in Yeast
The transformants Saccharomyces cerevisiae AH22R - /pPHO81-P25 and AH22R - /pPHO81-P31 containing the HBsAg gene expression plasmid and obtainable in Examples 9 and 10 are cultivated at 30° C. for 2 days in Burkholder medium and its low phosphoric acid medium. Cells are collected and washed with physiological saline solution. The cells are then treated with Zymolyase (Seikagaku Kogyo Co. Ltd., Japan) in accordance with the method of Miyanohara [A. Miyanohara, Proc. Natl. Acad. Sci. USA, 80, 1 (1983)] to form spheroplasts. After adding 0.1% of Triton X-100 for expediting extraction of HBsAg, the lysate is centrifuged at 15,000 rpm for 15 min at room temperature. The supernatant liquid was tested for the detection of HBsAg activity by means of Orthzyme II (manufactured by Dynabot K. K.).
EXAMPLE 12
Expression of lacZ Gene Using PHO81 Promoter
Using respectively 10 units of restriction enzyme ScaI and SmaI (manufactured by Takara Shuzo Co. Ltd., Japan ), 10 μg of pAC430 containing PHO81 gene (the region from the white box portion in FIG. 2 to the SalI site of YEp13) were digested in 100 μl of a reaction medium [33 mM Tris-acetic acid (pH7.9), 66 mM K-acetate, 10 mM Mg-acetate, 5 mM dithiothreitol] at 37° C. for 2 hours. The digest was applied to a 4% acrylamide gel and electrophoresed in buffer (89 mM Tris, 89 mM boric acid, 2.5 mM EDTA) at 150 V for 3 hours. Following the electrophoresis, the portion of the gel containing 2100 bp DNA fragment (ScaI-SmaI restriction fragment) was placed in a Corex tube for the destruction thereof, to which was then added 5 ml of a DNA extraction buffer of 0.5M (NH 4 )COOCH 3 , 10 mM Mg-acetate, 1 mM EDTA, 0.1% (w/v) SDS. The resultant mixture was allowed to stand overnight at 37° C. and filtered. The DNA fragment was precipitated by the addition of ethanol to the filtrate and recovered for use in the ligation reaction described below.
Plasmid pMC1587 (1 μg) was digested with 1 unit of restriction enzyme SmaI (manufactured by Takara Shuzo Co. Ltd.) in 50 μl of a reaction mixture (1 mM Tris, 10 mM NaCl, 0.6 mM MgCl 2 ) at 37° C. for 2 hours. The restriction DNA fragment was precipitated with ethanol and recovered. The above described DNA fragment (0.1 μg) from pMC1587 digested with SmaI was ligated with the ScaI-SmaI restriction fragment of 2100 bp(5 μg) using T4 DNA ligase to produce a plasmid pACZ403(FIG. 8). In the thus obtained plasmid, a portion of the PHO81 translational sequence located in the ScaI-SmaI DNA fragment of 2100 bp was ligated at the SmaI connecting site with the lacZ translational sequence located in the pMC1587, with the reading frames of both genes being ajusted.
The thus obtained plasmid pACZ403 was introduced into Saccharomyces cerevisiae AH22R - to obtain transformant Saccharomyces cerevisiae AH22R - /pACZ403(IFO-10207, FERM BP-1090). The transformant was cultured for 20 hours in the same manner as described in Example 11 and the cells were treated in the same manner as described in Example 11 to obtain the following results.
______________________________________ The expression of β-galactosidase unit/l______________________________________The medium containing high concentration 600of phosphoric acid (KH.sub.2 PO.sub.4 1.5 g/l)The medium containing low concentration 2600of phosphoric acid (KH.sub.2 PO.sub.4 0.3 g/l)______________________________________
EXAMPLE 13
Sequencing of PHO81 Gene
The DNA sequence of the BamHI-BanII fragment (about 2.6 kb) containing the PHO81 gene was determined according to the method of Maxam and Gilbert described in Example 7 and is shown in FIG. 9. In the base sequence, there exists a "stop codon" at about 2330 bp region.
The following references, which are referred to for their disclosures at various points in this application, are incorporated herein by reference.
Methods in Cell Biology, 12, 13-44(1975).
Gene, 8, 121 (1979).
J. Virol., 29, 555 (1979)
Gene, 8, 17 (1979).
Handbook of Genetics, p366, Plenum Press, New York(1974).
Mol. Cell. Biol., 2, 127 (1982).
Proc. Natl. Acad. Sci. USA, 80, 1 (1983).
Proc. Natl. Acad. Sci. USA, 76, 1035 (1979).
J. Bacteriol., 145, 1421 (1981).
Proc. Natl. Acad. Sci. USA, 75, 1929 (1978).
Nature, 275, 104 (1979).
Eur. J. Biochem., 41, 197 (1974).
Proc. Natl. Acad. Sci. USA, 74, 5463 (1977).
Proc. Natl. Acad. Sci. USA, 74, 560 (1970).
Mol. Cell. Biol., 4, 771 (1984).
Nature, 275, 104 (1978).
Proc. Natl. Acad. Sci. USA, 80, 1 (1983)
Proc. Natl. Acad. Sci. USA, 77, 4505 (1980).
Gene, 8, 121 (1979).
Proc. Natl. Acad. Sci. USA, 77, 2119 (1980)
Genet. Res., 6, (1965).
Nucleic Acids Res., 4, 1429 (1977).
Molec. Gen. Genet., 179, 421 (1980).
Nucleic Acids Res., 7, 1513 (1979).
J. Bacteriol., 113, 727 (1973).
Biochim. Biophys. Acta, 38, 460 (1960).
Proc. Natl. Acad. Sci. USA, 80, 3035 (1983).
Practical Methods in Molecular Biology, (1981). Springer-Verlag.
Proc. Natl. Acad. Sci. USA, 77, 5201 (1980).
J. Mol. Biol., 113, 237 (1977).
The Molecular Biology of the Yeast Saccharomyces, Life Cycle and Inheritance, Cold Spring Harbor Lab., 731 (1981).
Nucleic Acids Res., 10, 2625-2637 (1982). ibid 12, 857-872 (1984); ibid 12, 1137-1148(1984).
Molecular Cloning, Cold Spring Harbor Laboratory, 254-255 (1982).
J. Mol. Biol., 110, 119 (1977).
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The present invention relates to a DNA fragment having a promoter activity of PHO81 gene regulating the production of phosphatase, and which is obtainable from Saccharomyces cerevisiae.; a DNA fragment bearing a structural gene downstream from the above PHO81 promoter; a transformant containing a DNA fragment bearing the above PHO81 promoter; a transformant containing a DNA fragment bearing the above PHO81 promoter and a structural gene downstream from the PHO81 promoter; and a process for obtaining a gene product which includes culturing a transformant containing a DNA fragment bearing the above PHO81 promoter and a structural gene located downstream therefrom in a suitable medium until the gene product is formed and recovering the gene product from the culture. Pharmacologically important proteinous materials may be efficiently produced with the use of the above-described novel and potent promoter obtained from yeast which is a eukaryotic microorganism.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of now abandoned U.S. application Ser. No. 09/364,044, filed Jul. 30, 1999.
BACKGROUND OF THE INVENTION
The present invention relates to a novel potato variety and to the tubers, plants, plant parts, tissue culture and seeds produced by that potato variety.
The publications and other materials used herein to illuminate the background of the invention and, in particular cases, to provide additional details respecting the practice, are incorporated by reference and for convenience, are referenced in the following text by author and date and are listed alphabetically by author in the appended bibliography.
The potato is the world's fourth most important food crop and by far the most important vegetable. Potatoes are currently grown commercially in nearly every state of the United States. Annual potato production exceeds 18 million tons in the United States and 300 million tons worldwide. The popularity of the potato derives mainly from its versatility and nutritional value. Potatoes can be used fresh, frozen or dried, or can be processed into flour, starch or alcohol. They contain complex carbohydrates and are rich in calcium, niacin and vitamin C.
To keep the potato industry growing to meet the needs of the consuming public, substantial research and development efforts are devoted to the modernization of planting and harvesting of fields and processing of potatoes, and to the development of economically advantageous potato varieties. Through crossbreeding of potatoes, researchers hope to obtain potatoes with the desirable characteristics of good possibility, high solids content, high yield, resistance to diseases and pests and adaptability to various growing areas and conditions.
The U.S. acreage planted in potatoes has declined since the 1960s and 1970s, and this decline, coupled with increasing consumption, must be offset by higher useable yields. In some areas, diseases and pests damage crops despite the use of herbicides and pesticides. The problem of the golden nematode in the United States, presently endemic to portions of New York State, is one example of the destruction to susceptible potato varieties. Potato varieties with high yields, disease resistance and adaptability to new environments can eliminate many problems for the potato grower and provide more plentiful and economical products to the consumers.
For the potato chip processing industry, potatoes having high solids content, good shipping qualities and good finished chip color can increase production volumes and efficiencies and product acceptability. Potato varieties which yield low-solids tubers result in unnecessary energy usage during the frying process. Moreover, as solids content increases, the oil content of fried products decreases, which is a favorable improvement. Potato varieties in the warm southern tier of states are most in need of solids improvement overall, while those varieties grown and stored in the colder northern tier of states are most in need of the ability to recondition after cool or cold storage to increase their value for use in the potato chip industry. Reconditioning is necessary to elevate the temperature of the potatoes after cold storage and before further processing.
The research leading to potato varieties which combine the advantageous characteristics referred to above is largely empirical. This research requires large investments of time, manpower, and money. The development of a potato cultivar can often take up to eight years or more from greenhouse to commercial usage. Breeding begins with careful selection of superior parents to incorporate the most important characteristics into the progeny. Since all desired traits usually do not appear with just one cross, breeding must be cumulative.
Present breeding techniques continue with the controlled pollination of parental clones. Typically, pollen is collected in gelatin capsules for later use in pollinating the female parents. Hybrid seeds are sown in greenhouses, and tubers are harvested and retained from thousands of individual seedlings. The next year a single tuber from each resulting seedling is planted in the field, where extreme caution is exercised to avoid the spread of virus and diseases. From this first-year seedling crop, several “seed” tubers from each hybrid individual which survived the selection process are retained for the next year's planting. After the second year, samples are taken for density measurements and fry tests to determine the suitability of the tubers for commercial usage. Plants which have survived the selection process to this point are then planted at an expanded volume the third year for a more comprehensive series of fry tests and density determinations. At the fourth-year stage of development, surviving selections are subjected to field trials in several states to determine their adaptability to different growing conditions. Eventually, the varieties having superior qualities are transferred to other farms and the seed increased to commercial scale. Generally, by this time, eight or more years of planting, harvesting and testing have been invested in attempting to develop the new and improved potato cultivars.
Long-term, controlled-environment storage has been a feature of the northern, principal producing areas for many years. Potatoes harvested by October must be kept in good condition for up to eight months in temperatures that may drop to −30 degrees C. at times and with very low relative humidity in the outside air. Storages are well insulated, not only to prevent heat loss but also to prevent condensation on outside walls. The circulation of air at the required temperature and humidity is automatically controlled depending on the purpose for which the potatoes are being stored. Sprout inhibition is now largely carried out in storage as it has been found to be more satisfactory than the application of maleic hydrazide (MH30) in the field.
Proper testing of new plants should detect any major faults and establish the level of superiority or improvement over current varieties. In addition to showing superior performance, a new variety must be compatible with industry standards or create a new market. The introduction of a new variety will increase costs of the tuber propagator, the grower, processor and consumer; for special advertising and marketing, altered tuber propagation and new product utilization. The testing preceding release of a new variety should take into consideration research and development costs as well as technical superiority of the final variety. Once the varieties that give the best performance have been identified, the tuber can be propagated indefinitely as long as the homogeneity of the variety parent is maintained. For tuber propagated varieties it must be feasible to produce, store and process potatoes easily and economically.
Thus, there is a continuing need to develop potato cultivars which provide good processability out of storage, with minimal bruising, for manufacturers of potato chips and other potato products and to combine this characteristic with the properties of disease resistance, resistance to pests. The present invention addresses this need by providing the new variety as described herein.
SUMMARY OF THE INVENTION
According to the invention, there is provided a novel potato cultivar of the genus and species, Solanum tuberosum , designated FL1879. This invention thus relates to the tubers of potato variety FL1879, the plants and plant parts of potato variety FL1879 and to methods for producing a potato plant produced by crossing the potato variety FL1879 with itself or another potato variety. This invention further relates to hybrid potato seeds and plants produced by crossing the potato variety FL1879 with another potato plant.
In another aspect, the present invention provides for Single Gene Converted plants of FL1879. The single gene transferred may be a dominant or recessive allele. Preferably, the single gene transferred will confer such traits as herbicide resistance, insect resistance, resistance for bacterial, fungal or viral disease, uniformity and increase in concentration of starch and other carbohydrates, decrease in tendency of tuber to bruise and decrease in the rate of conversion of starch to sugars. The single gene transferred may be a naturally occurring gene or a transgene introduced through genetic engineering techniques.
DETAILED DESCRIPTION OF THE INVENTION
A novel potato cultivar of the present invention, which has been designated FL1879, has been obtained by selectively crossbreeding parental clones through several generations. The immediate parents of FL1879 were cultivars designated FL1207 and Snowden. These parent strains were selected for the ability to be processed into light-colored potato chips when stored several months at cold temperatures and for their properties of a high number of tuber sets and good yield potential, as well as high content of dry matter.
FL1879 cultivar has olive green foliage. This cultivar has medium, but ultimately vigorous vine growth and few white flowers and produces tubers which are characterized by a pale yellow flesh color, a good specific gravity, moderately high dry matter content, and a substantially smooth, slightly oval shape. As a chipping variety to be grown principally for processing out of storage, the most appropriate variety with which to compare FL1879 is the commercial cultivar Snowden, which is one of the parental lines. A comparison of FL1879 with Snowden reveals that FL1879 has semi-erect growth habit and produces oval, pale yellow fleshed tubers while Snowden's growth habit is more erect, has less compact plants, and produces round, white fleshed tubers. While both FL1879 and Snowden have white flowers that are similar, flowering is much more frequent in Snowden.
FL1879 has average yields slightly higher than Snowden and its solids are slightly lower. FL1879 is highly resistant to Tuber Early Blight, which is a significant benefit in the Southwest. The tubers produced by FL1879 are well-suited for the production of potato chips. A characteristic feature of the tubers is their comparatively good specific gravity relative to the standard commercial variety in a production area. The specific gravity generally ranges from about 1.070 to 1.079; however, it will be appreciated that specific gravities can vary substantially depending upon growing conditions and areas. Higher specific gravities are advantageous for chipping and other frying, applications, as they reduce the total energy and time required for the frying operation.
In addition to the specific gravity of the tubers of this invention, they also have an advantageous shape for commercial operations. The tubers are smooth skinned and generally lack knobs and other protuberances, as well as deep ridges or convolutions. Accordingly, they are amenable to efficient washing and peeling operations using large-scale automated equipment. Such shapes produce a high quality product with a minimal amount of waste. The tubers are generally oval in shape and have a size which is suited to the manufacture of potato chips. On average, these tubers have a mean length of 80 millimeters (range: 62-105 millimeters); a mean width of 73 millimeters (range: 60-90 millimeters); and a mean thickness of 52 millimeters (range: 40-68 millimeters) based upon a 100-tuber sample. Of course, the size of the tubers can vary over a relatively Wide range depending on growing conditions and locations. The slightly flattened shape of the tubers is advantageous, because it facilitates alignment in the slicing apparatus.
Among the more important characteristics of the potato cultivar of this invention is its resistance to tuber blemishes caused by early blight ( Altemaria solani ), which is a significant threat to production in the Southwest. Additionally, it has pale yellow flesh and produces attractive chips both fresh from the field and after storage from October through April. A comparison of the storage life of tubers from the parent cultivar, Snowden, and the cultivar of this invention illustrates that the cultivar of the invention has a storage life which is approximately eight months longer than that of Snowden.
Other advantageous properties of the plants of the present invention include its potential as a storage chipping variety for the northern states of the United States, as well as areas of Texas and New Mexico that grow chipping potatoes for storage.
In addition to the morphological characteristics and disease and pest resistance as described above, the plants of this invention are characterized by their protein fingerprint patterns. The protein “fingerprint” is determined by separating tuber proteins on an electrophoretic gel under certain defined conditions. The pattern of the proteins, attributable to their differential mobilities on the electrophoretic gel, have been found to be characteristic of the particular plant involved. This pattern has thus been termed a “fingerprint.” Isozyme fingerprints of all available North American potato varieties have revealed that no two varieties have the same pattern for the enzymes tested. (Douches and Ludlam, 1991). The Isozyme fingerprint of FL1879 has been established as distinct from that of any other variety tested, including Snowden (Douches and Ludlam, 1991). These techniques generally involve extracting proteins from the tuber and separating them electrophoretically.
Potato variety FL1879 has the following morphologic and other characteristics.
VARIETY DESCRIPTION INFORMATION
1.
Classification: Solanum Tuberosum L.
2.
Plant characteristics: (Observed at beginning of bloom)
Growth habit:
Semi-erect (30°-45° with ground)
Type:
Intermediate
Maturity (Days after planting-
135
DAP):
Maturity Class:
Late (121-130 DAP)
3.
Stem Characteristics: (Observed at early first bloom)
Stem (anthocyanin coloration):
Absent
Stem (wings):
Medium
4.
Leaf Characteristics: (Observed fully developed leaves located
in the middle one-third of plant):
Leaf (color):
Olive green/137A RHS
Leaf (pubescence density):
Medium
Leaf (silhouette):
Medium
Petioles (anthocyanin
Absent
coloration):
Terminal leaflet (shape):
Medium ovate
Terminal leaflet (shape of tip):
Cuspidate
Terminal leaflet (shape of base):
Obtuse
Terminal leaflet
Weak to medium
(margin waviness):
Primary leaflets (average pairs):
3
Primary leaflets (shape of tip):
Acuminate
Primary leaflets (shape):
Medium ovate
Primary leaflets (shape of base):
Lobed
5.
Inflorescence Characteristics:
Corolla (shape):
Pentagonal
Corolla (inner surface color):
White/155D RHS
Calyx (anthocyanin coloration):
Absent
Anthers (shape):
Narrow cone
Stigma (shape):
Capitate
Stigma (color):
137A RHS
6.
Tuber Characteristics:
Skin (predominant color):
Tan
Skin (texture):
Smooth
Tuber (shape):
Oval
Tuber (thickness):
Slightly flattened
Tuber (length):
80 mm (average)
Tuber (width):
73 mm (average)
Tuber (thickness):
52 mm (average)
Tuber eyes (depth):
Intermediate
Tuber (primary flesh color):
160D RHS
Tuber (prominence of
Slight prominence
eyebrows):
Tuber (number per plant):
Medium (8-15)
7.
Reaction to Diseases:
Bacterial ring rot foliar reaction
Susceptible
Bacterial ring rot tuber reaction
Susceptible
Late blight Phytophthora
Moderately resistant
infestans
Early blight
Resistant
Leaf roll (PLRV)
Not tested
Virus X
Not tested
Virus Y
Highly susceptible
8.
Reaction to Pests:
Golden nematode
Susceptible
Globodera rostochiensis
Persons of ordinary skill in the art will recognize that when the term potato plant is used in the context of the present invention, this also includes derivative varieties that retain the essential distinguishing characteristics of FL1879, such as a Single Gene Converted plant of that variety or a transgenic derivative having one or more value-added genes incorporated therein (such as herbicide or pest resistance. Backcrossing methods can be used with the present invention to improve or introduce a characteristic into the variety. The term backcrossing as used herein refers to the repeated crossing of a hybrid progeny back to the recurrent parents. The parental potato plant which contributes the gene for the desired characteristic is termed the nonrecurrent or donor parent. This terminology refers to the fact that the nonrecurrent parent is used one time in the backcross protocol and therefore does not recur. The parental potato plant to which the gene or genes from the nonrecurrent parent are transferred is known as the recurrent parent as it is used for several rounds in the backcrossing protocol. In a typical backcross protocol, the original variety of interest (recurrent parent) is crossed to a second variety (nonrecurrent parent) that carries the single gene of interest to be transferred. The resulting progeny from this cross are then crossed again to the recurrent parent and the process is repeated until a potato plant is obtained wherein essentially all of the desired morphological and physiological characteristics of the recurrent parent are recovered in the converted plant, in addition to the single gene transferred from the nonrecurrent parent.
The selection of a suitable recurrent parent is an important step for a successful backcrossing procedure. The goal of a backcross protocol is to alter or substitute a single trait or characteristic in the original variety. To accomplish this, a single gene of the recurrent variety is modified, substituted or supplemented with the desired gene from the nonrecurrent parent, while retaining essentially all of the rest of the desired genes, and therefore the desired physiological and morphological constitution of the original variety. The choice of the particular nonrecurrent parent will depend on the purpose of the backcross. One of the major purposes is to add some commercially desirable, agronomically important trait to the plant. The exact backcrossing protocol will depend on the characteristic or trait being altered or added to determine an appropriate testing protocol. Although backcrossing methods are simplified when the characteristic being transferred is a dominant allele, a recessive allele may also be transferred. In this instance, it may be necessary to introduce a test of the progeny to determine if the desired characteristic has been successfully transferred.
Likewise, transgenes can be introduced into the plant using any of a variety of established recombinant methods well-known to persons skilled in the art.
Many single gene traits have been identified that are not regularly selected for in the development of a new variety but that can be improved by backcrossing and genetic engineering techniques. Single gene traits may or may not be transgenic, examples of these traits include but are not limited to: herbicide resistance; resistance to bacterial, fungal or viral disease; insect resistance; uniformity or increase in concentration of starch and other carbohydrates; enhanced nutritional quality; decrease in tendency of tuber to bruise; and decrease in the rate of starch conversion to sugars. These genes are generally inherited through the nucleus. Several of these single gene traits are described in U.S. Pat. No. 5,500,365, U.S. Pat. No. 5,387,756, U.S. Pat. No. 5,789,657, U.S. Pat. No. 5,503,999, U.S. Pat. No. 5,589,612, U.S. Pat. No. 5,510,253, U.S. Pat. No. 5,304,730, U.S. Pat. No. 5,382,429, U.S. Pat. No. 5,503,999, U.S. Pat. No. 5,648,249, U.S. Pat. No. 5,312,912, U.S. Pat. No. 5,498,533, U.S. Pat. No. 5,276,268, U.S. Pat. No. 4,900,676, U.S. Pat. No. 5,633,434 and U.S. Pat. No. 4,970,168, the disclosures of which are specifically hereby incorporated by reference.
Deposit Information
A deposit of the Frito-Lay, Inc. proprietary potato cultivar FL1879 microtubers disclosed above and recited in the appended claims has been made with the American Type Culture Collection (ATCC), 10801 University Boulevard, Manassas, Va. 20110. The date of deposit was May 6, 2003. The deposit was taken from the same deposit maintained by Frito-Lay, Inc. since prior to the filing date of this application. All restrictions upon the deposit have been removed, and the deposit is intended to meet all of the requirements of 37 C.F.R. §1.801-1.809. The ATCC accession number is PTA-5177. The deposit will be maintained in the depository for a period of 30 years, or 5 years after the last request, or for the effective life of the patent, whichever is longer, and will be replaced as necessary during that period.
Hereinabove has been set out a new variety of potato, Solanum tuberosum , designated as FL1879, including its physical characteristics and qualities by way of illustration and example for purposes of clarity and understanding. It will be obvious that variations are possible within the scope of this invention, as limited only by the scope of the appended claims.
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A novel potato cultivar of the genus and species Solanum tuberomasum , designated FL1879, is disclosed. The invention relates to the tubers of potato variety FL1879, to the plants of potato variety FL1879, to the seeds of potato variety and to methods for producing hybrid potato variety. The invention further relates to potato variety tubers, seeds and plants produced by crossing the potato variety FL1879 with another potato plant, and to Single Gene Converted plants.
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FIELD OF THE INVENTION
This invention concerns a process for machining workpieces by means of a laser beam, whereby the radiation coming from the machining point on the workpiece surface is detected and processed to yield signals. The machining operation is regulated by means of at least one control parameter derived on the basis of these signals.
The invention also concerns a device for machining workpieces by means of a laser beam, with a measurement unit, a laser stimulating unit and an electronic control unit.
BACKGROUND OF THE INVENTION
German patent 3,424,825 describes a process whereby the laser intensity is maintained between defined limit values. For example, the intensity of the plasma luminance is detected continuously by a radiation sensor, and the laser intensity is regulated by modulation of the laser radiation in order to maintain the plasma and prevent an unwanted detonation wave. The control principle of this process is based on a two-point controller with the known disadvantages such as the dependence of the cutoff frequency of the controller on the time constant of the control circuit. Therefore, this process is not suitable for precision adjustment of the laser intensity in order to achieve precision removal of material from a workpiece.
German patent 3,926,859 discloses a process and a device for cutting or perforating workpieces, especially those made of metal, with a laser beam, where the machining point on the workpiece is monitored with a radiation sensor that measures the prevailing workpiece temperature by detecting the heat radiation. This patent describes a two-point controller that cuts off the laser beam on reaching an upper limit for the workpiece temperature and turns the laser on again on reaching a lower workpiece temperature. Therefore, the laser is pulsed by reaching the upper and lower workpiece temperatures.
It is known that lasers need a certain amount of time from stimulation to emission=of the laser radiation. This is especially true of solid-state lasers (e.g., an Nd:YAG laser) and for gas lasers (e.g., a CO 2 laser). With solid-state lasers the delay time or lag is higher by approximately one power of ten. In addition, the laser continues to pump after the laser beam has been switched off. The cutoff frequency of the two-point controller is determined by these specific time constants of the laser which also change with the pulse frequency of the laser (according to German patent 3,926,859). For this reason, the cutoff frequency of the laser pulses cannot be raised above a certain level because otherwise the laser pulses would overlap and would thus raise the minimum energy level in the machining operation. Due to the laser-specific time constants when using a two-point controller for controlling the laser beam, it is necessary to operate with a low cutoff frequency, which leads to relatively large power pulses. Therefore, the amount of material removed from the workpiece in the forward movement of the laser over the material in one layer cannot drop below a certain limit.
When the laser beam strikes the material, there is an increase in temperature within a very short period of time which is in the range of nanoseconds. The control parameter for controlling a laser such as the beam power must respond at least equally rapidly. If this is not the case, then such a control system becomes unstable.
The dynamics of the laser, that is, the system-specific response time and the continued pumping of the laser radiation after the system has been shut down, are effective in the control circuit with a two-point controller according to German patent 3,926,859, which detects the radiation of one pulse and regulates the same pulse with the signal thus derived, but this leads to laser pulses that cannot be reproduced accurately. Therefore, a controller that contains the time constants of the laser in the control circuit is not suitable for precision removal of material by machining in this way.
In addition, the inherent dynamics of lasers are approximately constant only at pulse frequencies that vary within certain very narrow limits. If a self-pulsing laser is used, then the frequency of the laser pulses changes constantly. Thus, the response time of the laser to stimulation pulses also varies, which thus makes precision machining with a very small depth of removal of material such as 1 μm virtually impossible.
SUMMARY OF THE INVENTION
The purpose of this invention is to provide a process and device for machining workpieces by means of a laser beam in such a way as to permit removal of more material and also reproducible precision removal of material from a workpiece while achieving a high surface quality.
This purpose is realized by this invention by a process whereby an actual distance between a reference point and the surface of the interaction zone of the machining point is determined, a setpoint/actual value deviation between a given setpoint distance and the actual distance detected is determined, at least one control parameter is derived by the control unit in accordance with the setpoint/actual value deviation, and the resulting control parameters are output to at least one controller.
Stimulation of the laser can be varied essentially without any influence of time constants by means of the control pulses generated by the process according to this invention. A time constant here, for example, is the period of time between the rising flank of a control pulse emitted to the laser stimulating unit and the onset of the laser pulse and thus the laser radiation. This results in a high reproducibility of the laser pulses with regard to time, so the respective control parameter can be controlled with a high degree of accuracy. This makes it possible to remove very fine layers of material in a reproducible and advantageous manner and with a constant thickness.
An advantageous embodiment of this invention is characterized in that in addition to determining the actual distance and determining the deviation between the setpoint distance and the actual distance, a machining depth that corresponds to the distance between the surface of the interaction zone and a base line is determined, the deviation in machining depth is determined from the machining depth and the deviation between the setpoint and actual value, and at least one control parameter is derived according to the machining depth deviation.
Due to the combination of the determination of distance from a reference point to the surface of the machining point and the depth of the machining point (zone of interaction), the actual machining depth can be determined for each layer of material removed during the machining operation. Thus, the control parameter contains a real process parameter that takes into account the amount of material converted, melted and burned at the machining point on the workpiece.
The above control processes can be used for CO 2 lasers as well as Nd:YAG lasers (CW lasers). In addition, the control system can process the control deviation in such a way that laser pulses are generated only when the machining operation has not yet reached the setpoint depth.
In another advantageous embodiment of this invention, the beam power of the laser can be adjusted as a control parameter by way of the control unit. For this purpose, amplitude-modulated, pulse width-modulated and/or frequency-modulated control pulses can be emitted to the laser stimulating unit. Furthermore, the relative speed between the workpiece and the laser beam can be varied as a control parameter by output of speed-modulated control pulses to a forward feed unit, for example.
In another advantageous embodiment of this invention, the relative speed of forward movement of the laser beam can be detected, the laser power can also be controlled in accordance with the measured value thus derived. The laser power can be read out from two two-dimensional matrices, for example, where one matrix contains a machining depth deviation that has been detected and/or a setpoint/actual value deviation in the measured distance value in one dimension and the radiation power in the other dimension. The other matrix may contain, for example, the relative speed of forward movement and the laser power. The laser power can be varied, for example, by an amplitude-modulated control pulse. These two matrices can be multiplied and/or folded in order to obtain the desired laser power. The above measures are especially advantageous for the end areas of a meandering pattern machining a workpiece.
In addition, the machining process can also be controlled by other controllers such as an adaptive optical system that is adjustable by way of piezoelectric elements, for example, so the laser beam can be defocused in a controlled manner, with an influence on the radiation power of the laser. In another example, the oxygen supply and/or the intensity of the laser radiation can also be controlled. For example, when using an Nd:YAG laser, a shutter that interrupts the path of the laser beam in a controlled manner may also be used as a control element. Such a shutter may be based on a mechanical, electrooptical or magnetooptical principle (Kerr effect, LC shutter, etc.), as desired.
Alternatively, two or more control parameters may also be used to regulate the process. With a two-parameter control system, a velocity modulation signal and a radiation power modulating signal may be used as control parameters to regulate the process. These control parameters can be determined in an advantageous manner in a multiprocessor system in real time parallel processing. This permits a great reduction in the computation time required to determine the control parameters, so the response times of the process variables as well as the control accuracy can be improved.
In addition, the depth of machining can also be detected according to this invention by means of a radiation sensor that detects the heat radiation emitted by the interaction zone and thus obtains a value that can be correlated with the volume of the interaction zone. Thus, the depth of machining can be determined by analyzing the intensities of different wavelengths. The radiation sensor yields a signal for the actual amount of material removed in machining. Through the combination of the measurement of the absolute depth (machining depth) of the machining point and the relative distance signals, influences such as changes in machining temperature, changes in flow conditions, changes in material composition, etc., can be detected during machining in a layer of material being removed from the workpiece. Very accurate control of the laser power is made possible in this way.
In another advantageous embodiment of this invention, the signals of the distance sensor and/or the radiation sensor are detected during output of a laser pulse and thus control pulses for at least one immediately following laser pulse are generated. Thus, the detection of the control parameters and the determination of the control pulses are uncoupled from the output of the control pulses. In this way, the inherent dynamics of the laser are separated from the control circuit and are no longer contained in the transmission element of the controller and thus in the control circuit. Since the frequency of the control pulses is varied only within certain limits, the inherent dynamics of the laser are also approximately constant. Therefore, a laser radiation power that is highly reproducible can be generated, as is necessary for machining defined layers of material having a small thickness.
In another advantageous embodiment of this invention, the actual distance and/or the machining depth are detected by means of a group of laser pulses and then averaged. In this way, fluctuations caused, for example, by electric disturbance in the signals detected can be compensated. These fluctuations can be caused by electromagnetic fields acting on the transmission lines of the sensors. In addition, detection of the measurement signals can be adapted to the computation power of the control unit in this way.
Furthermore, a first control pulse can be given at the start of machining. This is advantageous because at the start of machining no laser pulse has yet been applied to the workpiece, so the control parameter does not contain any information regarding the status of the process.
In linear machining in several successive layers in order to create a cavity in a massive workpiece, the actual measured distance can be compared with the setpoint distance of the last layer machined at the beginning of a new layer to be removed by machining. This yields a difference between the depth of machining actually achieved during the last machining layer and the setpoint depth of machining set for the last machining layer in an advantageous manner. This difference can then be used as the corrective value or factor for regulating additional machining layers. As a result of this correction, a deviation in the depth of machining can be compensated, whereas in the absence of such a correction this deviation would be additive from one machining layer to the next. This makes it possible to achieve a considerable increase in accuracy in machining.
To determine the control pulses which act as control parameters of the machining process to directly influence the radiation power of the laser, the nth derivations of the setpoint/actual value deviation and/or the machining depth deviation can also be determined. This makes it possible to achieve faster and more accurate system responses to changes in the input parameters. In addition to linear correlations, P, PI or PID control algorithms may also be used. Furthermore, control systems based on so-called fuzzy logic may also be used to determine the control parameters.
The control pulses for controlling the laser stimulating unit may be calculated from the setpoint/actual value deviation, the machining depth deviation or the difference in distances. To reduce computation time, however, it may also be advantageous to read out the control pulses or the control parameters from a matrix. The control pulses are stored in a read-only memory in this embodiment of the invention and can be read out of the matrix in a memory in the control unit as a function of the setpoint/actual value deviation, the machining depth deviation or the difference in distances. The control pulses here are determined under comparable conditions during experimental machining operations and stored for future reference.
The matrix values may also have a functional dependence on the relative speed between the workpiece and the laser beam. These velocity-dependent values can be stored temporarily, but determination of corresponding control parameters by reading them out of the matrix may also be advantageous (shortening the computation time). In this case, speed-dependent factors may be combined with the matrix value read out of the matrix by either addition and/or multiplication.
The control pulses may be calculated as absolute values or they may be read out of a matrix. To reduce computation time it may be advantageous not to calculate the control pulses as absolute values but instead to determine their increments or decrements. The required computation time for adding a small increment or subtracting a small decrement in comparison with the absolute value is shorter in comparison with the time required to process the absolute control pulses owing to the smaller number of bits required for the variables in the computation unit.
The laser pulses generated on the basis of the control pulses are specific for the system and have a time lag in comparison with the control pulses as a function of frequency. For example, if a CO 2 laser is controlled with 10 kHz control pulses, then the time constant between the control pulse and the respective laser pulse will be approximately 15 μsec. The start of the laser pulse has a range of variation of about ±2 μsec. This time fluctuation in the start of the laser light is referred to as jitter. This jitter effect can be reduced by having a prefix pulse precede the control pulse. This prefix pulse, whose area is not affected by the control parameters, has an amplitude that is excessive in comparison with that of the control pulses and it has a reduced pulse width in comparison with the control pulses. The start of the prefix pulse is regulated in such a way that the rising flank of the prefix pulse coincides with the rising flank of the control pulse. Furthermore, the response time, that is, the time constant between the control pulse and the respective laser pulse, is also reduced by the prefix pulse. With 10 kHz laser pulses of a CO 2 laser, response times of 3 μsec and a jitter of ±1 μsec can be achieved with a prefix pulse. By using the prefix pulse the possible variation in pulse frequency and the pulse pauses between successive laser pulses can be increased in an advantageous manner in order to change the laser power as a control parameter without modifying the response of the laser pulses to the control pulses so greatly that the desired reproducible precision machining is no longer assured. This change in pulse frequency by adding a prefix pulse preferably amounts to about 10±2 kHz for a pulsed CO 2 laser.
In another advantageous embodiment of this invention, the required ON time for the laser is reduced and implemented in a time-discrete manner. To do so, the laser is kept approximately at the temperature required for operation of the laser by simmering below the laser threshold. The energy introduced by simmering is just below the energy level that would be needed to raise the laser above the laser threshold. This is especially advantageous when the material is removed only in some areas in order to produce special contours in the workpiece. In doing so, the workpiece or the laser head is moved continuously during the operation and the laser is kept in a stimulated stated by simmering when passing over certain areas of the workpiece where no machining is to take place. During the time of machining between the individual laser pulses, simmering is not used because the laser is in its operating state anyway. Simmering assures that the first control pulse will also produce a laser pulse.
The problem on which this invention is based is also solved by a device for machining workpieces by means of the laser radiation emitted by a laser and is characterized in that the measurement unit has a distance sensor and a control unit. In an embodiment of this device, the measurement unit has a radiation sensor with whose signal the depth of machining is determined.
One of the main advantages of this invention is that the inherent dynamics of the laser can be separated from the control circuit of the controller and are not contained in the transmission element. In this way, it is possible to measure an actual laser pulse and the next laser pulse or subsequent laser pulses are regulated accordingly (in contrast with regulation of the measured actual laser pulse). In addition, the inherent dynamics of the laser are kept approximately constant by means of a pulse frequency that changes only within certain limits and by adding a prefix pulse before the control pulse. In addition, the response time between a control pulse and the respective laser pulse can be reduced by simmering and by adding a prefix pulse. Thus, the period of time that elapses between stimulation of the laser and emission of laser light is minimized, and the range of variation in the onset of the laser light (jitter) is also reduced.
In addition, this invention yields a very high pulse-to-pulse stability due to the reduction in range of scattering of the laser pulses.
Another important advantage of this invention is that three-dimensional control of the laser is made possible. By determining the distance between a reference point and the surface point of the machined location, the laser radiation can be directed to a location that is precisely defined geometrically in a plane. By adding the determination of the machining depth as a control parameter, the "effective depth" of the laser beam is also used to control the process. This permits an extremely accurate method of controlling the laser, which is an advantage in precision removal of material.
BRIEF DESCRIPTION OF THE DRAWING
The objects, advantages and features of this invention will be more readily perceived from the following detailed description, when read in conjunction with the accompanying drawing, in which:
FIG. 1 is a schematic equivalent circuit of a laser machining device;
FIG. 2 is a schematic sectional diagram of the machined location;
FIG. 3 shows a flowchart for carrying out the process according to this invention;
FIG. 4 is a flowchart of another embodiment for carrying out the process according to this invention; and
FIG. 5 shows a time-based flowchart with control pulses and the respective laser pulses.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The schematic equivalent circuit of FIG. 1 shows control unit 10 with central processing unit (CPU) 11, memory 12 with random access memory (RAM) and read-only memory (ROM), address bus and data bus 13, digital/analog (D/A) analog/digital converter (A/D) 14 and input/output (I/O) unit 15. Not shown in this schematic diagram are the customary input and output units for the control unit such as a keyboard, a display screen and a printer. In addition, control unit 10 may be connected to the program controller of a CNC machine and to a local area network (LAN) and/or a wide area network (WAN) for integration into a computer integrated manufacturing (CIM) system.
The control unit sends control pulses Pa,w,p by way of D/A converter 14 to laser stimulating unit 20 for controlling laser 30. Laser stimulating unit 20 may be, for example, an HF generator that is connected directly to laser electrodes of laser 30 and generates a glow discharge there. Laser 30 may be a solid-state laser or a gas laser which is usually operated in pulsed operation. Preferably, a CO 2 laser is used for removal of material by machining.
Laser 30 emits laser pulses Lp by way of the control pulses Pa,w,p controlled by laser stimulating unit 20. These laser pulses Lp are directed through an optical system (not shown) onto machining position or location 40. Machining location 40 is monitored by measurement unit 50. Measurement unit 50 contains distance sensor 52 and, optionally, radiation sensor 51.
For example, the heat radiation of the interaction zone between the laser radiation and the machined material, i.e., machined location 40 in the workpiece, can be detected by means of radiation sensor 51. The size of the interaction zone can be deduced from signal Sm of radiation sensor 51 picked up by control unit 10 from A/D converter 14. In this way, a value that corresponds to the depth of the zone of interaction can be determined.
Distance sensor 52 determines the distance between fixed reference point 44 (FIG. 2) and surface 45 of machining location 40. Signal Sa from distance sensor 52 is picked up by control unit 10 by way of I/O unit 15.
FIG. 2 depicts a machining operation in workpiece 41. Laser beam 42 and, optionally, an auxiliary gas, strike surface 45 of workpiece 41, forming machined location 40 in this sample diagram. The relative feed direction between workpiece 41 and laser beam 42 is indicated by arrow 43. Actual distance A ist is indicated between reference location 44, which may be on laser head 47, and surface 45 of machined location 40. This actual distance is measured by distance sensor 52. In addition, depth of machining Bt ist is shown between surface 45 of machined location 40 and base line 46. This depth can be determined by means of radiation sensor 51. Radiation sensor 51 and distance sensor 52 can be located on the axis of the laser beam or at some other geometric location (not shown).
A schematic flowchart of the process according to the embodiment in FIG. 3 shows a program sequence through which control unit 10 runs. This program sequence is stored at a defined address in the RAM or ROM and can be called up by an operator or according to a CNC-controlled system. In the first run through the program, program run counter z is set at zero at the start (step 100). In the first run through the program, control parameters A ist and/or Bt ist may be zero or may be incorrect, so step 101 determines whether this is the first run. If this is the case, stored values Pa 1 , Pw 1 and Pp 1 are used for the pulse amplitude, the pulse width and pulse pause (step 102). Then program run counter z is set at 1 (step 103) and next the program branches off to step 119. In step 120 the program is either terminated or it branches back to step 101. In the next run through the program, distance A ist is determined from signal Sa of distance sensor 52 (step 104). Distance A ist is calculated to step 104 in each run through the program or it is read out of a matrix. Then the program determines whether the current run through the program is the first run through the program (step 105). If this is the case, a distance difference (ΔA k ) is calculated which corresponds to the difference between the setpoint distance of last machining layer A soll k-1 and actual distance A ist k determined in step 104 (steps 106-108). If this run is not the first run through the program, then the program branches off directly to step 109 where, in order to form setpoint/actual value deviation ΔA i , the difference between setpoint distance A soll and actual distance A ist is formed (step 109). Setpoint distance A soll may be a value stored in the ROM, for example, or it may be a value input by an operator or a value determined by a CNC controller. In addition, setpoint/actual value deviations ΔA i can also be calculated separately for each run through the program or read out of the matrix.
After determining setpoint/actual value deviation ΔA i , control pulses Pa,w,p are determined as a function of setpoint/actual value deviation ΔA i (steps 110-119).
Control pulses Pa,w,p have a defined amplitude, pulse width and pulse pause, each component Pa, Pw and Pp being determined separately in this example. However, the determinations can also be combined, in which case characteristic values are determined to characterize the pulse amplitude, the pulse width and the pulse pause of control pulses Pa,w,p. If the program branches off to step 112 in step 110, the pulse width of control pulse Pa,w,p does not change and the preceding value of the pulse width is used for the next control pulse Pa,w,p. However, if pulse width modulation is performed, then the program branches off to step 111. In step 111 the next pulse width Pw i+1 can be determined as a function of the distance difference ΔA k (correction factor) and the setpoint/actual value deviation ΔA i . Steps 113-115 determine whether the pulse amplitude of control pulse Pa,w,p should be modified. If this is the case, then the program branches off to step 114, where pulse amplitude Pa i+1 for the next control pulse Pa,w,p can be determined as a function of distance difference ΔA k and setpoint/actual value deviation ΔA i . If this is not the case, then the previous pulse amplitude is used for the next pulse amplitude (step 115). Step 116 determines whether a pulse pause and thus the pulse repetition rate (pulse frequency) are to be modulated, which is then performed in step 117. In step 118 the preceding value is used for the next pulse pause component Pp i+1 . Then in step 119 the components of the pulse amplitude, the pulse width and the pulse pause are combined to form the final control pulse Pa,w,p. In steps 111 and 114 and/or 117 the pulse width component, the pulse amplitude component and the pulse pause component of the control pulses Pa,w,p can also be read out of matrices. These matrices may contain prestored values for the pulse width components, the pulse amplitude components and the pulse pause components of control pulses Pa,w,p as a function of at least setpoint/actual value deviation ΔA i . Moreover, as an additional dimension, a correction factor such as the distance difference ΔA k may also be used for the matrix. In steps 111, 114 and/or 117 the absolute value of each control pulse component is determined. However, increments or decrements which are then added to or subtracted from the existing absolute values may also be determined. Then in step 120 the program branches off (not shown) to step 100 or the program sequence is terminated.
FIG. 4 shows another flowchart for another embodiment of the process according to this invention. Function blocks that are identical to those described with regard to FIG. 3 will not be discussed in detail below. In step 205 machining depth Bt ist is determined as a function of signal Sm of radiation sensor 51. Machining depth Bt ist is then read out of a matrix. Then in step 206 setpoint/actual value deviation ΔA i is determined from the difference between setpoint distance A soll and actual distance A ist . Next, in step 207 machining depth deviation ΔBt i is determined from the difference between setpoint/actual value deviation ΔA i determined in step 206 and machining depth Bt ist . In the event machining depth deviation ΔBt i assumes a value not equal to zero (or greater than a limit value), then a change in the radiation power of laser 30 is necessary because the machining depth is too great or too small. However, if machining depth deviation ΔBt i is equal to zero (or is smaller than a limit value), then the control pulse Pa,w,p is not modified (steps 209, 210, 211). In step 213 a pulse width increment or decrement for the next pulse ΔPw i+1 is determined as a function of machining depth deviation ΔBt i . ΔPw i+1 can also be read out of a matrix. In step 215 the absolute value of the pulse width component Pw i+1 for the next control pulse is then determined by addition of the pulse width component of the last pulse and the increment or decrement. Instead of determining the increment or decrement (steps 213, 215), the absolute value of pulse width component Pw i+1 can also be determined. This determination can be performed by means of a calculation and/or by reading the value out of a matrix.
Steps 216 and 223 differ from steps 212 to 215 only in that the pulse amplitude components of control pulses Pa,w,p are determined in steps 216 to 219, and the pulse pause components are determined in steps 220-223, so what was described above also applies to these steps.
In step 224 the pulse amplitude components, the pulse width components and the pulse pause components are then combined to yield control pulse Pa,w,p. In step 225 the program then branches off (not shown) to the start (step 200) or the program sequence is terminated.
The decision as to whether pulse width modulation, pulse amplitude modulation and/or pulse pause modulation is to be performed (steps 111, 114, 117) can be made by the operator. The branching decisions can also be made by way of a subprogram (not shown) as a function of preset or determined process parameters.
FIG. 5 shows as an example four different control pulses Pa,w,p and the respective laser pulses Lp in a flowchart as a function of time. Control pulses Pa,w,p are generated by control unit 10, whereby laser 30 delivers laser pulses Lp with system-specific lag time t 1 , t 2 (response time, time constant). The response time t i , t 2 depends, for example, on the pulse frequency of successive control pulses Pa,w,p, the operating condition of the laser and the pulse form of control pulses Pa,w,p. In this diagram a control pulse Pa,w,p in the form of a square-wave signal is generated at time T i . This control pulse Pa,w,p causes laser pulse Lp which is delivered with a time lag of t i .
If a prefix pulse Pv is added before control pulse Pa,w,p at time T 2 , the result is a time lag t 2 of laser pulse Lp for which it holds that t 1 >t 2 . Thus the response time of the laser pulses is shortened by the prefix pulse. This also makes it possible to vary the pulse pause within certain limits without having too much influence on the reproducibility of the laser pulses with regard to precision removal of material.
The beam power of laser 30 can be varied by a pulse-to-pulse change in pulse amplitude ΔPa, pulse width ΔPw and pulse pause ΔPp of control pulses Pa,w,p. At time T 3 control pulse Pa,w,p has a pulse width that is larger by ΔPw in comparison with control pulse Pa,w,p at time T 2 , so control pulse Pa,w,p has a larger area and thus laser 30 emits a laser pulse with a higher power. At time T 4 the pulse amplitude is larger by ΔPa in comparison with time T 2 and the control pulse starts earlier by the amount ΔPp. Due to this increase in pulse amplitude by ΔPa, the power of the respective laser pulse Lp increases in accordance with control pulse Pa,w,p. Due to the offset in the control pulse by ΔPp, the average energy density of laser pulses Lp also increases as long as the area of the control pulses in the period of time in question is kept constant or at least is not reduced.
In addition, prefix pulse Pv reduces the jitter, which contributes toward optimization of the reproducibility of laser pulses Lp. With the optimized reproducibility of the laser pulses, the precision in control and thus the accuracy in machining to remove layers of material of the workpiece are also improved, so the depth of the layer machined can also be minimized. In addition, the machining quality, i.e., the peak-to-valley roughness in machining, can be improved by optimizing the reproducibility of laser pulses Lp and the possibility of reducing the laser power.
In addition, simmering of the laser can be used to move the laser over certain areas of the workpiece for flying machining (intermittent machining) of the workpiece. Simmering can be used, for example, when the laser has been turned off for a long period of time and is turned on only at the moment when the first laser pulse is generated, i.e., simmering is stopped on the descending flank of the laser pulse. Simmering also makes it possible to reduce the time lag t i , t 2 when the laser has been turned off for a long period of time (flying machining).
To determine setpoint/actual value deviation ΔA i and/or the deviation in the depth of machining ΔBt i , the nth derivations of the differences can be used instead of the differences themselves to determine the deviation. In addition, control algorithms can be used to determine setpoint/actual value deviation ΔA i and the deviation in the depth of machining ΔBt i (for example, P, I, PI and PID control algorithms). The advantage of using control algorithms is the faster response of the radiation power (or the control pulses) as a control parameter to the control parameters detected by the measurement equipment.
In view of the above description, it is likely that modifications and improvements will occur to those skilled in this technical field which are within the scope of the appended claims.
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A process for precision control of a laser beam for machining workpieces while achieving high surface quality. The actual distance between a reference location and the workpiece surface is determined. A setpoint/actual value deviation between a predetermined setpoint distance and the actual distance measured is also determined. Control parameters are determined by a control unit in accordance with the setpoint/actual value deviation. The resulting control parameter outputs are coupled to a laser control unit to control the beam power of the laser. The disclosure also includes the apparatus for accomplishing the process.
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CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable.
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
BACKGROUND OF THE INVENTION
This invention relates to pour spouts for containers of fluid, and more particularly to pour spouts which permit transfers of fluid (liquid) based on the influence of gravity at multiple flow rates, and without the risk of spills or overflow.
It is desirable to avoid overfilling of fuel to internal combustion engines in lawnmowers, tractors, personal water craft, chain saws and power tools, outboard motors, ATV recreational vehicles and even automobiles. Spilled fuel presents health and safety risks to people and the environment in general. As a result, many states have now passed environmental legislation which regulates pour spouts which can be used in conjunction with volatile fuels and other liquids.
The opportunity for spills have various causes. First, often times the gas tanks in the aforementioned internal combustion engines have very narrow openings which requires precise pouring and/or a facilitating pour spout or funnel to prevent spills.
Many times spills occur because the operator of the pour spout does not know when the receiving vessel is full. In these cases, overflows occur before pouring can be terminated.
Yet another cause of spills is the ineffective venting of the container from which the fluid is being transferred. The result of ineffective venting is an uneven fluid flow, and even in some cases surging of the fluid. Surges can cause splashing and an uneven flow makes it extremely difficult to predict fluid levels in the receiving vessel.
Another problem encountered by gravity influenced pour spouts is airlock caused by improper venting. Airlock occurs as a result of improper venting in combination with specific volume and viscosity parameters of the fluid being transferred. Such a condition can result in fluid which will not pour even when the container is inverted. This problem, while annoying, can normally be resolved by turning the container right side up again. However, this only increases the opportunity for spills.
Examples of prior spill-proof pour spouts include U.S. Pat. Nos. 4,598,743, 4,834,151, 5,076,333, 5,249,611, 5,419,378, 5,704,408, and 5,762,117. These pour spouts all have the following drawbacks; they do not provide multiple flow rate options and they do not provide childproof locks. The present invention solves these and other problems.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a pour spout for a container of fluid which will preclude the overflow of any receiving vessel into which the fluid is transferred.
Another object of the present invention is to provide a pour spout for a container which will eliminate spills when transferring fluid from the container to a receiving vessel.
Another object of the present invention is to provide a spill-proof pour spout that allows fluid to be transferred from a container to a receiving vessel at various flow rates.
Finally, it is an object of the present invention to provide a spill-proof pour spout with a childproof safety lock which prevents children from accidently spilling, pouring or dumping fluid from a container.
To achieve the foregoing objectives, the present invention provides, in a first embodiment, a pour spout for transferring fluid from a container to a vessel. The pour spout comprises a base having an inner sleeve extending outwardly therefrom, a conduit member located in the inner sleeve, and an outer sleeve slidingly engaging the inner sleeve. The conduit member has a fluid tube, an air tube and an end cap. The outer sleeve is in a first closed position wherein the outer sleeve contacts the end cap preventing fluid flow from the pour spout. The pour spout can only be opened by rotating the outer sleeve to a first or second indexed position. By rotating the outer sleeve relative to the inner sleeve, the outer sleeve is adapted to be slid to a first open position permitting fluid to flow at a first flow rate through the fluid tube and out of the pour spout. By further rotating the outer sleeve, the outer sleeve is adapted to be slid to a second open position permitting fluid to flow at a second flow rate through the fluid tube at a second flow rate and out of the pour spout.
In a second embodiment, there is provided a pour spout for transferring fluid from a container to a vessel. The pour spout comprises a base having an inner sleeve extending outwardly therefrom, a conduit member located in the inner sleeve and an outer sleeve slidingly engaging the inner sleeve. The conduit member has a fluid tube, a first air tube, a second air tube and an end cap. A biasing member urges the outer sleeve into an initial closed position that precludes the transfer of fluid through the pour spout. The base has a protrusion which coacts with the outer sleeve and a plurality of slots in the outer sleeve to facilitate an initial closed position, a first open position and a second open position. The outer sleeve also has a shoulder for coacting with the vessel to slide the outer sleeve relative to the inner sleeve from the closed position to either a first or a second open position.
These and other aspects and attributes of the present invention will be discussed with reference to the following drawings and accompanying specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a pour spout according to one embodiment of the present invention;
FIG. 2A is a first elevational view of a pour spout according to one embodiment of the present invention in a closed position;
FIG. 2B is a first elevational view of the pour spout shown in FIG. 2A in a first open position;
FIG. 2C is a first elevational view of the pour spout shown in FIGS. 2A and 2B in a second open position;
FIG. 3A is a second elevational view of the pour spout shown in the first open position of FIG. 2B;
FIG. 3B is a second elevational view of the pour spout shown in the second open position of FIG. 2C;
FIG. 4 is an elevational view of the pour spout shown in FIGS. 2A-2C without the outer sleeve and bias member;
FIG. 5 is an elevational view of the base of the pour spout shown in FIGS. 1-4;
FIG. 6 is an elevational view of the outer sleeve of the pour spout shown in FIGS. 1-3;
FIG. 7 is a top plan view of the outer sleeve shown in FIG. 6;
FIG. 8 is an elevational view of the conduit member shown in FIGS. 1-4;
FIG. 9 is a cross-sectional view of the two-piece fluid and air tube taken along line a—a in FIG. 8;
FIG. 10 is an elevational view of the back channel of the two-piece fluid and air tube shown in FIG. 9;
FIG. 11 is an enlarged cross-sectional view of the back channel of the two-piece fluid and air tube taken along line b—b in FIG. 10;
FIG. 12 is an elevational view of the air tube cover of the two-piece fluid and air tube shown in shown in FIGS. 8 and 9;
FIG. 13 is an enlarged top plan view of the air tube cover shown in FIG. 12;
FIG. 14 is an elevational view of a second embodiment of the conduit member;
FIG. 15 is an elevational view of a pour spout having the conduit member shown in FIG. 14 in a first open position;
FIG. 16 is an elevational view of a pour spout having the conduit member shown in FIG. 14 in a second open position; and
FIG. 17 is an elevational view of a third embodiment of the conduit member.
DETAILED DESCRIPTION OF THE INVENTION
While this invention is susceptible of embodiment in many different forms, there is shown in the drawings, and will be described herein in detail, specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.
Referring to FIGS. 1-13 there is shown a spill-proof pour spout 10 according to a preferred embodiment of the present invention. As shown in FIG. 1, the spill-proof pour spout 10 includes a base 20 having an inner sleeve 30 extending outwardly therefrom. A conduit member 40 is located in the inner sleeve 30 and includes a fluid tube 50 , a first and a second air tube 60 , 61 (see FIG. 9) and an end cap 70 . An outer sleeve 80 engages the inner sleeve 30 and is held in a normally closed position by a biasing member 90 , such as a spring or elastomeric member. In the normally closed position, the outer sleeve 80 is biased against the end cap 70 by the biasing member 90 , thereby preventing flow through the fluid tube 50 . The outer sleeve 80 is rotatably and slidably moveable with respect to the inner sleeve 30 to facilitate multiple positions of the pour spout 10 . In a preferred embodiment, the pour spout 10 is positionable in three indexed positions, a locked position as shown in FIG. 2A, a low flow position as shown in FIG. 2B, and a high flow position as shown in FIG. 2 C. It is to be understood, however, that the pour spout 10 can be provided with numerous other positions, including additional positions for additional flow rates.
When describing the functionality of the spill-proof pour spout 10 of the present invention, it will be presumed that the pour spout 10 is attached to a fluid-filled container, such as, for example, a gasoline container, and a user of the pour spout is attempting to transfer fluid from the container to a receiving vessel having a receptacle into which the spout can be inserted.
As shown in FIGS. 2A-2C, the outer sleeve 80 also includes a first slot 110 , a second slot 120 and a third slot 130 . The base 20 includes a protrusion 140 that cooperates with the slots 110 , 120 , 130 in the outer sleeve 80 to facilitate indexable positioning of the pour spout 10 . The outer sleeve 80 is rotatable with respect to the inner sleeve 30 so that the protrusion 140 can be aligned with one of the slots 110 , 120 , 130 . The first slot 110 facilitates a locked position. The outer sleeve 80 includes a detent 141 that maintains the protrusion 140 within the slot 110 in a locked position. The pour spout 10 can be unlocked when a sufficient force is applied to the outer sleeve 80 with respect to the inner sleeve 30 to allow the protrusion 140 to slide past the detent 141 . Once unlocked, the outer sleeve 80 can be rotated with respect to the inner sleeve 30 to allow alignment of the protrusion 140 with one of the slots 120 , 130 , which, in turn, allows the inner sleeve to be slid into an open position. As shown in FIGS. 3A and 3B, the outer sleeve 80 of the pour spout 10 includes a shoulder 100 having a lip 101 . The shoulder 100 of the outer sleeve 80 coacts with the receptacle of the receiving vessel to permit the outer sleeve 80 to slide relative to the inner sleeve 30 into an open position when pressure is applied to the spout 10 by the user. As shown in FIGS. 2B and 3A, a low flow open position is achieved when the outer sleeve 80 is slid such that the protrusion 140 is held against an end surface 142 of the slot 120 . In similar fashion, as shown in FIGS. 2C and 3B, a high flow position is achieved when the outer sleeve 80 is slid such that the protrusion 140 is held against an end surface 143 of the slot 130 .
It should be noted that in the locked position, the outer sleeve 80 is maintained in the normally biased closed position against the end cap 70 . In order to allow the protrusion 140 to rotate past the detent 141 , a plastic material may be utilized that allows some flexion of the detent and/or protrusion. Additionally, an elastomeric compression-type seal may be utilized below the end cap 70 that will allow the outer sleeve 80 to be slidably pushed against the end cap just enough to further compress the seal and allow the protrusion to rotate past the detent 141 .
Referring now to FIGS. 4 and 5, in the preferred embodiment illustrated, the base has a larger diameter than the inner sleeve 30 which extends outwardly from one end of the base 20 . This creates a step 150 that extends radially around one end of the base 20 . As shown in FIG. 1, the biasing member 90 in the preferred embodiment is a spring that is disposed around the inner sleeve 30 , with one end of the spring 90 resting on the step 150 . Referring once again to FIG. 5, at the end of the inner sleeve 30 opposite the base 20 , there is a notched portion 160 which receives the conduit member 40 as will be explained further below. The other end of the base 20 has a connector flange 25 that cooperates with a threaded collar of a container (not shown) to facilitate connection of the pour spout 10 to the container.
As shown in FIG. 6, the outer sleeve 80 is comprised of a first hollow tube portion 83 and a second hollow tube portion 84 . The first hollow tube portion 83 has a larger diameter than the second hollow tube portion 84 , thereby creating an inner annular step 85 around the outer sleeve 80 . The shoulder 100 extends from one end of the first hollow tube portion 83 of the outer sleeve 80 . The opposite end of the first hollow tube portion 83 of the outer sleeve 80 includes the slots 110 , 120 , 130 . As shown in FIG.1, when the outer sleeve 80 is placed over the inner sleeve 30 and biasing member 90 , the biasing member 90 is confined between, and bears against, the step 150 in the base 20 and the inner annular step 85 of the outer sleeve 80 . As mentioned above, the biasing member 90 keeps the pour spout 10 in a normally closed position with the second hollow tube portion 84 of the outer sleeve 80 forming a seal with the end cap 70 of the conduit member 40 . A top plan view of the outer sleeve 80 is shown in FIG. 7 .
In the preferred embodiment shown in FIGS. 8 and 9, the conduit member 40 includes the first and the second air tubes 60 , 61 , the fluid tube 50 and the end cap 70 . In this particular embodiment, the air tubes 60 , 61 form discrete channels that are separate from the fluid tube 50 . Alternatively, a single air tube can be utilized. A tip portion 41 of the conduit member 40 is exposed when the outer sleeve 80 is slid to either the first (See FIG. 2B) or the second (See FIG. 2C) open position. Referring to FIG. 1, in the tip portion 41 of the conduit member 40 , the fluid tube 50 diffuses to form a fluid discharge opening 51 adjacent the end cap 70 . As shown in FIGS. 8 and 9, a first air vent aperture 170 is in the tip portion 41 of the conduit member 40 and communicates with the first air tube 60 . The first air vent aperture 170 is transverse to the first air tube 60 and has the same diameter as the first air tube 60 . A second air vent aperture 180 is also located in the tip portion 41 of the conduit member 40 and communicates with the second air tube 61 . The second air vent aperture 180 is transverse to the second air tube 61 and has the same diameter as the second air tube 61 .
When the outer sleeve 80 is slid to the first open position (See FIGS. 2 B and 3 A), the end cap 70 and the second hollow tube portion 84 of the outer sleeve 80 no longer form a seal preventing fluid from flowing through the pour spout 10 . Instead, the second air vent aperture 180 and the fluid discharge opening 51 of the conduit member 40 are exposed to the ambient atmosphere (i.e., within the vessel). Air flows from the air vent aperture 180 through the second air tube 61 allowing fluid to flow from the container through the fluid tube 50 and out the fluid discharge opening 51 as a result of a pressure differential between the atmosphere and the pressure developed in the container. This venting means also allows for an even air to fluid volume displacement resulting in an even rate of fluid flow.
When the outer sleeve 80 is slid to the second open position (See FIGS. 2 C and 3 B), the first and second air vent apertures 170 , 180 and the fluid discharge opening 51 are exposed to the ambient atmosphere. Air flows from air vent apertures 170 , 180 through air tubes 60 , 61 allowing fluid to flow from the container through the fluid tube 50 and out the fluid discharge opening 51 . Because the pressure differential is greater when both air vent apertures are exposed, the fluid flow rate in the second open position of the pour spout 10 is greater than the fluid flow rate in the first open position of the pour spout 10 .
In a preferred embodiment illustrated in FIGS. 10-13, the conduit member 40 is constructed of two separate pieces for ease of manufacture: a fluid and air tube back channel 190 and an air tube cover 200 . Back channel 190 includes the fluid tube 50 , fluid discharge opening 51 , end cap 70 . A divider wall 191 runs from the end cap 70 to the opposite end of the back channel 190 . The divider wall 191 separates the fluid tube 50 from the air tubes 60 , 61 . However, in the preferred embodiment, a portion of the diameter of air tubes 60 , 61 are formed in the divider wall 191 . The portions of the air tubes 60 , 61 formed in the divider wall 191 are designated 60 ′, 61 ′ in FIGS. 10-11. In addition, the back channel 191 has a plurality of slots 193 and recessed grooves 194 for receiving tabs 201 and catches 202 from the air tube cover 200 . The remaining portions of the air tubes 60 , 61 are formed in the air tube cover 200 and are designated 60 ″, 61 ″ in FIG. 13 . The air tube cover 200 includes the air vent apertures 170 , 180 . The air vent apertures 170 , 180 are transverse to and intersect the semi-formed air tubes 60 ″, 61 ″. When assembled, the tabs 201 and catches 201 are inserted in the slots and snap fitted into the recessed grooves 194 . FIG. 9 illustrates the assembled two-piece conduit member 40 .
Another embodiment of the present invention is shown in FIGS. 14-16. In this embodiment, there is only a single air tube 60 in the conduit member 40 . As a result there is also only a single air vent aperture 170 . The diameter of the air vent aperture 170 is the same as the air tube 60 . With reference specifically to FIG. 15, when the outer sleeve 80 is slid into the first open position, a first portion of the air vent aperture 170 is exposed. As shown in FIG. 16, the entire air vent aperture 170 is exposed in the second open position. Alternatively, a greater portion of the air vent aperture 170 may be exposed in the second position compared to that of the first position. In all other respects, the embodiment illustrated in FIGS. 14-16 is the same as the embodiment illustrated in FIGS. 1-13 and discussed above.
In yet another embodiment illustrated in FIG. 17, there is a single air tube 60 in the conduit member 40 . However, rather than having a single air vent aperture 170 , there are first and second air vent apertures 170 , 180 which communicate with the single air tube 60 . The first and second air vent apertures 170 , 180 are transverse to, and have the same diameter as, the air tube 60 . In the first open position, only the first air vent aperture 170 is exposed. In the second open position, the first and second air vent apertures 170 , 180 are exposed. Alternatively, in each of the positions, only a portion of the air vent apertures 170 , 180 are exposed. In all other respects, the embodiment illustrated in FIGS. 14-16 is the same as the embodiment illustrated in FIGS. 1-13 and discussed above.
It should be noted that for all of the embodiments described, when an air vent aperture is exposed in a particular indexed position of the outer sleeve 80 , it may be partially covered by the outer sleeve 80 . The resulting partial exposure of an air vent aperture regulates the intake of air through the associated air tube(s), thereby governing the flow rate. By changing the amount in which the air vent aperture is exposed, pour spout designs having various multiple flow rate positions can be achieved. Thus, for certain flow rates, a given air vent aperture may not be fully exposed to the ambient atmosphere.
It should also be noted that the indexed positioning of the outer sleeve can be achieved through means other than a slot and protrusion combination. For example, a series of detents can be provided on either the outer surface of the inner sleeve or the inner surface of the outer sleeve that coact with a corresponding protrusion on an opposing surface. Such an arrangement would be within the skill of one of ordinary skill in the mechanical arts.
From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the spirit and scope of the invention. It is to be understood that no limitation with respect to the specific apparatus illustrated herein is intended or should be inferred. It is, of course, intended to cover by the appended claims all such modifications as fall within the scope of the claims.
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A spill-proof pour spout for transferring fluid from a container to a vessel comprising a base having an inner sleeve extending outwardly therefrom, a conduit member located in the inner sleeve, and an outer sleeve slidingly engaging the inner sleeve. The conduit member has a fluid tube, and air tube and an end cap. The outer sleeve is in a first closed position wherein the outer sleeve contacts the end cap preventing fluid flow from the pour spout. The pour spout can only be opened by rotating the outer sleeve to a first or second indexing position. By rotating the outer sleeve either clockwise or counterclockwise relative to the inner sleeve, the outer sleeve is adapted to be slid to a first open position permitting fluid to flow at a first flow rate through the fluid tube and out of the pour spout. By further rotating the outer sleeve either clockwise or counterclockwise, the outer sleeve is adapted to be slid to a second open position permitting fluid to flow at a second flow rate through the fluid tube at a second flow rate and out of the pour spout.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to a sports shoe, such as for example a roller skate or ice skate.
[0002] Adjustable-size skates are currently commercially available which are usually constituted by a shell divided into a heel unit and a separate toe unit, which are slidingly associated along an axis that lies longitudinally to the shoe.
[0003] A supporting frame for an ice-skating blade or for a plurality of wheels is associated with the heel unit in a downward region.
[0004] The user can insert his foot within a soft innerboot that is accommodated inside the shell and can then fasten his foot inside the sports shoe by activating closure means arranged transversely to the shell or transversely to the two flaps of the soft innerboot.
[0005] Said soft innerboot further has means that are elastically deformable at least in a longitudinal direction in order to allow an elongation that is equal to the elongation of the shell.
[0006] The main drawback of this known type of sports shoe is the fact that a selected elongation of the shell, obtained by sliding the toe unit forward with respect to the heel unit, is often not matched by an equally effective elongation of the soft innerboot.
[0007] Accordingly, there is the drawback of having available a known type of sports shoe that can be used comfortably for only part of the size range and not all over the size range for which the shoe was designed.
[0008] In particular, the elongation of the soft innerboot often must be achieved by inserting the foot in such innerboot, with consequent user discomfort.
[0009] Another important drawback consists in that due to manufacturing requirements the shell often does not surround the soft innerboot completely but does so only partially at the toe and heel.
[0010] Thereby, a further drawback is due to the fact that the exposed parts of the soft innerboot can be subjected to wear or damage.
SUMMARY OF THE INVENTION
[0011] The aim of the present invention is therefore to solve the noted technical problems, eliminating the drawbacks of the cited known art, by providing a sports shoe of adjustable size that allows the user to have at his disposal all the sizes planned during design.
[0012] Within this aim, an object of the present invention is to provide a sports shoe that is comfortable to wear regardless of the preset size.
[0013] Another important object of the present invention is to provide a sports shoe that allows to protect the soft innerboot against wear and any damage.
[0014] Another object of the present invention is to provide a sports shoe that is structurally simple and has low manufacturing costs.
[0015] This aim and these and other objects that will become better apparent hereinafter are achieved by a sports shoe, comprising a semirigid shell divided into a heel unit and a separate toe, unit, which are slidingly associated, and a soft innerboot that can be accommodated in said shell, characterized in that it comprises means for detachable interconnection between said soft innerboot and an element for at least partial covering and/or fastening of said soft innerboot, said element being associated with said toe unit and protruding therefrom.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Further characteristics and advantages of the invention will become better apparent from the detailed description of an embodiment of the sports shoe according to the present invention, illustrated by way of nonlimiting example in the accompanying drawings, wherein:
[0017] FIG. 1 is an exploded perspective view of an embodiment of the sports shoe according to the present invention;
[0018] FIGS. 2 and 3 are two further partially exploded perspective views of the sports shoe shown in FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] In the examples of embodiments that follow, individual characteristics, given in relation to specific examples, may actually be interchanged with other different characteristics that exist in other examples of embodiment.
[0020] With reference to the figures, the numeral 1 designates a sports shoe, such as for example a roller skate, with four wheels 2 arranged in line.
[0021] Said wheels 2 are associated, by way of mechanical means 3 of a known type, with a supporting frame 4 whose transverse cross-section is arch-shaped, i.e. is like an inverted U.
[0022] In particular, the wheels 2 are associated between the downward-pointing wings of the frame 4 .
[0023] A box-like heel unit, designated by the reference numeral 5 , is associated above the rear portion of said frame 4 and is open at the front and top.
[0024] At the front of the heel unit 5 , the frame 4 has, in an upward region, guides 6 for the longitudinal sliding of a toe unit 7 , from the lower surface of which, not shown, an edge 7 a protrudes laterally and frontally and is designed to contain the foot of the user.
[0025] The toe unit 7 and the heel unit 5 constitute a shell, generally designated by the reference numeral 8 , that is advantageously made of semirigid material and is adapted to contain a soft innerboot 9 for accommodating the foot of the user.
[0026] The soft innerboot 9 can be associated with the heel unit 5 advantageously by further interlocking means.
[0027] For example, such interlocking means are associated laterally with the soft innerboot 9 , approximately to the rear of the malleolar region, and comprise at least a pair of rigid cleats 10 , only one of which is shown in the figures.
[0028] Said cleats 10 can be arranged within complementarily shaped openings 11 formed in the heel unit 5 , so as to ensure mutual locking once the foot has been inserted in the skate.
[0029] The sports shoe 1 further comprises detachable interconnection means, designated by the reference numeral 12 , for interconnection between the soft innerboot 9 and an element for the at least partial covering and/or fastening of said soft innerboot 9 , such as for example a sheath or overshoe 13 .
[0030] Said overshoe 13 is associated with the toe unit 7 at its front region and has two lateral flaps, respectively designated by the reference numerals 14 a and 14 b , that protrude to the rear of said toe unit 7 toward the heel unit 5 .
[0031] As shown in FIG. 3 , said pair of flaps 14 a and 14 b affects or are adapted to enclose the soft innerboot 9 laterally, interposing itself partially between said innerboot and the sides of the heel unit 5 .
[0032] The connection between the overshoe 13 and the soft innerboot 9 is achieved by way of said detachable interconnection means 12 : in this particular embodiment, shown merely by way of example, said means 12 are advantageously constituted by a tongue 15 that protrudes from the innerboot 9 approximately proximate to the toe region, can be arranged through a slot 16 formed transversely in the overshoe 13 and is provided with engagement means, designated by the reference numerals 17 a and 17 b , for engagement with said soft innerboot 9 .
[0033] In particular, the engagement means 17 a and 17 b can be constituted advantageously for example by a press-stud.
[0034] The overshoe 13 , moreover, can comprise fastening means for fastening the shoe 1 around the user's foot, such as for example laces 18 guided between the flaps 14 a and 14 b of the overshoe 13 .
[0035] Operation of the sports shoe is therefore as follows: with reference to the figures, when the toe unit is moved forward, the overshoe is forced to follow such movement, thus applying to the soft innerboot a traction with a point of application located at the detachable interconnection means.
[0036] In this manner, the elongation of the soft innerboot occurs before foot insertion and is not due to the insertion of the user's foot.
[0037] It has thus been found that the invention has achieved the intended aim and objects, a size-adjustable sports shoe having been provided which allows the user to have at his disposal all the sizes planned during design.
[0038] The sports shoe according to the invention, moreover, is very comfortable regardless of the preset size, since the soft innerboot is deformed by the necessary extent before foot insertion.
[0039] Moreover, the overshoe preserves the soft innerboot from wear and any damage, since it covers the lower part of said innerboot, i.e., the part that is particularly subjected to contacts with the ground or with other objects.
[0040] The sports shoe, finally, is very simple from the structural standpoint and therefore has low manufacturing costs.
[0041] The invention is of course susceptible of numerous modifications and variations, all of which are within the scope of the appended claims.
[0042] The materials used, as well as the dimensions that constitute the individual components of the invention, may be more pertinent according to specific requirements.
[0043] Various means for performing functions as the ones required by the present invention and set forth in the illustrated preferred embodiment can be envisaged by those skilled in the art which are technically equivalent with those herein illustrated.
[0044] The disclosures in Italian Patent Application No. TV2002A000153 from which this application claims priority are incorporated herein by reference.
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A sports shoe comprising a semirigid shell divided into a heel unit and a separate toe unit, which are slidingly associated, the shell containing a soft innerboot that comprises a detachable interconnection for connection of an element for at least partial covering and/or fastening of the soft innerboot, the covering and/or fastening element being conveniently associated with the toe unit and protruding therefrom.
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This is a Continuation of application Ser. No. 07/393,298, filed Aug. 14, 1989, now abandoned.
FIELD OF THE INVENTION
Lipid membrane structures coupled with pharmacologically active burden.
DESCRIPTION OF THE PRIOR ART
At the time of the discovery that is this invention, the development of liposomal systems is well advanced. The literature provides specific instructions for making vesicles and liposomes by sonication, microfluidization, detergent dialysis and other techniques utilizing the phenomena of cavitation. One may refer to prior U.S. Pat. No. 4,603,044 for instruction both in making vesicles and supplying target molecules for directing the vesicle to the hepatocyte.
Applicant, as well as all known researchers heretofore, have endeavored to capture a core volume of the drug or other material during the formation of the vesicle. As a film of lipid material is sonicated, for example, most of it will form the vesicle configuration with bipolar walls and capture some of the media, in which it is formed, within the core volume.
Some have recognized that there are other means of associating the drug with the liposomal system. See publication "Uptake of Antineoplastic Agents into Large Unilamellar Vesicles in Response to a Membrane Potential" by Lawrence D. Mayer, Marcel B. Bally, Michael J. Hope and Pieter R. Cullis, published in 1985. Elsevier Science Publishers.
The above-referenced publication must be carefully categorized, because the teaching of the publication is considerably apart from the novelty of the present invention.
The publication stresses potassium ion diffusion potential to achieve effective interior concentrations. The publication assumes, as Applicant and all other researchers prior to this time have assumed, that the formation of vesicles produces a bladder configuration having an internal core volume. It is the placing of drugs or diagnostic material into that core volume that has been the prior art endeavor.
In this document, a generic term "burden" will be used to refer to the many substances that have been captured in vesicles of bipolar lipids. See "Definitions" below. This document will show a novel concept of diffusion loading and partitioning, which will include bipolar lipids.
Furthermore, the method of filling vesicles by formation in a water solution of the desired drug or diagnostic material has been expensive because the trauma of microfluidization, and other procedures causes a considerable degradation of the burden. Insulin is an outstanding example. Formation of vesicles heretofore in a bath of insulin solution has resulted in polymerization of considerable amounts of the insulin rendering the insulin molecules antigenic. Although the bath of insulin can be reused to form more loaded liposomes, each reuse produces a greater concentration of polymerized molecules and a lower grade of product. Insulin is exceedingly expensive and degradation of the bath causes a considerable cost factor in conventional manufacture of drug filled vesicles.
DEFINITIONS
Pharmacologically active burden: As used herein, is a drug, diagnostic substance, physical enhancement substance such as a skin moisturizer, perfume, dental plaque counter agent or fluoride, but not limited thereto. The invention is in the means and method of loading liposomes or fragments without limit to the particular substance constituting the burden.
Bipolar device: a liposome, and fragment particles of a lipid membrane structure.
Liposome and vesicle: Both bladder forms having bipolar walls. There is no clear consensus for selection of one term or the other, and therefor are considered interchangable in this specification.
SUMMARY OF THE INVENTION
This invention resides primarily in the discovery that a bipolar lipid, either in a bladder form or in fragments, will not only load a drug or diagnostic material by diffusion, such as in the case of a fully formed vesicle, but by partitioning in both types of structures.
Partitioning is the phenomena that exhibits some type of solubility of materials in a media which normally are considered to be insoluble in that media. For example, oil and water are said not to mix and generally this is true. Nevertheless, a mixture of the two, when separated, will exhibit a small amount of oil in the water and a small amount of water in the oil. This is known as partitioning.
With the discovery that partitioning is taking place both in fully developed vesicles and bipolar lipid fragments, it is then the discovery of this invention to join a targeting molecule and a drug or other burden together by means of a lipid intermediary.
It is, further, an object of the invention to load the core volume of vesicles, and to partition drug or diagnostic material to the walls thereof and to lipid fragments, both inside the membrane and outside the membrane.
It is the principal object of this invention to construct a fully operative targeted carrier for a drug or other burden without degrading trauma formerly associated with energy loading of vesicles and liposomes during formation in the presence of the burden.
Vesicles and liposomes are made in several different ways known to the art. (Gregory Gregoriadis, Liposomes Technology Vol. I, II, III, CRC Press, 1984). By whatever means employed, the general principal is that a lipid is mixed with water or a water-based solution, and energy is applied to cause the lipid to form into the bladder configuration. The formation process captures some of the water medium within the core volume.
GENERAL DISCLOSURE
Applicant distinguishes over all known prior art, including intensive literature studies, by the discovery that: a) vesicles can be manufactured in a buffer solution with none of the desired burden present, and thereafter supplied with the burden by means of diffusion and/or partitioning.
Study of the effort to diffuse insulin into a buffer solution in the core of vesicles disclosed that faulty vesicles, fragments of vesicles, and similar lipid particles, not only carry the desired drug or diagnostic material, but also took on a target molecule and acted in the same manner as fully developed vesicles and liposomes. No diffusion potential has been found to be necessary for producing fully effective targeted liposome structures either as vesicles or discontinuous lipids.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In the discussion that follows, the term dispersed phase will refer to those substances (i.e. generally lipids) that are dispersed throughout the dispersion medium. In other words, the dispersed phase is the discontinuous phase, whereas the dispersion medium is regarded and defined as the phase that is continuous. Buffer or water are examples of the continuous phase.
As a result of the invention, we have been able to target vesicles and liposomes to selected sites of action in vivo to elicit specific pharmacological responses. These targeted delivery systems are working examples of utilizing a structured and dispersed lipid phase that resides in a continuous aqueous medium to achieve beneficial results. This invention will extend the concept of targeted drug delivery to include those species in the dispersed phase of a continuous medium that have structures different from the classical liposomes and vesicles and yet still are capable of evoking the desired pharmacological response.
This invention employs dispersed phases to selectively sequester, entrap, embed, absorb or adsorb specific targeting molecules, such as biliverdin, monoclonal antibodies or diphosphonates, as well as molecules designed to inhibit reticuloendothelial (RES) uptake of the dispersed phase drug delivery system. The invention includes the entrapment, embedding or adsorption of drugs, vitamins, diagnostics, or combinations thereof, for the purpose of creating an efficacious drug delivery system. As a result, a dispersed phase delivery system is created in the dispersion medium which can be visualized and function as an isolated platform to which target, RES avoidance and drug molecules can be associated or attached.
The fact that the dispersed phase is lipid-like and may be composed of a variety of lipid molecules points to the versatility of lipid compositions that may be selected for dispersed phase applications.
Thus, it is now recognized according to this invention, that a compartmentalized core volume, such as encountered in vesicles or liposomes, is not necessarily a prerequisite for effective drug delivery. Instead, these new forms of dispersed phase drug delivery platforms rely on the phenomena of adsorption, partitioning, or on specific means of covalent or non-covalent attachment of molecules to achieve the desired objective. It is stressed that target molecules, RES avoidance molecules or biological actives such as drugs, diagnostics, hormones, vitamins, pesticides, plant nutrients or growth factors, enzyme inhibitors or activators, DNA and RNA gene fragments, therapeutics in general, anticancer agents, bone active agents, sunscreen, insect repellants and perfumes, and the like, are examples which we now associate effectively with targeted lipids.
Since dispersed phases have a large surface area due to their colloidal nature, numerous sites exist for surface adsorption and partitioning phenomena to occur. Likewise, dispersed phases offer sites where the partitioning of molecules may commence. A molecule is said to partition when it has preference for one phase over the other. Generally molecules partition more readily into phases that exhibit the same solubility properties as the molecules themselves. Thus partitioning is a matter of degree. Molecules that are similar in solubility properties are said to exhibit a high partitioning coefficient.
Throughout this specification the formation of the vesicles and their post formation loading according to this invention will be discussed with respect to insulin. It must, however, be clearly understood that any burden material that is capable of being captured by the vesicle will benefit by the teaching of this invention.
When a solution of insulin is employed as the medium in which the vesicles are formed, the high energy input of the vesicle formation procedure will subject the insulin to possible dimerization and polymerization reactions. If polymeric forms of insulin result, they will depart significantly from the desired, simple monocomponent entity. These polymeric forms of insulin can elicit immunogenic problems. Immunogenic considerations play an increasingly significant role as chronic dosing of a given drug is pursued.
In the practice prior to this invention, in order to form vesicles by microfluidization, sonication or other known processes, large volumes and concentrations of insulin are required. As an example, 1.48% W/V concentration of lipid microfluidized with the insulin concentration at 131.7 units/ml costs on the order of $5,000 U.S. or more per liter of solution. When the insulin which is not associated with the vesicle is removed, close to 99% of that insulin is either wasted or slated for recovery by recycle. Both processes are costly, not only in terms of raw material, but also in manufacturing time for personnel and equipment.
According to this invention, empty or blank vesicles are formed in an idealized sterile buffer solution. By empty it is meant that the sterile buffer solution is not the ultimate desired cargo for the vesicle. The vesicles are not literally empty; they are devoid of the intended cargo or burden and filled with the buffer. The buffer of choice has been 40.5 mM NaH 2 PO 4 --NaOH pH 7.3.
In the vesicle making procedure, after vesicles are manufactured or synthesized in sterile media or buffer, they may then be stored in this state for longer periods of time because there is an absence of either biologically or chemically active molecules which could interact or otherwise disrupt the vesicle. Therefore, storage of empty, but membrane permeable, vesicles is greatly facilitated and advantageous.
The invention is simplicity in its essence. A vesicle or permeable lipid membrane is formed in an environment of a sterile medium and having the core volume filled with that medium. The improvement of this invention comprises loading the core volume by immersing the prior formed vesicle in solution of the desired substance compatible with the core volume media. That is, the vesicles, which are said to be empty in respect to their content of the drug or diagnostic material, are filled through the naturally occurring physical phenomenon, thereby leading to a simple compartmentalization of insulin.
Prior art publication "Uptake of Antineoplastic Agents into Large Unilamellar Vesicles in Response to a Membrane Potential" supra, obtains core volume content by creating a K+ potential. In contrast the present invention is the discovery of the roll of post formation loading by diffusion without the need of first creating a potential.
If pores exist in a vesicle, then vesicle pores may be sealed up with an annealing process that is conducted at a temperature above the transition temperature of the membrane lipids. It is not necessary to seal the pores. When appropriate targeting molecules are introduced into the vesicle membrane, the vesicle can then be targeted to the intended site of action. In the example set forth below, hepatobiliary molecules on the surface of the vesicles are used to target the vesicle to the liver hepatocyte. In this particular example, the vesicle core volume contains insulin.
In order to test this invention, experiments have been completed which establish that the aforementioned procedure has great utility and efficacy in delivering insulin for the treatment of the diabetic state in a rat having the diabetic state induced by streptozotocin. Efficacy with the animal model relates to the significant decrease in peripheral blood or plasma glucose levels two hours post-dosing when compared to the controls with native insulin only.
A clear advantage is achieved in relation to the amount of native insulin used in synthesizing the hepatocyte directed vesicle insulin drug product. In this procedure, porous vesicles, which are said to be blank or empty, are incubated for a period of time of at least 20 minutes with the appropriate dosing solution and then injected into the animal. Note that the usual dose is employed. By incubating as described, some of the dose will be a burden of lipid targeted to the liver, and the remainder will be free to serve the peripheral system.
The vesicles used in the experiment were made by the principals of this invention simply by utilizing the process of diffusion and partitioning to encapsulate or compartmentalize anywhere from less than 1% to a few percent of the total insulin in solution. The encapsulated insulin is targeted by an hepatobiliary target molecule to the liver hepatocyte in order to achieve the desired pharmacological effect. See U.S. Pat. No. 4,603,044 for one example of targeting procedures. Thus, the need to synthesize vesicles by microfluidization or other means of vesicle formation, which requires large volumes and concentrations of insulin, is eliminated.
METHOD OF MANUFACTURE
In order to maximally incorporate core volume insulin, the solubilized external insulin needs to approach saturation levels. However, it is not necessary or even required, to load the core volume of the vesicle with insulin or any other biologically active drug, diagnostic material, molecule, or nutrient to the level or saturation. This specification teaching only illustrates that it is a practical procedure to load vesicles to a utility level in this fashion.
1) Preparation Procedure
The following lipids illustrated in Table I were mixed together and solubilized in CHCl 3 .MeOH (2:1 w/v) and dried down under vacuum before being hydrated in pyrogen-free distilled deionized water.
TABLE I______________________________________ Proto-IX DimethylCategory DPL CHOL DCP MPB-PE Ester Total______________________________________MW 733 387 546 980 591Mg 505.05 48.72 162.41 67.40 7.22 790.80u moles 689.02 125.89 297.45 68.78 12.22 1193.36mole 5.47 1 2.36 0.546 0.097ratiomole % 57.74 10.55 24.93 5.76 1.02 100%% by wt 63.87 6.16 20.53 8.53 0.91 100%______________________________________ 790.80 mg of lipid/72 ml of lipid Stock A = 10.98 mg/ml 790.80 mg of lipid/516 ml total volume = 1.53 mg of lipid/ml or 0.153% w/
The 790.80 mg of lipid was hydrated in 72.0 ml of PF (DeH 2 O) at 42° for 20 minutes by slow turning on the Buchi rotoevaporator. The hydrated lipid was then diluted to 516 ml total volume with enough 0.2M NaH 2 PO 4 --NaOH pH 7.3 such that the final concentration was 40.5 mM. The 516 ml of suspended lipid was allowed to stir for 15 minutes at ambient temperature before being processed in the microfluidizer at 50 p.s.i.g. head pressure resulting in 12,000 p.s.i.g. shear pressure. Following microfluidization the sample was centrifuged in the Sorvall RC-2B refrigerated centrifuge at 20,000 rpm (49,460×g) at 15° for 30 minutes. A small dilution was made in the preparation at this point, resulting in a final buffer concentration of 39.8 mM. The sample was filtered through a 0.2 u Acrocap filter and stored in the refrigerator under N 2 at 4° C.
2) Post-formation Loading Procedure
The post-formation loading procedure was performed by mixing 1.0 ml of vesicles in 39.8 mM NaH 2 PO 4 --NaOH pH 7.3 buffer with 1.0 ml of insulin stock solution prepared at a concentration of 0.874 mM in 15.1 mM NaH 2 PO 4 --NaOH pH 7.3 buffer. The mixing resulted in a suspension where the final concentration of insulin was 0.437 mM, and a final buffer concentration of 27.45 mM NaH 2 PO 4 --NaOH pH 7.3. The loading procedure was allowed to proceed for 18 hours at 4° C.
Following the incubation in the refrigerator at 4° for 18 hours, the vesicles were annealed at 45° C. for 20 minutes with slow turning on the Buchi rotoevaporator. The closing of the vesicle pores commences as annealing begins. The degree of leaking is a matter of operator choice, controlling the variables of time, temperature, and buffer, as known in the art.
The great advantage of vesicle loading by the above disclosure, is that no separation of filled vesicles from the media insulin is required. When a dose of insulin is required, the shelf supply of blank vesicles is mixed with the prescribed dose, and the mix used as an injection. All of the insulin is used. There is no degraded product. The success of this procedure is founded on the discovery that no specific portion of the insulin need be targeted to the liver. The liver, it has been found, will respond to any portion of the dose reaching the liver via the loaded vesicles. The free or native insulin is then used by the peripheral organs.
Having completely proven the discovery that formed vesicles with neutral core volume could be reverse loaded by diffusion, the evidence of laboratory work indicated that targeted units were reaching the hepatocyte even though there were few if any vesicles formed.
Accordingly, a run of vesicles was made by the classical sonication method and then the vesicles were separated from the solution by chromatography.
After this separation process, which is known to be very efficient and therefor could be expected to remove substantially all of the vesicle forms, the remaining dispersed phase showed examples of targetable membrane fragments, lipid particles and fragments each with a burden component and a targeting molecule.
When tested, these fragments and similar items performed as vesicles have in the past. Accordingly, the test thus conducted has proven the theory of partitioning to apply to these fragments and to thereby act as fully developed drug delivery systems.
Also, this experiment has conclusively shown that very small quantities of insulin partitioned into the lipid fragments has thereby been found to be sufficient to program the liver for proper glucose uptake and distribution.
In review, this disclosure recognizes that prior methods of vesicle loading generally results in degrading of the active burden as well as producing a defective vesicle wall structure through the introduction of active burden into the lipid domain.
The disclosure then compares the greatly reduced defect factor in vesicles formed in water or buffer with no active ingredient present with prior art.
Also, with no active ingredient present, shelf-life of blank vesicles is greatly extended.
Finally, the disclosure teaches incubating the blank vesicles in a physiologically active solution. Whether the result is diffusion, partitioning or some unknown attraction of active material and lipid forms, it is a fact that the new method of loading produces a result of far greater effectiveness, and great cost reduction.
Although vesicles of greater integrity result from formation in inactive media, the best loading requires purposely formed pores in the membrane wall. Diffusion loading can occur in perfectly formed vesicle walls, but deliberate pore formation allows greater and faster diffusion.
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The first part explains the discovery, and means to employ the discovery that whole, intact vesicles and liposomes are not the sole means of burden (drug) delivery by targeting molecules. The second part teaches the discovery of reverse loading of vesicles and liposomes to obtain fully functional core volume load of a useful burden without the trauma degradation of the active burden material, and with greatly extended shelf life.
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FIELD OF THE INVENTION
[0001] This invention relates to a multi-purpose article carrier for a personal mobility vehicle, such as a mobility scooter or other powered mobility vehicle, of the type used to transport a disabled person.
BACKGROUND OF THE INVENTION
[0002] Personal mobility vehicles, including but not limited to motorized mobility scooters and powered wheelchairs, have become common place for people with slight or severe disablements to move about independently. With the increased use of these vehicles, there is a demand for vehicles that may be modified to assist the user with transporting articles.
[0003] Personal mobility vehicles in and of themselves, have minimal means for transporting goods. Although devices for expanding the cargo capacity for personal mobility vehicles have been known in the art for quite some time, they are typically designed only for a single or dual purpose and have to be detached from the vehicle and a different device attached to carry out another purpose. For example, there are holder systems that are designed to hold walking aids such as crutches, canes, and walkers, which are described in U.S. Pat. No. 6,547,112. U.S. Publication No. 2012/0187265 also describes a carrier that is attached to a mobility vehicle, but it is limited to transporting minimal items that can fit into the base support of the carrier. There are other carriers that have been designed to attach to the back of the motorized vehicles in order to tow large quantities of goods, but these carriers are large, bulky, and decrease the maneuverability of the vehicle because they are in contact with the ground and are merely towed behind the vehicle. For example, U.S. Publication No. 2006/0220346 describes a trailer that can be attached to the rear of a motorized vehicle and U.S. Pat. No. 4,902,029 describes a luggage carrier that can be attached to the rear of a wheelchair. U.S. Pat. No. 7,967,174 describes a basket that can be secured to the back of a motorized vehicle to carry large quantities of goods, but this carrier is bulky and may tip the carrier over if there are heavy goods placed in the basket.
[0004] Thus, there is a need in the art for providing a multi-purpose article carrier for a personal mobility vehicle or other powered mobility vehicle that is compact and light weight so as to not interfere with the maneuverability of the vehicle. It is an object of this invention to provide an improved removable attachable multi-purpose carrier that is light weight and easy to install.
SUMMARY OF THE INVENTION
[0005] It is the purpose of the present invention to provide a multi-purpose article carrier for carrying an assortment of goods, which can be detachably connected to the back of a personal mobility vehicle or other motorized personal mobility device. Because the frame is suspended from the towed vehicle and does not come into contact with the road, it is no more difficult to drive a vehicle with this attachment than an ordinary personal mobility vehicle. Further, this device is light weight, easy to install, remove, and store.
[0006] The present invention can be used to carry various combinations of goods, including but not limited to, a cane, an oxygen tank, a walker, shopping bags, tote bags, lawn chairs, hangers while clothes shopping, small hand grocery baskets, or a custom storage bag that can be detachably connected to the article carrier. The present invention also includes the attachment of a safety flag, or the like, to the frame. It being understood that not all combinations of goods can be accommodated at the same time, e.g., an oxygen tank and a walker cannot be transported at the same time. The weight of the article carrier and its contents, combined with the weight of the rider, should not exceed the recommended weight capacity of the personal mobility vehicle.
[0007] The device anticipates the utilization of a female receiver that typically comes mounted under the seat of personal mobility vehicles. The receiver may also be mounted in other locations on the rear of the personal mobility vehicle in other embodiments. A mounting bar is provided at the bottom of the vertical strength member of this article carrier that just fits within the female receiver and is secured in place.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 illustrates the isometric view of the invention mounted to a personal mobility vehicle.
[0009] FIG. 2 illustrates the rear elevation view of the invention mounted to a personal mobility vehicle.
[0010] FIG. 3 illustrates the side elevation view of the invention mounted to a personal mobility vehicle.
[0011] FIG. 4 illustrates the top plan views of several embodiments of the invention. FIG. 4( a ) shows the top plan view of the embodiments without an oxygen tank holder and FIG. 4( b ) shows the top plan view of the embodiments that include an oxygen tank holder.
[0012] FIG. 5 is an isometric view of the first embodiment of the invention showing the frame joined together utilizing friction connectors and assembled with an oxygen tank holder assembly.
[0013] FIG. 6 is a side elevation view of the first embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled with an oxygen tank holder assembly.
[0014] FIG. 7 is a rear elevation view of the first embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled with an oxygen tank holder assembly.
[0015] FIG. 8 is a plan view of the first embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled with an oxygen tank holder assembly.
[0016] FIG. 9 is an isometric view of the second embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled without an oxygen tank holder assembly.
[0017] FIG. 10 is a side elevation view of the second embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled without an oxygen tank holder assembly.
[0018] FIG. 11 is a rear elevation view of the second embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled without an oxygen tank holder assembly.
[0019] FIG. 12 is a plan view of the second embodiment of the invention illustrating the frame joined together utilizing friction connectors and assembled without an oxygen tank holder assembly.
[0020] FIG. 13 is an isometric view of the third embodiment of the invention illustrating a welded frame assembled with an oxygen tank holder assembly.
[0021] FIG. 14 is a side elevation view of the third embodiment of the invention illustrating a welded frame assembled with an oxygen tank holder assembly.
[0022] FIG. 15 is a rear elevation view of the third embodiment of the invention illustrating a welded frame assembled with an oxygen tank holder assembly.
[0023] FIG. 16 is a plan view of the third embodiment of the invention illustrating a welded frame assembled with an oxygen tank holder assembly.
[0024] FIG. 17 is an isometric view of the fourth embodiment of the invention illustrating a welded frame assembled without an oxygen tank holder assembly.
[0025] FIG. 18 is a side elevation view of the fourth embodiment of the invention illustrating a welded frame assembled without an oxygen tank holder assembly.
[0026] FIG. 19 is a rear elevation view of the fourth embodiment of the invention illustrating a welded frame assembled without an oxygen tank holder assembly.
[0027] FIG. 20 is a plan view of the fourth embodiment of the invention illustrating a welded frame assembled without an oxygen tank holder assembly.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0028] For the purpose of illustrating the invention, there are four embodiments of the invention that are described. It should be understood that this invention is not limited to the precise arrangements and instrumentalities shown. Other objects, features and advantages of the present invention will become more fully apparent from the following detailed description of the preferred embodiments, the appended claims and the accompanying drawings herein.
[0029] One of the preferred embodiments of the device includes a frame, which is constructed of square hollow tube aluminum, or any other strong light weight material. However, the frame may be of any given shape and either hollow or solid depending on the need or the desire. The connectors are made of nylon, nylon composite, or other material having similar characteristics. Appropriate adhesive shall be used to insure a secure connection of the connectors to the tubing. Fasteners ( 39 ) such as thru-bolt with washers and lock nuts, screw post bolts or rivets or other fastening means known in the art, shall be used at locations indicated on FIGS. 6 and 10 . The color and finish of the present invention can vary depending on the need and desire. The preferred overall dimensions of the frame is about thirteen inches wide by about twenty-eight inches high, by about sixteen inches deep.
[0030] The first embodiment of the present invention is illustrated by way of example in FIG. 5 through FIG. 8 . In this embodiment the frame members are joined together by friction connectors and assembled with the oxygen tank holder assembly.
[0031] The base of the vertical strength member ( 5 ) is secured to the mounting bar ( 1 ) utilizing a three-way flat tee connector ( 2 ) and the tank support bar ( 3 ) is secured to the remaining horizontal leg of the three-way flat tee connector ( 2 ), extending towards the rear of the frame. A standard end cap ( 4 ) is inserted into the open end of the tank support bar ( 3 ). Across the top of the vertical strength member ( 5 ) the cross members ( 7 , 15 ) are secured in opposite positions, perpendicular to either side of the vertical strength member ( 5 ), utilizing a three-way flat tee connector ( 6 ) so that the cross members ( 7 , 15 ) are also in a perpendicular alignment to the mounting bar ( 1 ). Two horizontal arms ( 9 , 17 ) are secured at right angles to the ends of the cross members ( 7 , 15 ), mirroring about the vertical strength member ( 5 ) by using three-way corner connectors ( 8 , 16 ). The horizontal arms ( 9 , 17 ) extend towards the rear of the frame. Front posts ( 13 , 21 ) are secured to the vertical leg of the three-way corner connectors ( 8 , 16 ). Rear posts ( 11 , 19 ) are secured to the rear end of the horizontal arms ( 9 , 17 ) using two-way right angle connectors ( 10 , 18 ). Standard end caps ( 12 , 20 ) are inserted into the tops of the two rear posts ( 11 , 19 ) and a standard end cap ( 22 ) is inserted into the top of the front post ( 21 ). Threaded end cap ( 14 ) is inserted into the top of the front post ( 13 ).
[0032] A safety flag ( 29 ) is attached to the frame using a rod ( 28 ) and a threaded rod base ( 27 ), which is attached to a female threaded end cap ( 14 ), which is attached to a front post ( 13 ). The rod ( 28 ) is secured to the threaded rod base ( 27 ) using adhesive. The safety flag ( 29 ) can be a flag, pennant, or something of the sort and is secured to the top of the rod ( 28 ) using hog rings or any other convenient means known in the art. The safety flag assembly can easily be removed by unscrewing the rod base ( 27 ) from the female threaded end cap ( 14 ).
[0033] Two gripper clips ( 25 , 26 ) are attached by screws, rivets, or any other convenient means known in the art to the back of the vertical strength member ( 5 ) in order to transport a cane. Two cylindrical bands ( 23 , 24 ) are attached by screws, rivets, bolts, or any other convenient means known in the art to the rear of the vertical strength member ( 5 ) for means for use in transporting an oxygen tank. Two thumb screws are attached to each of the cylindrical bands ( 23 , 24 ) to tighten against and stabilize the oxygen tank.
[0034] This first embodiment of the frame is attached to the mobility vehicle by inserting a threaded bolt with knob, set screw, or other fastening means known in the art, using the threaded hold weldment, as typically found as part of the female receiver located on the personal mobility vehicle. After the mounting bar ( 1 ) has been inserted into the female receiver, it is secured by tightening the threaded bolt, through the two drilled holes ( 38 ) provided in the mounting bar portion of the frame, and against the opposite inside wall of the female receiver. A female receiver is well known in the art and is not disclosed or discussed further herein. When it is desired to remove the frame away from the personal mobility vehicle, the set screw or threaded bolt with knob is loosened and the frame is removed. The mounting bar portion of the frame may also be retained within the female receiver by any other means known in the art for securing a mounting bar.
[0035] The second embodiment of the present invention is illustrated in FIG. 9 through FIG. 12 . In this embodiment the frame members are joined together by friction connectors and assembled without the oxygen tank holder assembly.
[0036] The base of the vertical strength member ( 5 ) is secured to the mounting bar ( 1 ) using a two-way right angle connector ( 30 ). Across the top of the vertical strength member ( 5 ) there are two cross members ( 7 , 15 ) that are secured in opposite positions, perpendicular to either side of the vertical strength member ( 5 ) using a three way flat tee connector ( 6 ) so that the cross members ( 7 , 15 ) are also in a perpendicular alignment to the mounting bar ( 1 ). Two horizontal arms ( 9 , 17 ) are secured at right angles to the ends of the cross members ( 7 , 15 ) mirroring about the vertical strength member ( 5 ) using the three-way corner connectors ( 8 , 16 ). The horizontal arms ( 9 , 17 ) extend towards the rear of the frame. Two front posts ( 13 , 21 ) are secured to the vertical leg of the three-way corner connectors ( 8 , 16 ). Two rear posts ( 11 , 19 ) are secured to the rear end of the horizontal arms ( 9 , 17 ) using two-way right angle connectors ( 10 , 18 ). Standard end caps ( 12 , 20 ) are inserted into the tops of the two rear posts ( 11 , 19 ) and a standard end cap ( 22 ) is inserted into the top of the front post ( 21 ). A threaded end cap ( 14 ) is inserted into the top of the front post ( 13 ).
[0037] A safety flag ( 29 ) is attached to the frame using a rod ( 28 ) and a threaded rod base ( 27 ), which is attached to a female threaded end cap ( 14 ), which is attached to a front post ( 13 ). The rod ( 28 ) is secured to the threaded rod base ( 27 ) using adhesive. The safety flag ( 29 ) can be a flag, pennant, or something of the sort and is secured to the top of the rod ( 28 ) using hog rings or any other convenient means known in the art. The safety flag assembly can easily be removed by unscrewing the rod base ( 27 ) from the female threaded end cap ( 14 ).
[0038] Two gripper clips ( 25 , 26 ) are attached by screws, rivets, or any other convenient means known in the art to the back of the vertical strength member ( 5 ) in order to transport a cane.
[0039] This second embodiment of the frame is attached to the mobility vehicle by inserting a threaded bolt with knob, set screw, or other fastening means known in the art, using the threaded hold weldment, as typically found as part of the female receiver located on the personal mobility vehicle, and securing it by tightening it against the mounting bar ( 1 ) of the frame that has been inserted into the female receiver. A female receiver is well known in the art and is not disclosed or discussed further herein. When it is desired to remove the frame away from the personal mobility vehicle, the set screw or threaded bolt with knob is loosened and the frame is removed. The mounting bar portion of the frame may also be retained within the female receiver by any other means known in the art for securing a mounting bar.
[0040] The third embodiment of the present invention is illustrated in FIG. 13 through FIG. 16 . In this embodiment the frame members are welded together and assembled with the oxygen tank holder assembly.
[0041] The base of the vertical strength member ( 5 ) is welded at a set distance from the end of the mounting/tank support bar ( 36 ). A standard end cap ( 4 ) is inserted into the open end at the rear of the mounting/tank support bar ( 36 ). The cross member ( 31 ) is centered across the top of the vertical strength member ( 5 ) and welded so that the cross member ( 31 ) is in a perpendicular alignment to the mounting/tank support bar ( 36 ). Two horizontal arms ( 32 , 34 ) are welded at right angles to each end of the cross member ( 31 ) mirroring about the vertical strength member ( 5 ) extending towards the rear of the frame. Two front posts ( 13 , 21 ) are welded to the top of the corners where the cross-member ( 31 ) and horizontal arms ( 32 , 34 ) intersect. Two rear posts ( 33 , 35 ) are joined and welded to the rear ends of the horizontal arms ( 32 , 34 ). Standard end caps ( 12 , 20 ) are inserted into the tops of the two rear posts ( 33 , 35 ) and a standard end cap ( 22 ) is inserted into the top of the front post ( 21 ). A threaded end cap ( 14 ) is inserted into the top of the front post ( 13 ).
[0042] A safety flag ( 29 ) is attached to the frame using a rod ( 28 ) and a threaded rod base ( 27 ), which is attached to a female threaded end cap ( 14 ), which is attached to a front post ( 13 ). The rod ( 28 ) is secured to the threaded rod base ( 27 ) using adhesive. The safety flag ( 29 ) can be a flag, pennant, or something of the sort and is secured to the top of the rod ( 28 ) using hog rings or any other convenient means known in the art. The safety flag assembly can easily be removed by unscrewing the rod base ( 27 ) from the female threaded end cap ( 14 ).
[0043] Two gripper clips ( 25 , 26 ) are attached by screws, rivets, or any other convenient means known in the art to the back of the vertical strength member ( 5 ) in order to transport a cane. Two cylindrical bands ( 23 , 24 ) are attached by screws, rivets, bolts, or any other convenient means known in the art to the rear of the vertical strength member ( 5 ) for means for use in transporting an oxygen tank. Two thumb screws are attached to each of the cylindrical bands ( 23 , 24 ) to tighten against and stabilize the oxygen tank.
[0044] This third embodiment of the frame is attached to the mobility vehicle by inserting a threaded bolt with knob, set screw, or other fastening means known in the art, using the threaded hold weldment, as typically provided as part of the female receiver located on the personal mobility vehicle. After the mounting/tank support bar ( 36 ) has been inserted into the female receiver, it is secured by tightening the threaded bolt through the two drilled holes ( 38 ), provided in the mounting/tank support bar portion of the frame, and against the opposite inside wall of the female receiver. A female receiver is well known in the art and is not disclosed or discussed further herein. When it is desired to remove the frame away from the personal mobility vehicle, the set screw or threaded bolt with knob is loosened and the frame is removed. The mounting/tank support bar portion of the frame may also be retained within the female receiver by any other means known in the art for securing a mounting bar.
[0045] The fourth embodiment of the present invention is illustrated in FIG. 17 through FIG. 20 . In this embodiment the frame members are welded together and assembled without the oxygen tank holder assembly.
[0046] In this embodiment the vertical strength member and the mounting bar is a single bent piece known as the one piece mounting bar and vertical strength member ( 37 ). This piece has approximately a 90 degree bend. The cross member ( 31 ) is centered across the top of the vertical portion of the one piece mounting bar and vertical strength member ( 37 ) and welded so that the cross member ( 31 ) is in a perpendicular alignment to the mounting bar portion of the one piece mounting bar and vertical strength member ( 37 ). Two horizontal arms ( 32 , 34 ) are welded at right angles to each end of the cross member ( 31 ) mirroring about the vertical portion of the one piece mounting bar and vertical strength member ( 37 ) extending towards the rear of the frame. Two front posts ( 13 , 21 ) are welded to the top of the corners where the cross member ( 31 ) and the horizontal arms ( 32 , 34 ) intersect. Two rear posts ( 33 , 35 ) are welded to the rear ends of the horizontal arms ( 32 , 34 ). Standard end caps ( 12 , 20 ) are inserted into the tops of the two rear posts ( 33 , 35 ) and a standard end cap ( 22 ) is inserted into the top of the front post ( 21 ). A threaded end cap ( 14 ) is inserted into the top of the front post ( 13 ).
[0047] A safety flag ( 29 ) is attached to the frame using a rod ( 28 ) and a threaded rod base ( 27 ), which is attached to a female threaded end cap ( 14 ), which is attached to a front post ( 13 ). The rod ( 28 ) is secured to the threaded rod base ( 27 ) using adhesive. The safety flag ( 29 ) can be a flag, pennant, or something of the sort and is secured to the top of the rod ( 28 ) using hog rings or any other convenient means known in the art. The safety flag assembly can easily be removed by unscrewing the rod base ( 27 ) from the female threaded end cap ( 14 ).
[0048] This fourth embodiment of the frame is attached to the mobility vehicle by inserting a threaded bolt with knob, set screw, or other fastening means known in the art, using the threaded hold weldment, as typically provided as part of the female receiver located on the personal mobility vehicle, and securing it by tightening it against the portion of the one piece mounting bar and vertical strength member ( 37 ) of the frame that has been inserted into the female receiver. A female receiver is well known in the art and is not disclosed or discussed further herein. When it is desired to remove the frame away from the personal mobility vehicle, the set screw or threaded bolt with knob is loosened and the frame is removed. The portion of the one piece mounting bar and vertical strength member of the frame may also be retained within the female receiver by any other means known in the art for securing a mounting bar.
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This invention relates to a multi-purpose article carrier for a personal mobility vehicle, such as a motorized mobility scooter or other powered mobility vehicle, of the type used to transport a disabled person. The present invention provides a light weight, easily installed and removable means whereby the user can easily and temporarily expand the carrying capacity of the personal mobility vehicle. The present invention does not appreciably add to the wind resistance, does not damage the vehicle, and is easy to drive and maneuver, since no portion of the device touches the ground while the vehicle is moving, and is easy to store when not in use.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved file grinder and more particularly, to an improved abrading and cutting tool assembly for use with a hand-operated drive assembly, such as a reciprocating sander, adapted for use in construction and automotive fields.
2. Description of the Related Art
In general, conventional file grinders 1 known in the art include a plurality of teeth 3 and openings 6 disposed on a tool body 2 and a pair of handle engagements 4 attached to the tool body 2 by bolts 7 and having an arc portion 5 disposed thereon as shown in FIG. 1. However, these file grinders suffer from a number of problems such as, for example, they are difficult to abrade and cut the object and remove a great amount of dust therefrom; they cannot operate in triangular or rectangular holes of an object; their teeth become too dull in a short time period; and the file grinders are difficult to clean.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a newly improved file grinder, which eliminates the above problems encountered with conventional file grinders.
Another object of the present invention is to provide a newly improved abrading and cutting tool assembly for use in construction and automotive fields.
A further object of the present invention is to provide a file grinder which includes a plurality of blades as a composite structure, a plurality of longitudinal openings for freely removing a great amount of dust therethrough, and a pivotal handle whereby this file grinder can abrade and cut effectively and operate in triangular or rectangular holes.
Still another object of the present invention is to provide a file grinder which is a composite structure containing a plurality of blades and having a handle attached to one end of the file grinder so as to effectively operate in a tubular object.
Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Briefly described, the present invention provides an improved abrading and cutting composite structure containing a plurality of blades and openings, as a multipurpose tool in construction and automotive fields.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus, are not limitative of the present invention, and wherein:
FIG. 1 is a perspective view of a conventional file grinder;
FIG. 2 is a perspective view of a first embodiment of a file grinder according to the present invention;
FIG. 3 is a cross-sectional view of FIG. 1, taken along line 3--3;
FIG. 4 is a perspective view of a second embodiment of a file grinder according to the present invention; and
FIG. 5 is a perspective view of a third embodiment of a file grinder according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in detail to the drawings for the purpose of illustrating embodiments of the present invention, the file grinder, as shown in FIGS. 2 and 3, comprises a composite structure 11 containing a plurality of steel blades 12 and a plurality of steel spacer links 14 for forming a plurality of longitudinal cleaner channels or passages 21, so as to smoothly and effectively remove grinding dust of the object therethrough, and a handle 10. The blades are straight and elongated, as shown on FIGS. 2, 4 and 5. Each of the elongated blades has a substantially flat upper edge, an opposed lower edge, a predetermined thickness, and a median line defined by a line extending along the elongated blades at a position halfway between the upper edge and the lower edge. The passages 21 have a passage depth extending from the lower edge of the elongated blades to a depth beyond the median line, as shown in FIG. 3. The longitudinal passages 21 of the passage depth extend along substantially the entire length of the composite structure. The spacer links are entirely located between the upper edge and the median line, as shown in FIG. 3. The thickness of the spacer links is approximately equal to the thickness of the elongated blades, as shown in FIG. 3.
Each blade 12 is made of steel and includes a plurality of equally spaced toothed cutting edges 13 for abrading and cutting the object. The links 14 are fixed to the blades 12 by means of conventional methods such as welding.
The handle 10 defines a grasping portion 16, an end face 20, and a rod 17. The rod 17 has a distal end with an aperture therein pivotally connected to a top middle portion of the composite structure 11 by a threaded bolt 19 which is attached to the top of one of the links 14. A threaded nut 18 secures the rod 17 to the bolt 19. The handle 10 can be extended from the composite structure 11 at any angle (i.e. 360°) depending on the structure of the object to be abraded. For example, in order to abrade and cut a wide open space of the object, the handle 10 should extend from the composite structure 11 of the present invention at an angle of 90°. The threaded bolt, nut and aperture make up fastening means for fastening the rod to the composite structure.
The facing of the toothed cutting edges 13 provides a varied slope so as to effectively abrade and cut an object. Also the toothed cutting edges 13 are made of extremely hard material, such as sintered carbides, steels, etc. Also, the number of toothed cutting edges 13 in a certain length of the steel blades 12 can be determined based on the material of the object and grinding efficiency.
Referring in detail to FIG. 4, there is illustrated an additional embodiment of a file grinder in accordance with the present invention. The handle 10 is fixed to one end of the composite structure 11 by the bolt 19 attached to the top of composite structure 11, and the nut 18. The handle 10 is to be extended from the composite structure 11 so as to operate in all types of openings of an object.
Referring in detail to FIG. 5, there is illustrated a third embodiment of a file grinder in accordance with the present invention. The composite structure 11 without any handle 10 can be used by hand or attached to conventional apparatuses such as rollers, belts, etc. (not shown). One specific example is the attachment of the composite structure 11 to a rotator. Such an embodiment would include a flat rotating disk-like structure having at least one composite structure radially attached thereto, so that the composite structure provides a grinding surface for said rotator.
In manufacture, a plurality of steel blades 12 are aligned substantially parallel to one another as a bundle and several links 14 are mounted across the plurality of steel blades 12 by means of any conventional methods such as welding. As shown in FIGS. 2-5, and especially FIG. 3, this allows the blades to be secured together while allowing the outermost blades to define the maximum width of the composite structure. In other words, there is no need for fasteners to extend through the blades thereby increasing the overall width of the composite structure. Further, as shown in FIG. 2, the width as well as the height of the composite structure decreases at the opposed end portions of the composite structure. This is due to the decrease of the spacing which exists between each of the individual blades. As shown in FIG. 3, the spacing between each of the individual blades which form the longitudinal channels is approximately equal to the thickness of the individual blades. This spacing is continuous and uninterrupted along approximately the entire length of the composite structure. However, at the opposed end portions, this spacing is much less, as FIG. 2 illustrates. The decrease in spacing forms a tapered end portion at each opposed end portion of the composite structure, which, as FIG. 2 illustrates, tapers in both the width and height directions. The bolt 19 is fixed to the link 14 disposed on one end, as in FIG. 4, or the top portion of the bundle of the composite structure 11 of steel blades 12, as in FIG. 2. The handle 10 is pivotally attached to the bolt 19 by the nut 18. Thereafter, the handle 10 is adjusted according to specific jobs and the object shape and securely fixed to the composite structure 11. While the file grinder works on an object, the grinding dust can be smoothly separated therefrom through the longitudinal openings 21 so that the file grinder of the present invention can be effectively operated.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
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The present invention provides an improved abrading and cutting composite structure containing a plurality of blades and openings, as a multipurpose tool in construction and automotive fields.
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[0001] The present application constitutes a continuation-in-part of U.S. patent application Ser. No. 11/214,518, entitled PROCESS FOR GLASS-TO-GLASS SEALING OLEDS WITH DRY FILM ADHESIVE, naming James D. Sampica, Paul R. Nemeth and Vincent P. Marzen as inventors, filed Aug. 30, 2005, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0002] The present application constitutes a continuation-in-part of U.S. patent application Ser. No. 11/215,683, entitled PANEL-TO-PANEL LAMINATION METHOD FOR IMPROVED UNIFORMITY, naming Vincent P. Marzen, Paul R. Nemeth and James D. Sampica as inventors, filed Aug. 30, 2005, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0003] The present application constitutes a continuation-in-part of U.S. patent application having the United States Postal Service Express Mailing Label No. EM117518596US, entitled SUBSTRATE LAMINATION SYSTEM AND METHOD, naming Tracy J. Barnidge, Vincent P. Marzen, Paul R. Nemeth, and James D. Sampica as inventors, filed Jan. 18, 2008, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0004] The present application constitutes a continuation-in-part of U.S. patent application having the United States Postal Service Express Mailing Label No. EM117518675US, entitled SYSTEM AND METHOD FOR DISASSEMBLING LAMINATED SUBSTRATES, naming Tracy J. Barnidge, Vincent P. Marzen, Paul R. Nemeth, and James D. Sampica as inventors, filed Jan. 18, 2008, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0005] The present application constitutes a continuation-in-part of U.S. patent application having the United States Postal Service Express Mailing Label No. EM117518640US, entitled SYSTEM AND METHOD FOR COMPLETING LAMINATION OF RIGID-TO-RIGID SUBSTRATES BY THE CONTROLLED APPLICATION OF PRESSURE naming Tracy J. Barnidge, Vincent P. Marzen, Paul R. Nemeth, and James D. Sampica as inventors, filed Jan. 18, 2008, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0006] The present application constitutes a continuation-in-part of U.S. patent application having the United States Postal Service Express Mailing Label No. EM117518667US, entitled ALIGNMENT SYSTEM AND METHOD THEREOF, naming Tracy J. Barnidge, Vincent P. Marzen, Paul R. Nemeth, and James D. Sampica as inventors, filed Jan. 18, 2008, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0007] The present application constitutes a continuation-in-part of U.S. patent application having the United States Postal Service Express Mailing Label No. EM117518653US, entitled PLANARIZATION TREATMENT OF PRESSURE SENSITIVE ADHESIVE FOR RIGID-TO-RIGID SUBSTRATE LAMINATION naming Tracy J. Barnidge, Vincent P. Marzen, Paul R. Nemeth, and James D. Sampica as inventors, filed Jan. 18, 2008, which is currently co-pending, or is an application of which a currently co-pending application is entitled to the benefit of the filing date.
[0008] All subject matter of the Related Applications and of any and all parent, grandparent, great-grandparent, etc. applications of the Related Applications is incorporated herein by reference to the extent such subject matter is not inconsistent herewith.
BACKGROUND
[0009] Liquid crystal display (LCD) screens and other monitors may require rigid or semi-rigid substrates to be coupled to the display. These substrates may serve many purposes including optical enhancements, protection from impact, or environmental concerns, or sometimes to improve thermal operating range, such as heating elements. As such, robust lamination of multiple substrates, such as a rigid glass substrate to an LCD screen, may be desirable.
SUMMARY
[0010] The present disclosure is directed to a substrate lamination system and method.
[0011] A substrate lamination apparatus may comprise: (a) a vacuum chamber; (b) a flexible membrane; and (c) a substrate support.
[0012] A system for laminating substrates may comprise: (a) a vacuum chamber; (b) a flexible membrane; (c) a substrate support; (d) a vacuum pump; (e) a compressor; and (f) a control unit, wherein the control unit is configured to carry out the steps: (i) evacuating the vacuum chamber; and (ii) applying pressure to at least one of a first substrate and a second substrate.
[0013] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not necessarily restrictive of the claims. The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate examples and together with the general description, serve to explain the principles of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The numerous advantages of the disclosure may be better understood by those skilled in the art by reference to the accompanying figures in which:
[0015] FIG. 1 is an isometric view of a substrate lamination system.
[0016] FIG. 2 is an cross-sectional view of a substrate lamination system.
[0017] FIG. 3 top view of a substrate lamination system.
[0018] FIG. 4 is an isometric view of a substrate lamination system.
[0019] FIG. 5 is an isometric view of a substrate alignment insert.
[0020] FIG. 6 is a top view of a substrate mask.
[0021] FIG. 7 an schematic view of a substrate lamination system.
[0022] FIG. 8 is a high-level logic flowchart of a process.
[0023] FIG. 9 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0024] FIG. 10 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0025] FIG. 11 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0026] FIG. 12 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0027] FIG. 13 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0028] FIG. 14 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0029] FIG. 15 is a high-level logic flowchart of a process depicting alternate implementations of FIG. 8 .
[0030] FIG. 16 is a high-level logic flowchart of a process.
[0031] FIG. 17 is a high-level logic flowchart of a process.
[0032] FIG. 18 is a cross-sectional view of a substrate lamination system.
DETAILED DESCRIPTION
[0033] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here.
[0034] FIGS. 1 and 18 illustrate example systems in which one or more technologies may be implemented. A lamination system 100 may comprise a vacuum chamber 110 , at least one flexible membrane 120 , and a substrate support 130 .
[0035] The vacuum chamber 110 may be any container which is capable of being sealed so as to separate a space interior to the vacuum chamber 110 from a space exterior to the vacuum chamber 110 . For example, the vacuum chamber 110 may be a generally rectangular structure having a vacuum chamber body 111 and a vacuum chamber lid 112 . The vacuum chamber 110 may be constructed of any number of materials having sufficient strength so as to maintain a vacuum such as aluminum, steel, carbon fiber, plastics, and the like.
[0036] Referring now to FIG. 2 , the flexible membrane 120 may be disposed within the vacuum chamber 110 so as to partition the vacuum chamber 110 into at least a first compartment 121 and a second compartment 122 . For example, the flexible membrane 120 may be affixed to an underside of the vacuum chamber lid 112 by sealing the flexible membrane 120 about the periphery of the vacuum chamber lid 112 so as to partition the vacuum chamber 110 into a first compartment 121 formed by the flexible membrane 120 and the vacuum chamber body 111 and a second compartment 122 formed by the flexible membrane 120 and the vacuum chamber lid 112 .
[0037] The second compartment 122 may comprise an expansion portion 122 A and a plenum portion 122 B separated by a perforated plenum diffuser screen 123 . The perforated plenum diffuser screen 123 may serve to provide uniform distribution of airflow from the plenum portion 122 B into the expansion portion 122 A.
[0038] The flexible membrane 120 may be constructed from any flexible material capable of partitioning two compartments into separate pressure zones. For example, the flexible membrane 120 may be constructed of silicone rubber. The flexible membrane 120 may have one or more of the following physical characteristics: an elongation capacity of at least 100%; a tear strength of at least 30 psi; anti-static properties and/or an anti-static liner (e.g. polyester or polyethylene) disposed on one or more surfaces of the flexible membrane 120 .
[0039] In other exemplary embodiments, the lamination system 100 may comprise at least one lid positioning mechanism 113 . The lid positioning mechanism 113 may serve to maintain the vacuum chamber lid 112 in an open position with respect to the vacuum chamber body 111 . The lid positioning mechanism 113 may comprise a gas cylinder mechanism as depicted in FIG. 1 . In still further exemplary embodiments, the lid positioning mechanism 113 may comprise an actuated mechanism (e.g. a pneumatically actuated system, [not shown]) which may be extended or retracted manually or as part of an automated system controlled by a processing unit.
[0040] Referring now to FIGS. 3-18 , the substrate support 130 may be any device/structure capable of maintaining a first substrate 101 and a second substrate 102 in spatial separation when disposed within the vacuum chamber 110 . The substrate support 130 may maintain the first substrate 101 and/or the second substrate 102 in semi-horizontal positions as in FIG. 2 or in semi-vertical positions as in FIG. 18 . For example, the substrate support 130 may comprise at least one retractable support pin 131 . The retractable support pin 131 may be disposed within and project from a wall of the vacuum chamber body 111 . The retractable support pin 131 may be operably coupled to an actuating mechanism 132 . Further, the use of any number of substrate supports 130 supporting any number of substrates is fully contemplated by the presently described embodiments.
[0041] The cross-geometry of the tip of the retractable support pin 131 may be selected from any number of geometries including, but not limited to: cylindrical, square, hemispherical, trapezoidal, and the like. The geometry may be selected so as to minimize contact with a substrate while providing adequate substrate support.
[0042] The actuating mechanism 132 may comprise a motor 133 configured to translate the retractable support pin 131 in and out of the vacuum chamber 110 . The operation of the motor 133 and the corresponding insertion or retraction of the retractable support pin 131 may be controlled by a control unit 160 , as shown in FIG. 7 .
[0043] In other exemplary embodiments, the substrate support 130 may comprise a deformable support (e.g. a foam or putty structure; a spring structure) an electromagnetic support (e.g. an electromagnet operably couplable to a metallic element), retractable air cylinder or solenoid.
[0044] The first substrate 101 and/or second substrate 102 may be rigid or semi-rigid in nature such that, when supported by the substrate support 130 , the first substrate 101 and/or second substrate 102 do not deform to a degree such that they contact a layer disposed in a horizontal plane beneath the first substrate 101 and/or second substrate 102 , such as a pressure-sensitive adhesive layer 103 . For example, the first substrate 101 may comprise a display monitor (e.g. an LCD, LCOS, or LED screen). The second substrate 102 may comprise an opaque rigid or semi-rigid reinforcing layer (e.g. glass, plastic). The pressure-sensitive adhesive layer 103 may comprise commonly known acrylic or silicone based polymers.
[0045] Referring to FIG. 4 , the vacuum chamber 110 may further comprise a vacuum port 113 so as to provide a connection for a vacuum line (not shown) operably coupled to a vacuum pump 170 . The vacuum port 113 may be operably coupled to the vacuum chamber body 111 to provide a conduit between the first compartment 121 and the vacuum pump 170 .
[0046] The vacuum chamber 110 may further comprise a vacuum/pressurization port 114 so as to provide a connection for a vacuum/compressor line (not shown) operably coupled to a vacuum pump/compressor 180 . The vacuum/pressurization port 114 may be operably coupled to the vacuum chamber lid 112 to provide a conduit between the second compartment 122 and the vacuum pump/compressor 180 .
[0047] In still another exemplary embodiment, the lamination system 100 may comprise at least one locking mechanism 190 . The locking mechanism 190 may serve to secure the vacuum chamber lid 112 to the vacuum chamber body 111 so that the interior of the vacuum chamber 110 may be evacuated. For example, locking mechanism 190 may comprise an electromagnetic lock having an electromagnet 191 and a metal element 192 operably couplable to the electromagnet so as to maintain the vacuum chamber lid 112 and the vacuum chamber body 111 in a locked position, thereby creating an adequate seal via the flexible membrane 120 .
[0048] Referring again to FIG. 5 , the lamination system 100 may further comprise a substrate alignment insert 140 . The substrate alignment insert 140 may serve to align at least one the first substrate 101 and the second substrate 102 within the vacuum chamber 110 . The substrate alignment insert 140 may comprise a base portion 141 (e.g. the floor of the vacuum chamber body 111 or a separate base layer) and at least one substrate alignment guide 142 . For example, the substrate alignment guide 142 may comprise two substantially adjacent wall portions configured at a 90° angle with respect to one another and projecting from the base portion 141 so as to receive at least one substrate within the space defined by the angle of the wall portions.
[0049] In alternate exemplary embodiments, the substrate alignment guide 142 may be selected from brackets, pegs, grooves, bumps, slots, a recessed space within a body, and/or any other suitable mechanism for specifically positioning a substrate within the vacuum chamber 110 .
[0050] In an alternate exemplary embodiment, the base portion 141 of the substrate alignment insert 140 may further comprise a recessed region 145 suitable for receiving at least one of the first substrate 101 and the second substrate 102 .
[0051] Referring to FIG. 6 , the lamination system 100 may further comprise a carriage or substrate mask 150 . The substrate mask 150 may comprise a substantially planar mask body 151 defining a mask aperture 152 . The mask aperture 152 may be configured so as to fit around at least one substrate alignment guide 142 . For example, the mask aperture 152 may comprise alignment guide aperture portions 153 may be which allow the substrate mask 150 to be secured around at least one substrate alignment guide 142 . The substrate mask 150 may serve to protect portions of or the second substrate 102 which are outside the periphery of the mask aperture 152 , such as flexible circuitry 104 coupled to the first substrate 101 .
[0052] Referring again to FIG. 5 , in an alternate exemplary embodiment, the at least one substrate alignment guide 142 may comprise a substrate mask support portion 143 . The substrate mask support portion 143 may allow the substrate alignment guide 142 to support the substrate mask 150 in spatial separation from the base portion 141 when the substrate mask 150 is disposed atop the substrate alignment insert 140 .
[0053] In still another exemplary embodiment, the substrate alignment insert 140 and/or the substrate mask 150 may be removable from the lamination system 100 so as to allow for the lamination of different sizes of substrates. To effectuate the removal of the substrate alignment insert 140 and/or the substrate mask 150 , at least one handle member 144 may be provided.
[0054] In still further exemplary embodiments, lamination system 100 components may incorporate electrostatic discharge (ESD) prevention technologies. For example, the substrate alignment insert 140 and/or the substrate mask 150 may be constructed from materials having desirable ESD properties. Further, the substrate alignment insert 140 , the substrate mask 150 and/or any other lamination system 100 component may be connected to electrical ground via ground lines. Further, the lamination system 100 components may be subjected to ionization such that charged surfaces will dissipate that charge through controlled methods. Such ionization may be conducted prior to bringing sensitive substrates, such as sensitive electronic substrates into close proximity with the lamination system 100 .
[0055] Referring to FIG. 7 , the lamination system 100 may further comprise a control unit 160 . The control unit 160 unit may comprise vacuum control logic 161 , vacuum/pressurization control logic 162 and/or substrate support control logic 163 . The vacuum control logic 161 , vacuum/pressurization control logic 162 , and/or substrate support control logic 163 may comprise integrated logic (e.g. application specific integrated circuitry (ASIC), field programmable gate arrays (FPGA), digital signal processors (DSP)), a programmable logic controller (PLC) or one or more programs (e.g. firmware or software) configured to run on one or more processors (e.g. processors marketed by Intel® and AMD® integrated into personal computers (PCs)).
[0056] The vacuum control logic 161 may be configured to provide control signals to a vacuum pump 170 operably coupled to the vacuum chamber 110 via vacuum port 113 to create a vacuum within the first compartment 121 .
[0057] The vacuum/pressurization control logic 162 may be configured to provide control signals to vacuum pump/compressor 180 operably coupled to the vacuum chamber 110 via vacuum/pressurization port 114 to create a vacuum or pressurization within the second compartment 122 .
[0058] The substrate support control logic 163 may be configured to provide control signals to the actuating mechanism 132 to either insert or retract the retractable support pin 131 .
[0059] FIG. 8 illustrates an operational flow 800 representing example operations related to lamination of one or more substrates with a pressure sensitive adhesive. In FIG. 8 and in following figures that include various examples of operational flows, discussion and explanation may be provided with respect to the above-described examples of FIGS. 1 through 7 , and/or with respect to other examples and contexts. However, it should be understood that the operational flows may be executed in a number of other environments and contexts, and/or in modified versions of FIGS. 1 through 7 . Also, although the various operational flows are presented in the sequence(s) illustrated, it should be understood that the various operations may be performed in other orders than those which are illustrated, or may be performed concurrently.
[0060] After a start operation, the operational flow 800 moves to a disposing operation 810 , where disposing a pressure-sensitive adhesive layer between a substantially planar surface of a first substrate and a substantially planar surface of a second substrate may occur. For example, as shown in FIGS. 1 through 7 , the pressure-sensitive adhesive layer 103 may be disposed between the first substrate 101 and the second substrate 102 . Disposing operation 810 may be conducted in either a manual fashion (e.g. by an operator) or an automated fashion whereby an automated disposing apparatus (e.g. a robotic arm configured to dispose the pressure-sensitive adhesive layer 103 between the first substrate 101 and the second substrate 102 ) such as those commonly found in the manufacturing arts may be employed.
[0061] Then, in a disposing operation 820 , disposing the first substrate, pressure-sensitive adhesive layer and second substrate within a vacuum chamber may occur. For example, as shown in FIGS. 1 through 7 , the first substrate 101 , the second substrate 102 , and the pressure-sensitive adhesive layer 103 may be disposed within the vacuum chamber 110 . Disposing operation 820 may be conducted in either a manual fashion (e.g. by an operator) or an automated fashion whereby an automated disposing apparatus (e.g. a robot arm configured to dispose the pressure-sensitive adhesive layer 103 between the first substrate 101 and the second substrate 102 ) such as those commonly found in the manufacturing arts may be employed.
[0062] Then, in an evacuation operation 830 , evacuating the vacuum chamber may occur. For example, as shown in FIGS. 1 through 7 , the vacuum control logic 161 may cause the vacuum pump 170 to evacuate the first compartment 121 of the vacuum chamber 110 via vacuum port 113 . During vacuum operation 830 , the vacuum/pressurization port 114 or the inlet of the vacuum pump/compressor 180 may be sealed so as to limit any deformation of the flexible membrane 120 during the evacuation of the vacuum chamber 110 .
[0063] Then, in a pressure application operation 840 , applying pressure to at least one of a first substrate and a second substrate may occur. For example, as shown in FIGS. 1 through 7 , the vacuum/pressurization control logic 162 may cause the vacuum pump/compressor 180 to pressurize the second compartment 122 of the vacuum chamber 110 via vacuum/pressurization port 114 . The pressurization of the second compartment 122 may induce a deformation of the flexible membrane 120 in at least the general direction of the first substrate 101 , the second substrate 102 , and the pressure-sensitive adhesive layer 103 . Such a deformation may press the first substrate 101 , the second substrate 102 , and the pressure-sensitive adhesive layer 103 together, thereby attaching the pressure-sensitive adhesive layer 103 so as to laminate the first substrate 101 and the second substrate 102 to one another.
[0064] In other exemplary embodiments, the flexible membrane 120 may comprise a vacuum bag (not shown) which may be disposed within the vacuum chamber 110 , there by defining the first compartment 121 inside the vacuum bag and the second compartment 122 outside the bag. The vacuum bag may at least substantially surround the first substrate 101 , the second substrate 102 , and the pressure-sensitive adhesive layer 103 within the first compartment 121 .
[0065] FIG. 9 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 9 illustrates example embodiments where the disposing operation 810 may include at least one additional operation. Additional operations may include an operation 902 , and/or an operation 904 .
[0066] At the operation 902 , disposing a sheet of pressure-sensitive adhesive between a substantially planar surface of a first substrate and a substantially planar surface of a second substrate may occur. For example, as shown in FIGS. 1 through 7 , the pressure-sensitive adhesive layer 103 may be a preformed adhesive sheet which may be mechanically disposed between the first substrate 101 and the second substrate 102 .
[0067] At the operation 904 , coating at least a portion of at least one of the substantially planar surface of the first substrate and the substantially planar surface of the second substrate with a pressure-sensitive adhesive may occur. For example, as shown in FIGS. 1 through 7 , the pressure-sensitive adhesive layer 103 may be a cured-state polymer-based pressure sensitive adhesive composition which may be coated on a surface of at least one of the first substrate 101 and the second substrate 102 .
[0068] FIG. 10 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 10 illustrates example embodiments where the disposing operation 820 may include at least one additional operation. Additional operations may include an operation 1002 .
[0069] At the operation 1002 , co-aligning a portion of the first substrate with a portion of the second substrate may occur. For example, as shown in FIGS. 1 through 7 , the at least one of the first substrate 101 and the second substrate 102 may be placed within the substrate alignment insert 140 so as to maintain the substrate in a substantially static position during the vacuum creation operation 830 or the pressure application operation 840 . Such alignment may ensure that desired portions of at least one of the first substrate 101 and the second substrate 102 are contacted with the pressure-sensitive adhesive layer 103 while minimizing contact with undesired portions of the first substrate 101 and/or the second substrate 102 .
[0070] FIG. 11 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 11 illustrates example embodiments where the disposing operation 820 may include at least one additional operation. Additional operations may include an operation 1102 , an operation 1104 , and/or an operation 1106 .
[0071] At the operation 1102 , maintaining at least a portion of at least one of the first substrate and second substrate in spatial separation from the pressure-sensitive adhesive layer may occur. For example, as shown in FIGS. 1 through 7 , during the vacuum creation operation 830 , portions of at least one of the first substrate 101 and the second substrate 102 are maintained in spatial separation from the pressure-sensitive adhesive layer 103 by the substrate support 130 so as to allow for a substantially complete evacuation of air between the substrate and the pressure-sensitive adhesive, thereby limiting the entrainment of air between the first substrate 101 and the second substrate 102 . Further, at the operations 1104 and 1106 , supporting at least one of the first substrate and the second substrate on a support pin may occur. For example, as shown in FIGS. 1 through 7 , a retractable support pin 131 may maintain at least one of the first substrate 101 and the second substrate 102 in spatial separation from the pressure-sensitive adhesive layer 103 .
[0072] FIG. 12 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 12 illustrates example embodiments where the disposing operation 820 may include at least one additional operation. Additional operations may include an operation 1202 , and/or an operation 1204 . Further, at the operation 1202 , supporting at least one of the first substrate and the second substrate a deformable support may occur. For example, as shown in FIGS. 1 through 7 , the substrate support 130 may include a deformable support such as a foam, putty structure or a spring having sufficient spring forces such that the substrate support 130 remains in an expanded configuration until a pressure is applied to at least one of the first substrate 101 and the second substrate 102 , such as by the expansion of the flexible membrane 120 . Further, at the operation 1204 , supporting at least one of the first substrate and the second substrate on at least one electromagnetic support may occur. For example, as shown in FIGS. 1 through 7 , the at least one of the first substrate 101 and the second substrate 102 may be operably coupled to a metal element which may be contacted to an electromagnet disposed within the vacuum chamber 110 , such as to the vacuum chamber lid 112 . Upon the application of power to the electromagnet, the metal element operably coupled to the at least one of the first substrate 101 and the second substrate 102 may be magnetically attracted to the electromagnet, thereby supporting the at least one of the first substrate 101 and the second substrate 102 is spatial separation from the pressure-sensitive adhesive layer 103 .
[0073] FIG. 13 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 13 illustrates example embodiments where the evacuation operation 830 may include at least one additional operation. Additional operations may include an operation 1302 , and/or an operation 1304 .
[0074] At the operation 1302 , evacuating a first portion of the vacuum chamber to a first pressure may occur. For example, as shown in FIGS. 1-7 , the second compartment 122 may be evacuated via vacuum/pressurization port 114 . The evacuation of the second compartment 122 may occur prior to closing the vacuum chamber lid 112 atop the vacuum chamber body 111 so as to maintain the flexible membrane 120 in close proximity to the vacuum chamber lid 112 and avoid contact between the flexible membrane 120 and at least one of the first substrate 101 and the second substrate 102 prior to pressure application operation 840 .
[0075] At the operation 1304 , evacuating a second portion of the vacuum chamber to a second pressure may occur. For example, as shown in FIGS. 1-7 , the first compartment 121 may be evacuated via vacuum port 113 . The evacuation of the first compartment 121 may occur after closing the vacuum chamber lid 112 atop the vacuum chamber body 111 so as to remove substantially all air from the interior of the first compartment 121 . During evacuation operation 1304 , a pressure differential may be maintained between the first compartment 121 and the second compartment 122 where the first pressure in the second compartment 122 is lower than the second pressure than the first compartment 121 .
[0076] During evacuation operation 1304 , a pressure differential may be maintained between the first compartment 121 and the second compartment 122 where the first pressure in the second compartment 122 is lower than the second pressure than the first compartment 121 .
[0077] FIG. 14 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 14 illustrates example embodiments where the pressure application operation 840 may include at least one additional operation. Additional operations may include an operation 1402 , and/or an operation 1404 .
[0078] At the operation 1402 , expanding a flexible membrane by the application of pressure to a surface of the flexible membrane may occur. For example, as shown in FIGS. 1 through 7 , a pressure may be exerted on the surface of the flexible membrane 120 facing the second compartment 122 . Further, at the operation 1404 , expanding a flexible membrane by the application of air pressure to a surface of the flexible membrane may occur. For example, as shown in FIGS. 1 through 7 , the vacuum/pressurization control logic 162 of the control unit 160 may cause the vacuum pump/compressor 180 to pressurize the second compartment 122 of the vacuum chamber 110 via the vacuum/pressurization port 114 . Pressurization of the second compartment 122 may cause the flexible membrane 120 to expand, thereby contacting at least one of the first substrate 101 and the second substrate 102 and pressing the first substrate 101 , the pressure-sensitive adhesive layer 103 and the second substrate 102 together to attach to the pressure-sensitive adhesive layer 103 and laminate the first substrate 101 to the second substrate 102 .
[0079] In particular applications, a differential pressure between an evacuated first compartment 121 and a pressurized second compartment 122 of from about 20 to 7600 torr and, more particularly, about 760 torr may be desirable. However, the amount of pressure applied to the second compartment 122 and the corresponding expansion of the flexible membrane 120 may be a function of the pressure required to effectively attach a selected pressure-sensitive adhesive layer 103 or the sensitivity of the first substrate 101 and the second substrate 102 , as would be determinable by one of skill in the art. As such, any range of differential pressures between the first compartment 121 and the second compartment 122 is fully contemplated by this disclosure.
[0080] FIG. 15 illustrates alternative embodiments of the example operational flow 800 of FIG. 8 . FIG. 15 illustrates example embodiments where the pressure application operation 840 may include at least one additional operation. Additional operations may include an operation 1502 . Further, at the operation 1502 , masking a portion of at least one of the first substrate and second substrate from contact with the flexible membrane may occur. For example, as shown in FIGS. 1 through 7 , the substrate mask 150 may be affixed to the substrate alignment insert 140 such that it provides a barrier between the flexible membrane 120 and at least one of the first substrate 101 and the second substrate 102 . Such a configuration may limit the contact area of the flexible membrane 120 to particular portions of at least one of the first substrate 101 and the second substrate 102 within the area defined by the mask aperture 152 during flexible membrane 120 expansion.
[0081] FIG. 16 illustrates an operational flow 1600 representing example operations related to lamination of one or more substrates with a pressure sensitive adhesive. FIG. 16 illustrates an example embodiment where the example operational flow 800 of FIG. 8 may include at least one additional operation. Additional operations may include an operation 1610 , and/or an operation 1612 .
[0082] After a start operation, a disposing operation 810 , a disposing operation 820 , and a vacuum creation operation 830 , the operational flow 1600 moves to a contacting operation 1610 , where contacting at least one of the substantially planar surface of the first substrate and the substantially planar surface of the second substrate to the pressure-sensitive adhesive layer may occur. For example, as shown in FIGS. 1 through 7 , at least one of the first substrate 101 and the second substrate 102 may be moved from a supported position where at least one of the first substrate 101 and the second substrate 102 is maintained in spatial separation from the pressure-sensitive adhesive layer 103 to a contacted position where at least one of the first substrate 101 and the second substrate 102 is brought into physical contact with the pressure-sensitive adhesive layer 103 . Further, at the operation 1612 , retracting a support pin may occur. For example, as shown in FIGS. 1 through 7 , the retractable support pin 131 of the substrate support 130 which may support at least one of the first substrate 101 and the second substrate 102 in spatial separation from the pressure-sensitive adhesive layer 103 may be retracted so as to allow at least one of the first substrate 101 and the second substrate 102 to be brought into physical contact with the pressure-sensitive adhesive layer 103 .
[0083] FIG. 17 illustrates an operational flow 1700 representing example operations related to lamination of one or more substrates with a pressure sensitive adhesive. FIG. 16 illustrates an example embodiment where the example operational flow 800 of FIG. 8 may include at least one additional operation. Additional operations may include an operation 1710 and/or an operation 1720 .
[0084] After a start operation, a disposing operation 810 , a disposing operation 820 , a vacuum creation operation 830 , and a pressure application operation 840 , the operational flow 1700 moves to a heating operation 1710 , where heating at least one of the first substrate, pressure-sensitive adhesive layer, and second substrate may occur. For example, as shown in FIGS. 1 through 7 , the first substrate 101 , the second substrate 102 and the pressure-sensitive adhesive layer 103 may be heated by a heating element internal to the vacuum chamber 110 or disposed within an external heating apparatus, such as an autoclave. Such heating may serve to further set the pressure-sensitive adhesive layer 103 . In particular applications, the heating may occur in an environment having a temperature of from about ambient to 200° C. and, more particularly, about 80° C.
[0085] Further, at operation 1720 , pressurizing an environment containing the first substrate, pressure-sensitive adhesive layer, and second substrate may occur. For example, the first substrate 101 , pressure-sensitive adhesive layer 103 and the second substrate 102 may be disposed in a pressure vessel in which the pressure may be elevated above ambient pressures. The elevated pressure may be from about 760 torr to about 7600 torr and, more particularly about 1520 torr.
[0086] Operations 1710 and 1720 may be conducted over a period of time of from about 2 to 5 hours. However, the amount of heat and pressure applied and the timing therefore may be a function of the heat and pressure required to effectively attach a selected pressure-sensitive adhesive layer 103 or the sensitivity of the first substrate 101 and the second substrate 102 to heat and/or pressure, as would be determinable by one of skill in the art. As such, any range of temperatures and pressures is fully contemplated by this disclosure.
[0087] It is believed that the lamination systems and methods and many of their attendant advantages will be understood by the foregoing description, and it will be apparent that various changes may be made in the form, construction and arrangement of the components thereof without departing from the scope and spirit of the invention or without sacrificing all of its material advantages, the form herein before described being merely an explanatory embodiment thereof. It is the intention of the following claims to encompass and include such changes.
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The present disclosure is directed to a substrate lamination system and method.
A substrate lamination apparatus may comprise: (a) a vacuum chamber; (b) a flexible membrane; and (c) a substrate support.
A system for laminating substrates may comprise: (a) a vacuum chamber; (b) a flexible membrane; (c) a substrate support; (d) a vacuum pump; (e) a compressor; and (f) a control unit, wherein the control unit is configured to carry out the steps: (i) evacuating the vacuum chamber; and (ii) applying pressure to at least one of a first substrate and a second substrate.
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FIELD OF THE INVENTION
This relates to the elimination of cardiac arrhythmia, particularly, atrial flutter by interrupting signals crossing the so-called isthmus region of the heart through electrophysiological (EP) treatment.
BACKGROUND OF THE INVENTION
Cardiac arrhythmia presently affects approximately 2 million people in the United States alone. A first type of arrhythmia, atrial fibrillation, is the disorganized depolarization of a patient's atrium, with little or no effective atrial contraction. Various uncoordinated stages of depolarization and repolarization, due to multiple reentry circuits within the atria, cause, instead of intermittent contraction, quivering in a chaotic pattern that results in an irregular and often rapid ventricular rate. A second type, atrial flutter, is a condition in which atrial contractions are rapid (250 to 300 beats per minute), but regular. In many instances, a circus movement caused by reentry is probably present. The condition is such that the ventricles are unable to respond to each atrial impulse so that at least a partial atrioventricular block develops. Either condition may be chronic or intermittent. It is atrial flutter that the present invention is most intended to address.
Prior methods for treating a patient's arrhythmia include the use of antiarrhythmic drugs such as sodium and calcium channel blockers or drugs which reduce the Beta-adrenergic activity. Other methods include surgically sectioning the origin of the signals causing the arrhythmia, or the conducting pathway for such signals. However, the surgical technique is quite traumatic and is unacceptable to a large number of patients. A more frequently used technique to terminate the arrhythmia involves destroying the heart tissue which causes the arrhythmia by heat, e.g., applying a laser beam or high frequency electrical energy, such as RF or microwave, to a desired arrhythmogenic site on the patient's endocardium. In the latter method, intravascular (EP) devices can be used to form contiguous lesions within a patient's atrial chamber to provide results similar to the surgical segregation techniques in terminating the arrhythmia but with significantly reduced trauma.
Typically, an EP device is advanced within a patient's vasculature and into a heart chamber and a lesion is formed at the site of interest when RF electrical energy is emitted from electrodes of the device. RF ablation techniques produce lesions of a generally small area. Consequently, several lesions are typically needed to completely ablate the area of the average arrhythmogenic site. As such, a major problem of RF ablation techniques is forming a lesion of the requisite size, which completely ablates the area of interest but does not unnecessarily destroy surrounding healthy tissue. There has been a need for ablation devices which allow for improved monitoring of the creation of a lesion, to generate linear lesions of a requisite length. The present invention satisfies this need.
It is well known that in order to effectively produce lesions using EP devices that contact with or proximity to target tissues is key. Various devices used to improve contact with sites of interest in the heart other than the isthmus region are known in the art. Basket-shaped or volume filling devices like basket-shaped catheters which expand to contact opposing heart wall sections, such as that disclosed in U.S. Pat. Nos. 5,228,442 and 5,908,446 to Imran and U.S. Pat. No. 5,465,717 to Imran et al., are known. Another device to provide efficient contact between the treatment device and a site of interest is disclosed in U.S. Pat. No. 5,482,037 to Borghi where a catheter having an electrode on a flexible member which is shaped by a control wire forms a manipulable unit adapted to achieve configurations advantageous for providing a section capable of improved contact of the electrode with tissue. U.S. Pat. No. 5,879,295 to Li et al. discloses a device having multiple electrodes that may be manipulated in a similar manner, except that the two control wires are connected apart from each other near the distal end of the device. Such a configuration allows for the formation of more complex shapes in using the device. Further, U.S. Pat. No. 5,895,417 to Pomeranz et al. discloses a catheter having a resilient, looped end with a section with electrodes. Either end of the loop may be advanced or drawn back to provide various shapes in order that the effective section of the catheter may better conform to a region. The non-active section of the loop may be used to bias the loop against a wall opposite the ablating electrodes portion to press the electrodes into improved contact with the wall it abuts.
Also, steerable or deflectable tip catheters and catheters with preformed curved sections that may be straightened for delivery purposes have been used to provide an electrode interface region conformable with particular regions in the heart. EP devices having simple J or C-shaped curved sections are known. U.S. Pat. No. 5,170,787 to Lindegren discloses a catheter utilizing a J-shaped preformed wire wherein the device has an ablating electrode at the tip. Also, there are EP devices where the curved shape is extended. U.S. Pat. Nos. 5,673,695 and 5,860,920 to McGee et al. disclose a device with a generally-circular or pigtail electrode array that may conform to the circumferential geometry of a selected annulus region in the heart. Both preformed and deflectable means of achieving the desired shape are disclosed therein. U.S. Pat. No. 5,462,545 to Wang et al. discloses a device having electrodes where the device may be formed in a planar spiral and a corkscrew configuration in addition to a generally circular shape. Further, U.S. Pat. No. 5,823,955 to Kuck et al. discloses an EP device with a distal end portion curving in one direction and switching back in an opposite direction. In all, such shapes are provided to enable improved accessibility to and/or interface with a treatment site in the heart.
The present invention also addresses the need for improved accessibility to and/or interface with the heart wall. However, the present invention meets the challenges presented in the treatment of arrhythmia by forming lesions between the tricuspid annulus and the inferior vena cava, i.e., in the “isthmus” region of the heart. Such lesions may be highly effective in treating atrial flutter by breaking abnormal circuits. While the isthmus has become an area of increasing interest, treating the region is complicated by the irregularity of the anatomical geometry and variation of the region from one patient to another. Ridges, crevasses, bumps and the like make uniform contact with the atrial wall for ablation and/or mapping in this region difficult. None of the devices noted above can perform effectively in RF ablation of the isthmus region.
The present invention provides a device and methods specifically adapted to face the challenges in ablating the isthmus region. An EP device utilizing variations on a shape having particular functional advantages is provided. The advantageous shape of the device allows it to be manipulated in a new manner which forms part of the invention.
SUMMARY OF THE INVENTION
This invention is directed to a electrophysiology (EP) device suitable for mapping functions and/or forming ablations or lesions in the isthmus region of a human patient's heart. The EP device of the invention has electrodes along the outer surface of the device and may have temperature sensors to work in concert with the electrodes. When prepared for use the catheter-like device assumes a shape specialized to advantageously interface with the isthmus region to form lesions. Lesions formed may be made in the form of linear ablations particularly suitable for eliminating or minimizing atrial flutter and/or fibrillation by isolating sections of the patient's atrial wall.
The EP device of the invention generally comprises an elongated shaft having a lumen and a proximal section, a distal section, and a plurality of at least partially exposed electrodes disposed on an outer surface of the distal section. A pre-formed forming member is provided in the lumen to shape the distal section of the device transition. Generally, the distal section is shaped in the form of a modified or flattened pigtail configuration with at least a terminal anchor region, and an intermediate interface region. A plurality of electrodes are spaced along a length of the interface section. Also, a tip may be provided at the end of the anchor region. The tip may be any typical atraumatic tip or a smooth, rounded member preferably comprising a radiopaque material. As with the electrodes, the tip may be connected to an electrical energy source to form an active or “hot” member to serve as an ablating electrode.
The electrodes on the distal shaft section form a lesion from within a patient's heart chamber when electrical energy, preferably RF energy, is emitted therefrom. The electrodes may be combination sensing and ablation electrodes which are capable of ablation and detection of electrical activity from within the patient's body. In a preferred embodiment, the electrodes on the device (including the tip, if desired) are independent, for monopolar mode use with an electrode in contact with the exterior of the patient's body for ablation. Alternatively, the electrodes may be configured in a bipolar mode for use as pairs of sensing electrodes on the shaft. A presently preferred electrode is in the form of a helical coil for improved device flexibility, although other designs are suitable including cylindrical bands, arcuate bands, strands, ribbons or the like. For high resolution sensing, the electrodes on the interface section or region may be spaced in a compact array. For sensing or ablating regions other than those opposing the interface region, additional electrodes, possibly closely packed, may be provided on the catheter as well.
A presently preferred embodiment of the invention includes at least one temperature sensor provided to monitor lesion formation placed between adjacent electrodes. To form an effective lesion in the tissue of the heart, the tissue generally should reach a temperature between about 50° C. to 70° C. Above this temperature, extensive tissue damage beyond the desired treatment site may occur as steam forms and ruptures tissue. However, to effectively ablate an arrhythmogenic site, individual lesions formed by adjacent electrodes must come together to form one continuous lesion that completely ablates an area of interest. If there are gaps in-between the lesions, they may not terminate the arrhythmia. By monitoring the tissue temperature, the physician is able to ensure that adequate heating is achieved so adjacent lesions meet or overlap to form as continuous a lesion as possible in view of the anatomical/geometric challenges presented. Such monitoring also allows a physician to avoid over-heating tissue which could cause the charring of the tissue and coagulation of surrounding blood.
To further avoid excessive temperatures, the device of the invention may also include fluid directing passageways which extend radially or longitudinally to facilitate delivery of cooling fluid. The temperature sensors may be thermocouples, although other suitable temperature sensors may be used, such as thermistors or other temperature sensing means.
The shaft of the distal section of the EP device is formed at least in part of individually-insulated electrical conductors that are electrically connected to individual electrodes on the distal section. Preferably the electrical conductors are braided. Individual wires in the distal shaft section are typically connected to temperature sensors, and, in the case of thermocouple temperature sensors, have a distal end which forms the temperature sensor. The temperature conductor wires may be braided with the electrical conductor wires. A plurality of polymer strands formed of nylon, DACRON® or the like may also be braided either with the wires or braided separately and incorporated into the sheath. Where an electrically hot tip is to be used in the catheter, the forming wire itself may be the electrical conductor. The proximal ends of the conductor wires are typically connected to individual pins of a multi-pin connector for energy and data delivery to whatever control unit and/or energy source the EP device is coupled.
The shaped end of the catheter will typically be straightened by a delivery sheath at some point prior to introduction into a guiding catheter. However, the EP device of the present invention may be constructed so as to be remotely manipulable into its desired shape using such structure as known to those with skill in the art, as for typical deflectable catheters. Also, the device may use a shape-memory alloy that assumes the desired shape when a preset temperature of the metal is reached. Naturally, such a device could be activated by heat of the body or by the application of electrical energy causing resistive heating of the material. To remove the device, especially where a preformed core member is utilized, the delivery or guide sheath may be used to once again straighten the device.
Depending upon its construction, the EP device of the invention may be used alone or with a variety of shaped or shapeable guide members. In one presently preferred embodiment, the EP device is used with a deflectable guiding catheter having a lumen which slidably receives the EP device of the invention and a distal section that can be deflected in either of two directions away from the guiding catheter longitudinal axis, such as a NAVIPORT® unit as described in copending application Ser. No. 09/001,249, filed Dec. 30, 1997, titled Deflectable Guiding Catheter to Qin, et al.
Once delivered through the inferior vena cava into the right atrium, the EP catheter is used by manipulating the device so as to hook the end of the device within the tricuspid valve of the heart. The end which passes into this region, whether it seats between cusps or not, serves as an anchoring portion when the surgeon partially retracts the catheter. This retraction puts tensile stress on the form of the EP device causing it to straighten somewhat. As it straightens, the interface portion of the catheter having electrodes is biased against at least a portion of the myocardial tissue of the isthmus. When in such close proximity, ablation may effectively occur. Preferably, this is performed by selecting only those electrodes in contact with the target tissue and applying RF energy to each (independently or in combination) and monitoring the temperature of tissue elevated by the heat generated as a result of the RF energy until a desired temperature is reached. Such steps may be carried out progressively by retracting or advancing the anchor region of the catheter to alter which tissue the interface region is biased against upon retraction. Further, upon complete retraction of the anchor region from the tricuspid valve, the hot tip may be placed into contact with tissue in difficult to reach recesses where upon RF energy is applied to ablate the tissue site and form a full, linear lesion made.
The catheter of the invention is configured for effective EP treatment of the isthmus region of a mammalian heart. This is to be achieved by a combination of the advantages provided by features of the catheter including, but not limited to, the shape of the catheter and placement of electrodes of the temperature sensors for monitoring of the lesion formation, and the RF active ablating tip disclosed. Ablation of the isthmus of a heart to treat atrial flutter and/or atrial fibrillation is further to be achieved by the method of manipulating the catheter as described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic view of portions of a human heart showing the isthmus region.
FIG. 2 is a diagrammatic view of the EP device of the invention in its constrained configuration.
FIG. 3 is a partial cross-sectional view of the same EP device shown in FIG. 2 taken along the lines 3 — 3 .
FIGS. 4 a and 4 b are diagrammatic views of exemplary shapes for the forming member employed in the EP device of the invention.
FIGS. 5 a - 5 d are a series of diagrammatic views demonstrating the EP device of the invention when unconstrained and in various stages of use.
FIG. 6 is a diagram for material of an ememplary form of a forming member of an embodiment of the EP device shown in FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
Before explaining the invention in detail, it is to be understood that the invention is not limited to the embodiment described or as shown in the figures and that elements of the EP device may be variously included or disincluded without departing from the invention. In point of fact, any conventional construction may be employed which is suitable for producing an ablation or micro-ablation device, which may be set in the shape disclosed that is critical to the functionality of the invention in treating the isthmus region of the heart.
FIG. 1 diagrammatically illustrates the target region for treatment by the EP device of the invention. The heart 10 is shown in isolation with right atrium 12 open. Generally, the isthmus region is the area 14 bounded by the tricuspid valve 16 anteromedially and the inferior vena cava 18 posterolaterally. At least a significant portion of this region is more formally referred to as the “posterior isthmus” or “inferior vena cava-tricuspid isthmus.” A section of the isthmus 14 known as “septal isthmus” 20 is generally considered to be the posterior-inferior part of the right atrium 12 . Further, a portion of the isthmus 14 known as the “isthmus quadrilateral” has been defined. This is the section of the right atrial wall that is identified as the region bounded by the extension line 22 of the eustachian valve 24 and ridge from the terminal crest 26 , the hinge line 28 of the septal leaflet 30 of the tricuspid valve 16 , a line 32 traced between the superior extent 34 of the ridge of the eustachian valve 24 and the tricuspid valve 16 orifice at the base of the triangle of Koch 36 , and finally by a line 38 , spanning the termini of lines 22 and 28 .
One study of this region, titled “The Architecture of the Atrial Musculature Between the Orifice of the Inferior Caval Vein and the Tricuspid Valve: The Anatomy of the Isthmus” by J. Cabrera et al., observed the following measurements (in mm) among a sample of healthy human heart specimens:
Line No.
Mean +/− Standard Deviation
Range
22
31 +/− −5
22-47
28
33 +/− −5
20-43
32
26 +/− −4
16-32
38
31 +/− −4
19-40
In addition to the large variances in the size of the isthmus quadrilateral, marked differences in the atrial wall forming the region were noted. Such differences in the texture in the form of ridges or tribiculation further complicate treating the isthmus.
As previously stated, the EP device of the invention and the manner of employing it are provided to enable effective treatment of the isthmus region despite its variation in structure both within a heart and among patients. As shown in FIG. 2, the EP device 40 of the invention generally comprises an elongated shaft 42 having a proximal section 44 a distal section 46 , an electrical connector 48 on the proximal end of the device 44 , a plurality of electrodes 50 on the distal shaft section 46 , a plurality of temperature sensor members 52 on the distal shaft section 46 with at least one temperature sensor between the electrodes 50 , and a smooth, rounded tip 54 at the distal end of the device. A presently preferred material for the tip 54 is a radiopaque metallic material such as platinum, gold, stainless steel and alloys of each. The EP device 40 illustrated in FIG. 2 is shown in a straightened configuration constrained by guide member 56 . Upon removal of member 56 , the device 40 assumes its working shape.
In FIG. 3, an embodiment of the EP device 40 in the form of a catheter with a core member or forming member 58 set within a lumen 60 extending within the catheter body, shaft or sheath 62 is shown. The forming member 58 is connected to the tip 54 by suitable method such as insertion within a recess in the tip 54 and using silver alloy braising paste to secure each. The connection may be conducting so that the tip 54 serves as an electrically “hot” member with member 58 functioning as an electrical lead.
The forming member 58 is preferably a NITINOL (or other Ni—Ti alloy) wire at a maximum diameter of about 0.01 in (0.25 mm) to about 0.020 in (0.051 mm). The distal section 46 preferably has a nominal diameter of about 0.014 in (0.36 mm). Though not shown, the forming member 58 , and preferably a distal section thereof, may be tapered and/or flattened. Where member 58 is wire, it may be shaped into an appropriate form through controlled heating while constrained in a forming fixture. An exemplar procedure is to preheat an oven to 1184° F. (640° C.) and then to heat a forming fixture loaded with NITINOL wires from room temperature to 977° F. (525° C.) in that oven. Following this, the form and wire(s) will be quenched in room temperature tap water. The exemplary wire 58 treated in this manner was DSC tested and displayed the profile depicted in FIG. 6 .
Use of other types of wire for forming member 58 is contemplated in the invention such as stainless steel wire, music wire, titanium wire or superelastic or shape-memory wire other than the alloys of Ni—Ti. Use of other shaping methods within the level of skill in the art, such as cold-forming the wire, are also contemplated. Further, a composite material such as made with carbon fiber, KEVLAR®, DACRON® or fiberglass, may be used for the forming member 58 .
Also it is to be understood that the forming member 58 need not be a central member disposed within a catheter body 62 . Other constructions not shown where the EP device is provided an appropriate shape for its intended purpose will suffice. A differently configured forming member or multiple members may be integrated in to the catheter body 62 to provide the required shape of the EP device. Alternately, the catheter body 62 itself may be constructed of a material or in a manner where no separate forming member is needed. The lumen 60 may either remain or not.
In the illustrated EP device embodiment presently preferred, after the tip 54 is affixed to the wire 58 and the subassembly is cleaned, the forming member 58 is provided with a partial jacket 70 extending 4 in (10 cm) to 6 in (15 cm) proximally from the shoulder section 64 of the tip. The jacket 70 comprises an insulating polyester heat shrink tubing originally about 0.0035 in (0.089 mm) thick and sized to slip over the forming wire 58 prior to heating.
As illustrated in FIG. 3, for the preferred catheter body subassembly 62 , a first polymeric layer 72 comprises a polyamide tube originally at 75 in (190 cm) with 0.16 in ID×0.018 in OD upon which is braided, at 24 pitch width, thermocouple wires 74 and electrical conductors 76 . Over the distal 3.15 in (8 cm) of the braid, a second polymeric layer 78 comprising a thin-walled (originally 0.003 in (0.076 mm) tetrafluoroethylene hexafluoro propylene vinylidene fluoride mixture (THV) or other fluorropolymer is laminated. This structure is formed over a TEFLON® beading 86.6 in (220 cm)×0.15 in OD (3.8 mm) which is removed when the subassembly 62 is complete.
After exposing selected sections of braided wire, electrode coils 50 optionally in the form of helical coils of platinum/iridium and temperature conducting thermocouple bands 82 preferably of gold are connected to the appropriate wires with gold-tin wire solder. Interelectrode spacing 68 is preferably between about 1 mm to about 3 mm and most preferably 2 mm in order to accommodate a temperature sensor between electrodes. In a preferred embodiment, the exposed length 100 of the electrodes is between about 2 mm and about 8 mm. In a preferred embodiment of the device 40 , the electrical conductors 76 are formed of 36 AWG copper wire having a polyimide insulating coating of about 0.0005 inch thick (0.013 mm) and temperature sensors 84 are T-type thermocouples formed by connecting thermocouple wires 74 comprising 41 AWG copper and constantan wires having a polyimide insulating coating of about 0.00025 in (0.007 mm) to about 0.0005 in (0.013 mm) thick. In the embodiment of the EP device illustrated in FIG. 3, the distal ends of the thermocouple wires are joined together so that the thermocouple formed therefrom measures the temperature at the interface of the two wires. Alternatively, the distal ends of the thermocouple wires may be individually secured to the conducting member 76 in a spaced-apart configuration so that the thermocouple measures the temperature along the length of the conducting member 76 between the distal ends of the thermocouple wires.
In a presently preferred embodiment as shown in FIG. 2, about 4 to about 12 coil-type electrodes 50 are provided on the distal portion 46 of the EP device. An 8 electrode coil variation is pictured. In addition, the device 40 may be adapted or configured so tip 54 may is a “hot” tip to also serve as an electrode. The thermocouple wires 74 and electrical conductor wires 76 and core wire 58 are to be in electrical communication with connector 48 . Presently, a 26 pin connector (available through LEMO USA) is preferred. Where the invention is to be produced without temperature sensors, a hot tip or fewer electrodes, a connector with a lower pin count, e.g. 9 to 16 pins, may be preferred.
Referring again to FIG. 3, a third polymeric layer 86 comprising THV or other fluoropolymer having an initial 0.052 in ID (1.3 mm)×0.061 in OD (1.55 mm) may be laminated over the thermocouple conducting members 82 , between electrodes 50 and the remainder of the body 62 . The third polymeric layer 86 may cover at least the ends 80 of the electrodes 50 as shown to prevent exposure of a sharp metallic edge of the electrode to tissue. Alternatively, where the third polymeric layer 86 does not partially cover the electrode ends 80 , any gaps between electrodes 50 and thermocouples may be filled-in with an adhesive (preferably LOCTITE 3811, available from 3M) and cured using ultraviolet light (UV). Optionally, the polymeric layer 86 may cover all but the portions of the electrodes 50 intended to interface with the isthmus region.
The polymeric jacket 86 covering conducting member 82 insulates the temperature sensors 84 from noise (e.g. RF noise) present as a result of the energy sent to the electrodes 50 . In an alternative embodiment, however, the jacket may be omitted altogether, for example, where filtering capability against signal noise is provided. Similarly, the thermocouple may be attached directly to the electrode coil for a faster and more accurate response where the noise from the electrode energy is otherwise filtered. Such filtering may be accomplished by hardware known to those with skill in the art, including an appropriately programmed general purpose computer.
As shown in FIGS. 2 and 3, the preferred EP device 40 is prepared for use by inserting a proximal portion of the forming member 58 (shown in variations of its basic shape in FIGS. 4 a and 4 b ) into the lumen 60 leaving at least the shaped portion 88 of the forming member 58 exposed. Next, a restraining guide or tube 56 is provided over the distal end of the catheter body 62 . Optimally, the guide 56 has a length of about 3 in (7.6 cm) and is sufficiently stiff to fully straighten and hold straight the shaped portion of the forming member 58 which is drawn into the catheter body 62 after the wire is cooled below the M f (martinsite finish temperature) point of the Ni—Ti material selected. When the core member 58 returns to room temperature, the less-curved and consequently less-stressed portions of the wire will change into an austenetic phase. When optional tip 54 is used, after member 58 is drawn into the catheter body 62 , shoulder section 64 is laminated with THV resin (preferably THV 200, available from 3M) to the edge 66 of the distal end 46 of the catheter body sheath 62 .
When the restraining guide 56 is removed from the EP device 40 (as illustrated in the FIGS. 2 and 3 in its constrained configuration), it has an unconstrained shape similar to that pictured in FIG. 5 a which is substantially like that of the bare forming members 58 shown in FIGS. 4 a and 4 b. Such a form is assumed by the complete assembly since the catheter body 62 will preferably conform, in large part, to the shape of the forming member 58 . Where a stiffer catheter body or sheath 62 is to be used, it may be advantageous to use a heavier forming member to overcome its resistance. The EP device may not, however, be so stiff that manipulation according to the invention will damage tissue, particularly the tricuspid valve 16 . On the other hand, it may not be so flexible that it will be ineffective for its intended use. The construction as set forth above is within the acceptable range to enable use of the EP device.
The overall size of the shapes may be varied to account for different-sized hearts. Shapes structurally equivalent in nature are intended to be covered by the invention. However, the shape of the unconstrained EP device 40 comprises at least an “anchor” region or section 90 an “interface” region or section 92 . The anchoring portion 90 of the EP device 40 and corresponding section of the forming member 58 is a section between about 0.4 in (10 mm) and about 0.6 in (15 mm), oriented substantially as shown in FIGS. 4 a, 4 b or 5 a. The interface portion 92 of the EP device 40 and forming member 58 is a section between about 3 in (76 mm) and about 5 in (127 mm) and is likewise oriented substantially as shown relative to the shaft 94 . At least a majority of the electrodes 50 are located along the interface portion 92 in the assembled EP device 40 . However, either more or less may be provided according to the physiological requirements of a given patient, especially in view of the optimal length of the interface section 92 . The interface section 92 is optimally in the shape of a compound curve as shown. Provision of such a curve, or other inwardly-tending or bowed/arcuate profile greatly assists in biasing the catheter body 56 against the isthmus region upon retraction of the device 40 . Additionally, section 92 may include at least a portion which is straight. The first region or anchor region 90 as variously described may be curved or be at least partially straight as well. Transition regions between the various sections may be small, large or blended curves. Preferably, where simple curves are used, they will variously have radii of curvature between about 0.1 in (2.5 mm) and about 0.5 in (13 mm). Most preferably, each transition has a radius of curvature of 0.3 in (7.6 mm).
Of course, in addition to describing the portions of the EP device in functional terms, it is also possible to express them as first, second and third sections or the like corresponding to the portions 90 , 92 and 94 , respectively. The geometric relation of these sections to one another may be considered in vector notation, radial coordinates or otherwise. An angle a defined by a tangent to the end 96 of the first section 90 and a central portion 98 of the second section 92 may be between about 60° and about 90°. More preferably between 60° and 70°; most preferably at 70°. An angle β defined by tangents to a central, most convex portion 98 of the second section 92 and the third section 94 may be between about 30° and about 90°; most preferably about 90°. It is specifically stated that any specific angle, range of angles, or combination of angles or ranges of angles and/or of lengths disclosed with the exemplar instances provided is expressly considered to be part of the invention.
As noted above, the shape of the EP device 40 , imparted in the preferred embodiment by forming member 58 , enables the way it may function in the setting of the human heart to treat a site at or near the isthmus region 14 . Such function is illustrated in FIGS. 5 a - 5 d.
As shown in FIG. 5 a, upon introduction into the right atrium, section 90 of the device is hooked in the region of the tricuspid valve 16 by advancement in the direction of the arrow. It may be placed between leaflets or on leaflets of the valve 16 . As shown in FIG. 5 b, upon retraction of the EP device 40 , section 92 is forced into contact with the isthmus region 14 . Retraction of the device as shown provides contact pressure with the atrial wall in the desired area of the isthmus to form a lesion. Depending on the construction of the EP device 40 and tensile force applied in retraction, the atrial wall at the isthmus may actually be deformed slightly to place the electrodes 50 in contact with heart tissue otherwise at the bottom of a crevasse or the like. Increased bowing of the interface section 90 , will facilitate the application of greater pressure by the catheter body 56 in the isthmus region 14 to achieve such ends.
Upon achieving the intended contact, it may be desired to use the electrodes to first sense electrical activity or “map” the site with which contact has been achieved. When sensing electrical activity essentially all of the electrodes 50 can be simultaneously employed. Whether after mapping or simply after achieving the contact as diagrammatically pictured in FIG. 5 b, electrical energy (preferably RF energy) is transmitted to the electrodes 50 to ablate the tissue. When performing the ablation, the typical procedure is to direct the RF current to one or two electrodes at the most distal end of the EP device to perform the first ablation and then continue proximally one or two electrodes at a time until an ablation of desired length is obtained in the atrial chamber. This will reduce the overall power requirements for the EP device 40 . The temperature sensors (if included in the EP device) detect the temperature of the heart wall between the adjacent electrodes, so that the electrical power delivered to each electrode can be controlled by a suitable device (such as an RF generator or other device) to control the temperature in a desired manner, and to gauge when a continuous lesion has been formed and, therefore, when to move proximally to the next electrodes. However, simultaneous delivery of RF energy to either a select number or all electrodes is possible (with or without the use of a multiple channel temperature sensing device) where a sufficient power source is provided. Feedback of the temperature data can be used to modulate the power and prevent thrombus formation in the preferred use. Cooling fluid (possibly delivered through a lumen in the device) may be used, either independently or in combination with temperature feedback control as described in copending application, Ser. No. 08/629,057, titled Linear Ablation Device and Assembly to Schaer.
Depending on the success in forming a complete lesion, as may be indicated by temperature sensors on the EP device, or as by using the electrodes to sense electrical activity with the electrodes 50 after an ablation, the EP device may be reset and biased at another location in the isthmus region following substantially the same steps as above. Where a complete ablation in a region has been formed by virtue of the successful manipulation of the specially-adapted shape of the EP device, or where a successful lesion formed is to be lengthened or where it is simply desired to form a lesion at a different site, the steps of resetting the anchor region of the EP device in the vicinity of the tricuspid valve and retracting to bias the shape against the heart wall are simply repeated.
Further, use of the EP device that does not involve the hooking and retraction steps discussed above is possible. As shown in FIG. 5 c, section 92 may simply be advanced so that the electrodes 50 contact an area near the septal isthmus 20 for ablation. Used in this manner, section 90 may even be placed in the tricuspid valve. Further, as shown in FIG. 5 d, the device may be retracted so that region 90 is clear of the tricuspid valve 16 altogether so the tip 54 points into the atrial wall in the isthmus region 14 . When the EP device is retracted so the electrically “hot” tip 16 is effectively dragged into or is otherwise placed at a site, as shown in FIG. 5 d, electrical RF current may follow in order to ablate the tissue around the tip 16 . Because of the shape of the EP device, it may be manipulated so the tip 54 will be forced into site of interest to achieve acceptable contact for ablation.
Each of these uses of the EP device may be employed to start a lesion, to complete one or to fully ablate a particular site requiring treatment.
In addition to where the device of the invention is an integrated unit as shown in the figures with the catheter body 62 and forming member 58 attached to one another, the device and methods described are also contemplated where the device is of a deflectable construction or where the device is in the form of a shaping member like the forming wire used in conjunction with an over-the-wire EP catheter somewhat like that disclosed in U.S. Pat. No. 5,895,355 titled Over-the-Wire EP Catheter to Schaer. The additional steps of manipulating the catheter to form one or more variations of the shape of the EP catheter disclosed herein for a deflectable catheter or inserting the forming wire once the device is otherwise prepared for use with an over-the-wire catheter are expressly considered to be part of the invention.
While the invention has been described herein in terms of certain preferred embodiments, methods of use and preparation for use, a variety of modifications and improvements may be made to the present invention without departing from the scope thereof. Also, those features of the invention discussed above, as related to the figures, are merely preferred and consequently may be varied without departing from the scope of the invention. Furthermore, it is to be understood that the manipulated shapes formed by the EP device in carrying out the treatment method or methods described herein also form part of the invention. Finally, all U.S. patents and applications, to which reference has been made, especially in describing possible variations in the present invention are incorporated by reference in their entirety herein.
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An intravascular electrophysiology (EP) device for the mapping and/or formation of lesions along the isthmus region of a heart that has particular utility in the treatment of atrial flutter. The EP device of the invention has an elongated shaft with a proximal section, a compound-curved or modified pigtail-shaped distal section, and a plurality of at least partially exposed electrodes disposed on an outer surface of the distal section. The electrodes are spaced along a length of the distal section and may be interspersed with at least one temperature sensor located between electrodes. The shape of the distal end of the device enables manipulation of the device by inserting its distal end in the tricuspid valve and retracting the device to bias the section having electrodes along the isthmus to achieve acceptable contact with the region so high frequency (e.g., RF) electrical energy delivered to the electrodes on the distal section of the EP device will form a lesion. Sections of the isthmus where treatment is desired but not reached by the section of the device biased against tissue by retraction may be ablated by repeating the steps of hooking the tricuspid valve at a different end location of the device and retracting to bias the electrodes against different tissue, simply advancing the section with electrodes to the desired site or retracting the device so a tip connected to an RF source will drop into a desired site where ablation may occur.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a precipitation hardened copper alloy, and more particularly, to a Cu—Ni—Si alloy suitable for the use in various components of electronic equipment.
[0003] 2. Description of the Related Art
[0004] Copper alloys for electronic materials used in various components of electronic equipment such as lead frames, connectors, pins, terminals, relays, and switches are required to achieve a balance between high strength and high electrical conductivity (or thermal conductivity) as basic characteristics. In recent years, high integration, miniaturization and thickness reduction of electronic components are in rapid progress, and in this respect, a demand for a copper alloy to be used in the components of electronic equipment is rising to higher levels.
[0005] From the viewpoints of high strength and high electrical conductivity, the amount of use of precipitation hardened copper alloys is increasing in replacement of conventional solid solution hardened copper alloys represented by phosphor bronze and brass, as copper alloys for electronic materials. In a precipitation hardened copper alloy, as a supersaturated solid solution that has been solution-hot-treated is subjected to an aging treatment, fine precipitates are uniformly dispersed, so that the strength of the alloy increases, the amount of solid-solution elements in copper decreases, and also, electrical conductivity increases. For this reason, a material having excellent mechanical properties such as strength and spring properties, and having satisfactory electrical conductivity and thermal conductivity is obtained.
[0006] Among precipitation hardened copper alloys, Cu—Ni—Si copper alloys, which are generally referred to as Corson alloys, are representative copper alloys having relatively high electrical conductivity, strength, stress relaxation characteristic, and bending workability in combination, and constitute one class of alloys for which active development is currently underway in the industry. In this class of copper alloys, an enhancement of strength and electrical conductivity can be promoted by precipitating fine Ni—Si intermetallic compound particles in a copper matrix.
[0007] It has been known that the precipitation state of Ni—Si compound particles influences on the alloy characteristics.
[0008] Japanese Patent No. 3797736 (Patent Document 1) describes an invention including particles of Ni—Si compound particles with the particle size of equal to or greater than 0.003 μm and smaller than 0.03 μm (small particles), and particles with the particle size of 0.03 μm to 100 μm (large particles) and the ratio between the numbers of small particles and large particles is 1.5 or greater. In addition, the small particles with the particle size of smaller than 0.03 μm increase strength and heat resistance alloy, but rarely contribute to shear workability. Meanwhile, the large particles with the particle size of 0.03 μm or greater rarely contribute to an increase in strength and heat resistance of the alloy, but intensively receive stress at the time of a shear process, become sources of microcrack, and significantly increase the shear workability. In addition, it is mentioned that the copper alloy described in Japanese Patent No. 3797736 has significant shear workability together with strength and heat resistance required as copper alloy for electric and electronic component.
[0009] Japanese Patent No. 3797736 describes a method of producing copper alloy as follows.
[0010] 1) Since grains are especially likely to be coarse if Ni content is 4 wt% or greater and Si content is 1 wt % or greater, molten metal after addition of Ni and Si is maintained at the temperature of 1300° C. or greater (or 5 minutes or greater, both are completely melted, and a cooling rate in a mold from a casting temperature to a solidifying temperature is 0.3° C./second or greater, in order to control measurements of grains into a desired scope.
[0011] 2) Heat material after hot rolling is subjected to rapid cooling under water, and the material further subjected to cold rolling is heated at 500 to 700° C. for 1 minute to 2 hours to precipitate large particles. After that, the material is additionally subjected to cold rolling, and heated at 300 to 600° C. for 30 minutes or greater to precipitate small particles at this time.
[0012] 3) Without performing rapid cooling at the time of cooling if hot rolling finishes, the material is maintained at 500 to 700° C. for 1 minute to 2 hours to precipitate large particles, and then subjected to rapid cooling. After the material is further subjected to cold rolling, the material is heated at 300 to 600° C. for 30 minutes or greater to precipitate small particles at this time.
[0013] In view of particle sizes of Ni—Si precipitates und other precipitates in the composition of copper alloy, and a relation between a ratio of distribution density and prevention of grains front being coarse, Japanese Patent No. 3977376 (Patent Document 2) describes precipitates X made from Ni and Si, and precipitates V that do not contain one or both of Ni and Si. and describes that a particle size of the precipitates X is 0.001 to 0.1 μm, and a particle size of the precipitates Y is 0.01 to 1 μm. In addition, in order to achieve compatibility between strength and bending workability, it is described that the number of the precipitates X is 30 to 2000 times of the number of the precipitates Y, and the number of the precipitates X is 10 8 to 10 12 per 1 mm 2 , and the number of the precipitates Y is 10 4 to 10 8 per 1 mm 2 .
[0014] Japanese Patent No. 3977376 describes a method of producing the copper alloy as follows.
[0015] If an ingot is subjected to hot rolling, the ingot is heated at the heating rate of 20 to 200° C./hour, subjected to hot rolling at 850 to 5050° C. for 0.5 to 5 hours, and subjected to rapid cooling so that the finishing temperature of the hot rolling is 300 to 700° C. Accordingly, the precipitates X and Y are generated. After the hot rolling, a desired plate thickness is obtained by combining, for example, solution treatment, annealing, and cold rolling.
[0016] The purpose of the solution treatment is to solid-solubilize Ni and Si precipitated at the time of casting and heating treatment again, and to perform recrystallization at the same time. The temperature of the solution treatment is adjusted according to the added amount of Ni. For example, the temperature is adjusted to 650° C. if the Ni amount is equal to or greater than 2.0 and less than 2.5% by mass, to 800° C. if the Ni amount is equal to or greater than 2.5 and less than 3.0% by mass, to 850° C. if the Ni amount is equal to or greater than 3.0 and less than 3.5% by mass, to 900° C. if the Ni amount is equal to or greater than 3.5 and less than 4.0% by mass, to 950° C. if the Ni amount is equal to or greater than 4.0 and less than 4.5% by mass, and to 980° C. if the Ni amount is equal to or greater than 4.5 and equal to or less than 5.0% by mass.
[0017] International Publication No. 2008/032738 (Patent Document 3) describes a copper alloy strip material for electrical electronic equipment which includes a copper alloy, containing 2.0 to 5.0 mass % of Ni, and 0.43 to 1.5 mass % of Si, with the balance being Cu and unavoidable impurities, and in which three types of intermetallic compounds A, B, and C including 50 mass % or greater of Ni and Si in total are contained, the intermetallic compound A has a compound diameter of equal to or greater than 0.3 μm and equal to or less than 2 μm, the intermetallic compound B has a compound diameter of equal to or greater than 0.05 μm and less than 0.3 μm, and the intermetallic compound C has a compound diameter of greater than 0.001 μm and less than 0.05 μm.
[0018] In addition, disclosed is a method of producing a copper alloy strip material for electrical/electronic equipment including a step of reheating a copper alloy ingot containing 2.0to 5.0 mass % of Ni and 0.43 to 1.5 mass % of Si with the balance being Cu and unavoidable impurities at 850 to 950° C. for 2 to 10 hours, a step of performing hot rolling the reheated copper alloy ingot for 100 to 500 seconds to obtain a copper alloy strip material, a step of performing rapid cooling the copper alloy strip material subjected to hot rolling to a temperature of 600 to 800° C. and a step of performing an aging heat treatment on the copper alloy strip material subjected to rapid cooling, at 400 to 550° C. for 1 to 4 hours.
Patent document 1: Japanese Patent No. 3707736 Patent document 2: Japanese Patent No. 3977376 Patent document 3: International Publication No. 2008/032738
SUMMARY OF THE INVENTION
[0022] The copper alloy described in Japanese Patent No. 3797736 is only reviewed with regard to the ratio between the numbers of small particles and large particles, and is not described the number density of the particles. In addition Japanese Patent No. 3797736 describes the respective precipitation of large particles and small particles by perforating aging twice, but it is difficult to precipitate the small particles in a second aging since the concentration of Ni and Si to be solid-solubilized is lower than that of the particles in a first aging, and favorable influence on strength is insufficient since the number density and the particle size are small (see Comparative Example 5 described below). A technique of performing aging twice has a problem in that controlling the particle size and the density is difficult since the amount of Ni and Si to be solid-solubilized changes depending on the first aging.
[0023] In the copper alloy described in Japanese Patent No 3977376, the particle size of the Ni—Si compound particles is only controlled in the scope of 0.001 to 0.1 μm, and the influence on the alloy characteristic by the Ni—Si compound particles with greater particle size is not reviewed. The large particles described in Japanese Patent No. 3977376 are precipitates that do not contain one or both of Ni and Si. These large particles become coarse depending on the amount of additive elements or the temperature condition, and it is likely to exert adverse influence on bending workability.
[0024] In a process for producing the copper alloy described in International Publication No. 2008/032738, the condition in which large particles precipitate out is extremely unclear. In addition, in the method of producing the copper alloy described in International Publication No. 2008/032738, the solution treatment is carried out by performing heating at 950° C. for 20 seconds, but it is understood that the particle size exceeds 30 μm and the particles become coarse, if the solution treatment is performed in grains with the Ni concentration of 3.3% by mass exemplified in the document.
[0025] Therefore, the purpose of the invention is to enhance the characteristics of Corson alloy by strictly controlling the distribution state of Ni—Si compound particles.
[0026] The inventors of the invention conducted thorough investigations in order to solve the problems described above, and the inventors found that it is possible to obtain Corson alloy with excellent balance between strength and electrical conductivity and satisfactory bending workability classifying Ni—Si compound particles that precipitate out in a copper matrix into Ni—Si compound particles that mainly precipitate out in grains and that base a particle size of equal to or greater than 0.01 μm and less than 0.3 μm (small particles) and Ni—Si compound particles that mainly precipitate out to grain boundaries and that have a particle size of equal to or greater than 0.3 μm and less than 1.5 μm (large particles), and by controlling the respective sizes and number densities. In specific, the inventors found that it is effective that the small particles are controlled so that the size is equal to or greater than 0.01 μm and smaller than 0.3 μm, and the number density is 1 to 2000/μm 2 , the large particles are controlled so that the size is equal to or greater than 0.3 μm and smaller than 1.5 μm, and the number density is 0.05 to 2/μm 2 .
[0027] According to an aspect of the invention that has been completed based on the findings, there is provided a copper alloy for electronic materials which contains 0.4 to 6.0% by mass of Ni and 0.1 to 1.4% by mass of Si, with the balance being Cu and unavoidable impurities, including small particles of Ni—Si compound having a particle size of equal to or greater than 0.01 μm and smaller than 0.3 μm and large particles of Ni—Si compound having a particle size of equal to or greater than 0.3 μm and smaller than 1.5 μm, and in which the number density of the small particles is 1 to 2000/μm 2 and the number density of the large particles is 0.05 to 2/μm 2 .
[0028] According to an embodiment, the copper alloy for electronic materials related to the invention is such that a maximum value of a density ratio per field with regard to the small particles is 10 or smaller if a unit area of 0.5 μm×0.5 μm is set to one field and 10 fields selected from a surface area of the copper alloy of 100 mm 2 are observed, and a maximum value of a density ratio per field with regard to the large particles is 5 or smaller if a unit area of 20 μm×20 μm is set to one field and 10 fields selected from a surface area of the copper alloy of 100 mm 2 are observed.
[0029] According to another embodiment, the copper alloy for electronic materials related to the invention is such that a ratio of an average particle size of the large particles with regard to an average particle size of the small particles is 2 to 50.
[0030] According to still another embodiment, the copper alloy for electronic materials related to the invention is such that an average grain size indicated by a circle-equivalent diameter is 1 to 30 μm if observed from a cross section in a thickness direction parallel to a rolling direction.
[0031] According to still another embodiment, the copper alloy for electronic materials related to the invention is such that a maximum value of a ratio of particle sizes of neighboring grains is 3or less in length in the thickness direction parallel to the rolling direction.
[0032] According to still another embodiment, the copper alloy for electronic materials related to the invention contains at least one selected from the group consisting of Cr, Co, Mg, Mn, Fe, Sn, Zn, Al, and P in an amount of 1.0% by mass in total.
[0033] According to still another embodiment of the invention, there is provided a wrought copper product made from the copper alloy for electronic materials related to the invention.
[0034] According to still another embodiment of the invention, there is provided an electronic component prepared with the copper alloy for electronic materials related to the invention.
[0035] According to still another aspect of the invention, there is provided a method of producing the copper alloy related to the invention, the method including performing the following steps in order: melting and casting ingot having a desired composition after maintaining molten metal obtained by melting materials containing Ni and Si at 1130 to 1300° C. if Ni concentration is 0.4 to 3.0% by mass and maintaining the molten metal at 1250 to 1350° C. if Ni concentration is 3.0 to 6.0% by mass; performing hot rolling after heating at 800 to 900° C. if Ni in the ingot is less than 2.0% by mass, at 850 to 950° C. if Ni in the ingot is equal to or greater than 2.0% by mass and less than 3.0% by mass, at 900 to 1000° C. if Ni in the ingot is equal to or greater than 3.0% by mass and less than 4.0% by mass, and at equal to or greater than 950° C. if Ni in the ingot is 4.0% by mass or greater; performing cold rolling; performing a solution treatment at a solution treatment temperature y(° C.) indicated by y=125x+(475 to 525) if x is Ni concentration (% by mass) in the ingot; and performing an aging treatment.
[0036] According to the invention, it is possible to more effectively enjoy the benefit to an alloy characteristic owing to Ni—Si compound particles precipitated in copper matrix, so the characteristics of Corson alloy may increase.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 is a photograph illustrating large particles in a cross-section in the thickness direction parallel to the rolling direction when observing copper alloy (which is processed by 0%) of the invention by SEM;
[0038] FIG. 2 is a photograph illustrating the large particles in a cross-section in the thickness direction parallel to the rolling direction when observing copper alloy (which is processed by 66%) of the invention by TEM;
[0039] FIG. 3 is a photograph illustrating small particles in cross-section in the thickness direction parallel to the rolling direction when observing copper alloy (which is processed by 0%) of the invention by TEM; and
[0040] FIG. 4 is a photograph illustrating the small particles in a cross-section in the thickness direction parallel to the rolling direction when observing copper alloy (which is processed by 99%) of the invention by TEM.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0041] (Amounts of Addition of Ni and Si)
[0042] Ni and Si form a Ni—Si compound particle (such as Ni 2 Si) as an intermetallic compound when subjected to an appropriate heat treatment, and strength may he enhanced without deteriorating electrical conductivity.
[0043] If the amounts of addition of Si and Ni are too small, the desired strength may not be obtained, and if the amounts are too large, strength may be enhanced, but electrical conductivity significantly decreases so that hot workability deteriorates. In addition, since hydrogen may be solid-solubilized in Ni, and blowholes may be caused at the time of melting and casting, if the amount of addition of Ni is large, fractures may be caused by an intermediate process. Since Si reacts with C or reacts with O, if the amount of addition is large, quite a lot of inclusions may be formed and fractures may be caused at the time of bending.
[0044] Here, an appropriate amount of addition of Si is 0.1 to 1.4% by mass and preferably 0.2 to 1.0% by mass. An appropriate amount of addition of Ni is 0.4 to 6.0% by mass and preferably 1.0 to 5.0% by mass.
[0045] Precipitates of Ni—Si compound particles are generally formed in a stoichiometric composition, and the mass ratio of Ni and Si approximates to the mass composition ratio of Ni 2 Si (Atomic Weight of Ni×2:Atomic Weight of Si×1) that is an intermetallic compound, that is, the mass ratio of Ni and Si is Ni/Si=3 to 7, or preferably 3.5 to 5, so that satisfactory electrical conductivity may be obtained. If the ratio of Ni is higher than the mass composition ratio described above, the electrical conductivity is likely to decrease, and if the ratio of Si is higher than the mass composition ratio described above, the hot workability is likely to deteriorate due to coarse Ni—Si grains.
[0046] (Amounts of Addition of Other Elements)
[0047] (1) Cr and Co
[0048] Cr and Co are solid-solubilized in Cu, and coarsening of grains at the time of performing a solution treatment is suppressed. In addition, strength of an alloy is enhanced. At the time of an aging treatment, silicide is formed and precipitates out, so it impossible to contribute to an increase in strength and electrical conductivity. Since the electrical conductivity of the additive elements rarely decreases, the additive elements may be added as much as desired, but if the amounts of addition are large, adverse influence is exerted on the characteristics. Here, one or both of Cr and Co may be added up to 1.0% by mass in total, and preferably 0.005 to 1.0% by mass.
[0049] (2) Mg and Mn
[0050] Since Mg or Mn reacts with O, a deoxidation effect of molten metal may be obtained. In addition, Mg and Mn are elements that are generally added to increase alloy strength. The most famous effect is to increase a stress relaxation characteristic what is called a creep resistance characteristic. In recent years, current flow becomes high according to the high integration of electronic equipment, and materials may be deteriorated due to heat in a semiconductor package that has low heat dissipation property such as BGA type, so that a failure may be caused. Especially, in case of vehicle installation, decrease due to heat around an engine may be caused, so heat resistance is an important task. Therefore, Mg and Mn are elements that may be added as much as desired. However, if amounts of addition are too large, adverse influence on bending workability may not be disregarded. Here, one or both of Mg and Mn may be added up to 0.5% by mass in total, and preferably 0.005 to 0.4% by mass.
[0051] (3) Sn
[0052] Sn has a similar effect as Mg. However, since the amount that is solid-solubilized in Cu is large unlike Mg, Sn is added if more heat resistance is required. Meanwhile, if the amount increases, the electrical conductivity significantly decreases. Accordingly, Sn may be added up to 0.5% by mass, and preferably 0.1 to 0.4% by mass. However, if both of Mg and Sn are added, total concentration of both elements is set up to 1.0% by mass and preferably up to 0.8% by mass for suppressing an adverse influence on electrical conductivity.
[0053] (4) Zn
[0054] Zn has an effect that suppresses solder embrittlement. However, if amount of addition is large, electrical conductivity decreases. Therefore, Zn may be added up to 0.5% by mass and preferably 0.1 to 0.4% by mass.
[0055] (5) Fe, Al, and P
[0056] These elements may also increase the alloy strength. The elements may be added as necessary. However, if the amounts of addition are large, the characteristics may he deteriorated according to the additive element. Therefore, the elements may be added up to 0.5% by mass, and preferably 0.005 to 0.4% by mass.
[0057] If Cr, Co, Mg, Mn, Sn, Fe, Al, and P described above exceed 1.0% by mass in total, manufacturability is likely to be impaired. Therefore, the total amount of these elements is preferably adjusted to 1.0% by mass or less, and more preferably to 0.5% by mass or less.
[0058] (Ni—Si Compound Particles)
[0059] According to the invention, Ni—Si compound particles precipitated in a copper matrix are classified into two types of small particles and large particles, and number density, particle sizes, and further interrelation thereof may be controlled. According to the invention, the small particles refer to Ni—Si compound particles with particle sizes of equal to or greater than 0.01 μm and smaller than 0.3 μm, and the large particles refer to Ni—Si compound particles with particle sizes of equal to or greater than 0.3 μm and smaller than 1.5 μm. The small particles are particles that mainly precipitate out in the grains and the large particles are particles that mainly precipitate out to grain boundaries. In addition, Ni—Si compound particles refer to particles in which both of Ni and Si are detected from element analysis. The small particles mainly contribute to heat resistance and strength of the alloy, and the large particles mainly contribute to micronization of grains and maintenance of electrical conductivity. Here, FIG. 1 illustrates large particles in a cross-section in the thickness direction parallel to the rolling direction when observing a copper alloy (which is processed by 0%) of the invention by SEM. FIG. 2 illustrates the large particles in a cross-section in the thickness direction parallel to the rolling direction when observing the copper alloy (which is processed by 66%) of the invention by TEM. FIG. 3 illustrates small particles in a cross-section in the thickness direction parallel to the rolling direction when observing the copper alloy (which is processed by 0%) of the invention by TEM. FIG. 4 illustrates the small particles in a cross-section in the thickness direction parallel to the rolling direction when observing the copper alloy (which is processed by 99%) of the invention by TEM.
[0060] Ni—Si compound particles precipitated into grains may be precipitates generally as fine as about tens of nanometers. Among them, since Ni—Si compound particles smaller than 0.3 μm have flux pinning by dislocation, the dislocation density becomes high. Therefore, the strength of the entire alloy is likely to increase. Since Ni—Si compound particles with these particle sizes have small distance between particles and large in number, it is likely to contribute to strength. In addition, since there is an effect of preventing the movement of dislocation at the time of heating, heat resistance increases.
[0061] However, if large strain is applied to particles with this size, in particular, Ni—Si compound particles smaller than 0.01 μm are sheared, and the surface area of the sheared particles decreases, so the shear strength decreases. Accordingly, the dislocation density does not increase without leaving dislocation loop. Accordingly, Ni—Si compound particles smaller than 0.01 μm is not likely to contribute to strength. The sheared particles may be solid-solubilized in the copper parent phase again, and may cause the decrease of electrical conductivity. In addition, since the sheared particles do not work as nucleation sites of recrystallization, the recrystallized grains are likely to become coarse. The coarse grains have adverse influence on strength or bendability.
[0062] Accordingly, it is advantageous to control the number density of small particles with particle size of equal to or greater than 0.01 μm and smaller than 0.3 μm. Small particles significantly contribute to the increase of strength, but are likely to decrease electrical conductivity if there are too many small particles. Therefore, it is necessary to adjust the number density of small particles to 1 to 2000/μm 2 in order to achieve the balance between the strength and the electrical conductivity. The number density of the small particles may be measured through a texture observation with a transmission, electron microscope.
[0063] Meanwhile, Ni—Si compound particles precipitated to the grain boundaries may be precipitates with sizes of approximately hundreds of nanometers to several micrometers. Among them, Ni—Si compound particles equal to or greater than 0.3 μm and smaller than 1.5 μm may work as strong particles that are not likely to be sheared. The heat resistance and strength of the alloy may increase in the same manner as small particles, but since the particle sizes are large, so the number of particles is small and the distance between particles are large so that the contribution to the heat resistance and the strength is smaller than that of the small particles. However, since the particles are rarely sheared though large stain is applied thereto, the electrical conductivity is not likely to decrease. In addition, the particles that are not sheared may work as nucleation sites at the time of recrystallization. Accordingly, it is likely to form grains finer than the large particles. Fine grains especially contribute to strength and bendability. If particles with the size of greater than 1.5 μm increase, Ni and Si to be used for forming small particles are deficient, so the strength is likely to decrease. If Ag plating or the like is carried out on a material, the plating thickness may partially become large. Therefore, it is likely to form defects of protrusion.
[0064] Accordingly, it is advantageous to control the number density of the large particles equal to or greater than 0.3 μm and smaller than 1 μm. The large particles contribute to the increase of electrical conductivity or the miniaturization of grains, but the number density of small particles is likely to decrease if there are too many large particles. Therefore, if the ratio between the numbers of the large particles and small particles is not set to an appropriate scope, balance between both of strength and electrical conductivity may collapse. In specific, if there are many large particles, strength may decrease and if there are many small particles, electrical conductivity may decrease. Therefore, in order to achieve balance between strength and electrical conductivity, the number density of particles in the scope of equal to or greater than 0.3 μm and smaller than 1.5 μm is required to be adjusted to 0.05 to 2/μm 2 . The number density the large particles may be measured through a texture observation with a scanning electron microscope.
[0065] In addition, if an aging treatment is carried out as a final process, precipitated particles strain matrix. At this time, if dispersion is carried out in an uneven density, stress is generated due to the uneven strain and remains. If the remaining stress is large, stress is not relieved even by strain relief annealing. In addition, if the large particles converge into a cluster state, unevenness is formed due to the difference from the circumference at the time of plating or etching so that defects in the form of protrusion may be formed. Further, if cold rolling is carried out after an aging treatment, the particles dispersed in the uneven density have different work hardening property from area to area, so uneven formation occurs. In addition to increase the remaining stress, sometimes this may be a cause of fractures. Especially, if the large particles converge into a cluster state, fractures may originate from the portion. Therefore, it is preferable that the small particles and the large particles exist in the even distribution in the copper alloy respectively.
[0066] Accordingly, it is preferable that the maximum value of the density ratio per field with regard to the small particles be 10 or smaller, if the unit area of 0.5 μm×0.5 μm is set to one field and 10 fields randomly selected from the surface area of the copper alloy of 100 mm 2 are observed, and that the maximum value of the density ratio per field with regard to the large particles be 5 or smaller if the unit area of 20 μm×20 μm is set to one field and 10 fields randomly selected from the surface area of the copper alloy of 100 mm 2 are observed.
[0067] The effect of exploiting the advantages of both the small particles and the large particles and complementing the defects of both particles may be increased by controlling the difference between average particle sizes of the small particles and the large particles to an appropriate scope. It is preferable that the ratio of the average particle size of the large particles with regard to the average particle size of the small particles be 2 to 50.
[0068] It is advantageous that the grains are fine in terms of strength and bendability, but if the grains are too small, the balance between the large particles precipitated to the grain boundaries and the small particles precipitated into the grains collapses. Therefore, if copper alloy of the invention is observed in a cross-section in the thickness direction parallel to the rolling direction, it is preferable that a particle size of grains indicated by circle-equivalent diameter be 1 to 30 μm.
[0069] In addition, it is understood that the sizes of the precipitates are like is to be different in the grain boundaries of the grains and in the grains. Therefore, the uneven sizes of the grains mean that precipitated particles are uneven and it is not preferable for the reasons above. Especially, if it is assumed that the rolling process is deformation in the thickness direction, aligning the length of the grains in the thickness direction significantly influences the plastic deformation property in this direction. In recent years, the plate thickness tends to be small, so if the number density of the grains with regard to the plate thickness is uneven, it is expected that fractures may occur from the portion as an origination. For this reason, it is preferable that the particle sizes of the grains be even in length of the thickness direction parallel to the rolling direction. Accordingly, it is preferable that the maximum value of the ratio of the particle sizes of neighboring grains be 3 or smaller in length in the thickness direction parallel to the rolling direction.
[0070] (Producing Method)
[0071] Next, a description is made to a method of producing a copper alloy according to the invention. The copper alloy according to the invention is based on the conventional method of producing Cu—Ni—Si alloy and may be produced through a partially specific process.
[0072] First, by using an atmosphere melting furnace, raw materials such as electrolytic copper, Ni, and Si are melt, so that molten metal with a desired composition is obtained. At this time, in order to prevent particles form coarsening, it is important to maintain molten metal after addition of Ni and Si in the temperature of 1130 to 1300° C. if the Ni concentration is 0.4 to 3.0% by mass, and in the temperature of 1250 to 1350° C. if the Ni concentration is 3.0 to 6.0% by mass, In this manner, since the melting/holding temperature changes depending on the Ni concentration, the generation of the large particles may be appropriately controlled.
[0073] Subsequently, the molten metal is cast into an ingot. Next, hot rolling is carried out after heating at 800 to 900° C. if Ni in the ingot is less than 2.0% by mass, at 850 to 950° C. if Ni in the ingot is equal to or greater than 2.0% by mass and less than 3.0% by mass, at 900 to 1000° C. if Ni in the ingot is equal to or greater than 3.0% by mass and less than 4.0% by mass, and at equal to or greater than 950° C. if Ni in the ingot is equal to or greater than 4.0% by mass. If the large particles are not sufficiently dissipated or miniaturized in a heat treatment before the hot rolling, the solution treatment is not likely to be carried out, so that large particles remain. In a Cu—Ni 2 Si phase diagram, as the Ni concentration, is high, the temperature of solid solubilization is high. Therefore, the temperature of a heat treatment is set high as the Ni concentration becomes high. If a temperature is lower than the temperature described above, Ni and Si are not sufficiently solid-solubilized. If a temperature is higher than the temperature described above, the solid solubilization is facilitated but breaking may occur due to the interaction between the coarsely recrystallized grains at a high temperature and the product generated at a high temperature. Therefore, it is not preferable. By adjusting the plate thickness at the time of finishing hot rolling to be thinner than 20 mm, cooling is carried out quickly, so that the precipitation of precipitates that does not contribute to the characteristic may be prevented. At this point, the hot rolling may be finished, at the high temperature of 600° C. or greater, but if the solution treatment at a later process is difficult, it is effective to finish the hot rolling at a lower temperature.
[0074] Next, cold rolling is carried out. The cooling rate at a solution treatment described below becomes fast by performing the cold rolling, so that the precipitation of solid-solubilized Ni and Si may be suppressed adequately. The plate thickness after the cold rolling is preferably 1 mm or less, more preferably 0.5 mm or less, and most preferably 0.3 mm or less.
[0075] Next, a solution treatment is carried out. In the solution treatment, Ni—Si composition is solid-solubilized in the Cu matrix and at the same time the Cu matrix is recrystallized. According to the Cu—Ni 2 Si phase diagram, as the temperature is high, the solid solubilization of Ni and Si is facilitated. Therefore, in the conventional art, a solution treatment has been generally performed at a temperature higher than the temperature of the solid solubilization according to the Cu—Ni 2 Si phase diagram. This is to prevent coarse particles that remain due to the insufficient solution treatment from becoming defects since these particles generate defects in electrodeposition in plating. After reviewing these particles, it is understood that the cause exists in the cooling procedure in the hot rolling process after casting and reheating treatments. However, since it is difficult to control the cooling in any processes and Ni and Si may be solid-solubilized in a lump by a solution treatment, the process has rarely attracted an attention in the conventional art. Meanwhile, as a performance required to connectors in recent years, since the characteristics of the material is deficient at the design stage, a bending process that requires high load has been demanded. In this regard, as a result of a review for improving the characteristics of conventional alloy, it is understood that the problem would be solved by leaving no coarse precipitates in a solution treatment and controlling grains to have the size of 5 to 30 μm. The conventional producing method was not able to achieve one of the both, so it has been selected to cover the characteristic with other alternatives rather than making defects in plating. That is, instead of coarsening the grains, strengths has been increased by increasing the working degree of subsequent cold rolling. However, if the working degree increases, bendability decreases, so that deformation processing may not be carried out in the recent connectors. Optimization of the density difference between large particles and small particles and bendability owing to low working degree of cold rolling may be improved by controlling the grains.
[0076] Therefore, in the invention, the condition of the solution treatment is strictly controlled. Specifically, in order to sufficiently solid-solubilize additive elements, especially Ni, a solution treatment temperature of a certain degree or greater is selected according to the Ni concentration. However, if the temperature is too high, the grains sizes become too large, so that the high temperature is not always preferable. In specific, if Ni concentration is high, the temperature is set to be high. As a rough standard, the temperature is set to be approximately 650 to 700° C. in 1.5% by mass of Ni, 800 to 850° C. in 2.5% by mass of Ni, and 900 to 950° C. in 3.5% by mass of Ni. In a more generalized manner, if it is assumed that x the Ni concentration (% by mass) in the ingot, a solution treatment is carried out at a solution treatment temperature, y (° C.) indicated by y=125x+(475 to 525). Therefore, in setting the precipitation state of the large particles and small particles to a scope defined in the invention, it is important to adjust the time and the temperature of the solution treatment such that the grains sizes after the solution treatment is set in the scope of 5 to 30 μm if viewed from the cross section perpendicular to the rolling direction. In addition, if the plate thickness of material at the time of the solution treatment is large, though the plate is cooled after the solution treatment, a sufficient cooling rate may not be obtained, and it is likely that solid-solubilized additive elements precipitate out during the cooling. Accordingly, it is preferable that the plate thickness at the time of performing the solution treatment be equal to or smaller than 0.3 mm. In addition, in order to suppress the precipitation of the additive elements, the average cooling rate of from the solution treatment temperature to 400° C. is preferably 10° C./second or greater, and more preferably 15° C./second or greater. These cooling rates may be achieved by air cooling if the plate thickness is approximately equal to or thinner than 0.3 mm, but water cooling is more preferable. However, if the cooling rate is too high, the shape of the product becomes bad, so that the cooling rate is preferably less than or equal to 30° C./second, and more preferably less than or equal to 20° C./second.
[0077] After the solution treatment, an aging treatment is carried out without performing cold rolling. If the cold rolling is carried out, the dislocation density increases and the precipitation of the precipitates is facilitated, since defects in a parent phase such as grain boundaries, vacancies, and dislocations become a preferential precipitation site. Accordingly, the precipitation is facilitated by performing cold rolling, but the particles precipitated to the grain boundary are large particles as described above, so that the ratio of the precipitates intended in the invention, collapses. Further, recently, it has been known that the grain boundaries formed by the cold rolling are different in characteristics from the grain boundaries after the heat treatment (after the solution treatment). The grain boundaries formed by the cold rolling are mainly configured by dislocation, and it is understood that the energy of the grain boundaries is higher in the grain boundaries by the cold rolling. Accordingly, though it is assumed that the grains after the solution treatment and the grains after the solution treatment and the cold rolling have the same sizes, the particles precipitated in the aging after that are totally different. It is possible to change the characteristics (to change the balance between strength and electrical conductivity) by using these phenomena to intentionally increase large particles, but the overall characteristic (bendability and etching, characteristic) intended by the invention may not be achieved. The decrease of the bending workability may be suppressed depending on the condition of solution treatment (deficient precipitates in the aging due to insufficient solution treatment), but it is difficult to sufficiently draw the function of the materials, since the solution treatment is insufficient. If the cold rolling is carried out between the solution treatment and an aging treatment, strength and electrical conductivity is a little bit high, but the bending workability may decrease and also the precipitates may not be distributed as intended by the invention. Accordingly, in the invention, the cold rolling is not performed after the achievement of the desired grains and the solid solubilization state by she solution treatment.
[0078] In addition, the condition of an aging treatment in the invention is important, it is preferable to control the distribution state of large particles and small particles by a single aging treatment for producing the copper alloy according to the invention. Japanese Patent No. 3797736 employs a method in which large particles and small particles precipitate out by performing an aging treatment twice, but, as generally known in the art, once precipitates precipitate out, Ni and Si concentration that are solid-solubilized in the copper decreases, so Ni and Si hardly diffuses and thus the precipitation becomes difficult. Therefore, the number density of small particles may not be obtained as intended in the invention. In addition, since a second aging treatment influences the size of the precipitation particles previously generated in a first aging treatment, it is difficult to control the particle diameter or the density.
[0079] In order to adjust large particles and small particles to be a desired scope by a single aging treatment, it is a precondition to appropriately perform a solution treatment as a preceding process, but it is important to adjust the temperature and the time to an appropriate scope. The strength and the electrical conductivity are increased by the aging treatment. The aging treatment may be carried out for 0.5 to 50 hours at the temperature of 300 to 600° C., but be carried out for a short time if a heating temperature is high, and be carried out for a long time if the heating temperature is low. This is because the Ni—Si compound particles tend to be coarse if an aging treatment is carried out for a long time at a high temperature, and the Ni—Si compound particles do not sufficiently precipitate out if an aging treatment is carried out for a short time at a low temperature. As a preferred example, an aging treatment may be carried out for approximately an aging time, z (h) indicated by z=−0.115 t+61 if the heating temperature t (° C.) is equal to or higher than 300° C. and lower than 500° C., and for approximately an aging time, z (h) indicated by z=−0.0275 t+17.25 if the heating temperature t (° C.) is equal to or higher than 500° C. and lower than 600° C. For example, it is preferable that an aging treatment be carried out for approximately 15 hours at 400° C. for approximately 2 to 5 hours at 500° C., and for approximately 0.5 to 1 hour at 600° C. In order to obtain higher strength, the cold rolling may be carried out after the aging. In the case of conducting cold rolling after aging, a stress relief annealing (a low temperature annealing) may be carried out after the cold rolling.
[0080] The copper alloy according to the invention may be processed into various wrought copper product, such as a plate, a strip, a pipe, a rod, and a wire, and further the copper alloy according to the invention may be used in an electronic component such as a lead frame, a connector, a pin, a terminal, a relay, a switch, a thin film for a secondary battery, which is required to reconcile high strength and high electrical conductivity (or thermal conductivity).
EXAMPLE
[0081] Hereinafter, specific examples of the invention will be described, but these examples are provided to help better understanding of the invention and its advantages, and are not intended to limit the invention by any means.
[0082] Copper alloys with various component compositions indicated in Tables 1 to 4 were melted in a high frequency melting furnace, were maintained at each melting holding temperature, and were cast into an ingot having a thickness of 30 mm. Thereafter, this ingot was heated at each reheating treatment temperature, then was hot rolled at 850 to 1050° C. for 0.5 to 5 hours (the material temperature at the time of completion of hot rolling was 500° C.) to obtain a plate thickness of 10 mm, and then surface grinding was applied by a thickness of 8 mm in order to remove scale at the surface. Subsequently, after the plate thickness becomes 0.15 mm or 0.10 mm by the cold rolling, solution treatment was earned out under the conditions indicated in Tables 1 to 4. Subsequently, aging treatment was applied under the various conditions indicated in Tables 1 to 4 in an inert atmosphere. In addition, the plate thickness of 0.10 mm was obtained by further cold rolling the plate thickness of 0.15 mm. In this manner, each of the produced specimens with the plate thickness of 0.10 mm was evaluated. Tables 1, 3, and 4 indicate manufacture examples of Cu—Ni—Si copper alloy, and Table 2 indicates a manufacture example of Cu—Ni—Si copper alloy in which Mg, Cr, Sn, Zn, Mn, Co, Fe, and P were appropriately added. In addition, Comparative Examples 9 to 11 were subjected to cold rolling under the condition indicated in Table 3 between solution treatment and aging treatment, respectively.
[0083] Characteristic evaluations were carried out with regard to each of the alloys obtained in this manner, and the results are described in Tables 1 to 4.
[0084] Tensile tests in the direction parallel to the rolling direction were carried out with regard to strength, and tension strength and 0.2% yield strength (MPa) were measured.
[0085] Electrical conductivity (% IACS) was determined by measuring the volume resistivity by a double bridge method.
[0086] As a bendability test, W bending tests in a good way (a direction in which a bending axis is perpendicular to a rolling direction) and a bad way (a direction in which a bending axis is the same direction as a rolling direction) were carried out according to JIS H 3130 to measure an MBR/t value which is a ratio of minimum radius (MBR) with regard to plate thickness (t) in which fractures may not occur.
[0087] After the solution treatment, a cross section in the thickness direction parallel to the rolling direction was cut by a fine cutter, then a cold resin embedding was performed, and then mirror polishing (1 micron buff) treatment was carried out. Subsequently, electrolytic polishing was carried out and grains were observed using a scanning electron microscope (SEM) (trade name: HITACHI-S-4700). With regard to grains sizes, an average value of 10 grains in the width in the processing direction was determined.
[0088] It is possible to measure the grains sizes of a final product by the method described below. First, the cross section in the thickness direction parallel to the rolling direction was subjected to electrolytic polishing, and the sectional structure was observed by SEM, and the number of grains per unit area was counted. In addition, the size of the entire observation field of vision was added up, the resultant was divided by the counted total of the grains, and then the dimension per one grain was calculated. According to the calculated dimension, a diameter of a true circle (a circle-equivalent diameter) with a dimension the same as the calculated dimension may be calculated, and the diameter may be designated as an average grains sizes.
[0089] The particle sizes of large particles and small particles may be observed from any cross sections. In the examples, with regard to the cross section parallel to the rolling, direction of the product, large particles are observed by a scanning electron microscope HITACHI-S-4700), and small particles are observed by a transmission electron microscope (HITACHI-H-9000). In addition, small particles are observed in 10 fields of vision randomly selected from the surface area of the copper alloy of 100 mm 2 if the unit area of 0.5 μm×0.5 μm is set to one field of vision. Large particles are observed in 10 fields of vision randomly selected from the surface area of the copper alloy of 100 mm 2 if the unit area of 20 μm×20 μm is set to one field of vision. In this manner, by observing 10 fields of vision, the test was performed so that approximately 100 particles may be observed, respectively. Photographing was carried out at a magnification ratio of 500 to 700 thousand times if the sizes of the precipitates were 5 to 100 nm, and at a magnification ratio of 50 to 100 thousand times if the sizes of the precipitates were 100 to 5000 nm. However, it is difficult to observe precipitates with the size smaller than 5 nm. It is possible to observe precipitates with the size greater than 5000 nm with a scanning electron microscope.
[0090] With regard to the particles observed in this manner, the dimension was calculated by a long diameter and a short diameter of each particle, the diameter of a true circle (a circle-equivalent diameter) having the same dimension as the calculated dimension was calculated from the calculated dimension, and the calculated diameter was able to be a particle diameter. Particles were classified into large particles and small particles according to the particle sizes, the particle diameters were respectively aggregated with the number of particles, the sum of the particle diameters was divided by the number of particles to obtain an average particle diameter, and the sum of the numbers of the particles was divided by the total dimension of the observation field of vision, so that the number density was obtained. Here, the long diameter refers to the length of the longest line segment among line segments that pass the center of a particle and have intersection points with the border line as both ends, and the short diameter refers to the length of the shortest line segment among line segments that pass the center of a particle and have intersection points with the border line as both ends.
[0091] It was confirmed that the observed particles were Ni—Si compound particles by a method of element mapping with a scanning electron microscope equipped with EDS, especially a field emission electron microscope that is precise in element analysis, and that the small particles were Ni—Si compound particles by a method of element mapping with a transmission electron microscope equipped with EELS.
[0092] However, in final products, the dislocation was significantly high and it was difficult to observe the precipitates. In this case, for the easier observation, it is preferable to perform a stress relief annealing at the temperature of approximately 200° C. at which precipitation was not carried out. In addition, an electrolytic polishing method is used for preparing a sample for a general transmission electron microscope, but the measurement may be carried out by preparing a thin film by FIB (Focused Ion Beam).
[0000]
TABLE 1
Alloy
Cold
Precipitate
Composition
Preparation Condition
Working
Large
Small
First
Melting/
Releasing
Solution
Aging
After
Par-
Par-
Additive
Holding
Treatment
Treatment
Size Ratio of
Condition
Aging (Per-
ticle
ticle
Element
Temper-
Temper-
Temper-
Neigh-
Temper-
formed: ◯,
Diam-
Diam-
(wt %)
ature
ature
ature
boring
ature
Time
Not Per-
eter
eter
Ni
Si
(°C.)
(° C.)
(° C.)
(μm)
Grain
(° C.)
(h)
formed: X)
(nm)
(nm)
Example 1
1.50
0.35
1180
800
750
18
1.6
600
0.5
◯
308
65
Example 2
1.50
0.36
1190
820
750
23
1.4
575
1
◯
553
54
Example 3
1.50
0.32
1200
830
750
15
1.7
550
2
X
354
52
Example 4
1.50
0.37
1200
650
750
23
2.3
525
3
X
794
96
Example 5
1.50
0.32
1210
670
750
22
1.3
500
3
X
663
21
Example 6
1.50
0.32
1200
800
750
15
1.5
450
10
◯
1291
45
Example 7
1.50
0.33
1200
800
750
14
1.6
400
50
X
658
50
Example 8
2.50
0.50
1250
850
800
14
1.1
600
0.5
◯
393
128
Example 9
2.50
0.53
1270
880
800
16
2.5
575
1
X
660
67
Example 10
2.50
0.60
1260
800
800
20
1.4
550
2
X
531
52
Example 11
2.50
0.52
1250
950
850
17
1.6
525
4
◯
595
52
Example 12
2.50
0.56
1280
900
850
14
1.8
500
3
X
850
25
Example 13
2.50
0.56
1250
920
850
15
1.1
475
7
◯
667
42
Example 14
2.50
0.55
1250
810
850
17
1.9
400
20
X
507
23
Example 15
3.50
0.85
1250
900
900
8
1.5
575
1
◯
776
58
Example 16
3.50
0.86
1250
810
900
6
1.3
550
2
X
418
118
Example 17
3.50
0.79
1250
920
900
11
1.5
525
3
X
609
194
Example 18
3.50
0.72
1290
930
950
10
1.5
500
3
◯
658
26
Example 19
3.50
0.74
1290
950
925
3
1.4
475
5
◯
1213
258
Example 20
4.50
1.24
1290
980
925
17
1.7
450
10
◯
676
299
Example 21
5.50
1.32
1300
980
950
18
2.1
425
25
◯
1104
221
Example 22
2.50
0.56
1250
880
850
24
1.1
600
14
◯
775
44
Example 23
2.50
0.54
1250
910
850
25
1.8
580
30
◯
798
52
Maximum
Maximum
Precipitate
Density
Density
Size Ratio
Large
Small
Ratio
Ratio
Evaluation
Between
Particle
Particle
between
between
Elec-
Large
Number
Number
Fields of
Fields of
0.2%
trical
Particle and
Density
Density
Vision of
Vision of
Tension
Yield
conduc-
Bending Workability
Small
(piece/
(piece/
Large
Small
Strength
Strength
tivity
GW
BW
Particle
μm 2 )
μm 2 )
Particle
Particle
(MPa)
(MPa)
(% IACS)
(MBR/t)
(MBR/t)
Example 1
4.7
0.27
5
3.3
1.2
612
606
56
0.0
0.0
Example 2
12.1
0.38
3
1.7
1.0
628
624
52
0.0
0.0
Example 3
68
0.76
469
1.2
1.7
570
555
49
0.0
0.0
Example 4
83
0.19
1033
1.3
1.4
616
594
47
0.0
0.0
Example 5
31.6
0.56
1427
2.5
1.0
631
616
44
0.0
0.0
Example 6
28.7
0.84
19
1.3
1.0
671
659
46
0.2
0.0
Example 7
13.2
0.65
703
1.2
1.9
634
620
47
0.0
0.0
Example 8
3.1
0.06
17
4.4
1.1
775
759
42
1.0
0.7
Example 9
9.9
0.27
1088
3.2
1.1
742
731
45
0.0
0.0
Example 10
10.2
1.41
1024
1.0
1.1
744
731
44
0.2
0.2
Example 11
11.4
0.23
17
3.7
2.1
792
772
43
0.7
0.9
Example 12
34.0
1.33
507
4.6
1.2
778
753
41
0.6
0.6
Example 13
15.9
1.62
58
3.3
2.0
808
796
39
1.0
0.8
Example 14
22.0
0.80
908
2.4
1.0
753
726
42
0.5
0.5
Example 15
13.4
1.15
29
4.3
1.6
924
908
32
1.4
1.2
Example 16
35
1.07
739
3.8
1.2
867
836
34
1.0
1.0
Example 17
31
1.72
1009
3.4
1.1
865
837
34
1.0
1.0
Example 18
25.3
1.80
22
4.1
1.9
907
904
31
1.4
1.2
Example 19
4.7
1.05
14
4.5
4.1
813
890
31
1.4
1.4
Example 20
2.3
0.81
38
2.0
1.6
929
918
28
1.4
1.4
Example 21
5.0
0.65
92
4.0
1.7
932
912
27
1.4
1.4
Example 22
17.6
0.38
50
3.5
3.2
756
721
45
1.0
0.6
Example 23
15.3
0.39
63
3.5
1.5
778
744
46
1.0
0.6
indicates data missing or illegible when filed
[0000]
TABLE 2
Alloy
Cold
Precipitate
Composition
Preparation Condition
Working
Large
First
Melting/
Releasing
Solution
Ratio
Aging
After
Par-
Additive
Second
Holding
Treatment
Treatment
Length of
of length
Condition
Aging (Per-
ticle
Element
Additive
Temper-
Temper-
Temper-
Crystal
of Neigh-
Temper-
formed: ◯,
Diam-
(wt %)
Element
ature
ature
ature
Grain
boring
ature
Time
Not Per-
eter
Ni
Si
(wt %)
(°C.)
(° C.)
(° C.)
(μm)
Grain
(° C.)
(h)
formed: X)
(nm)
Example 24
2.50
0.50
Mg0.1
1250
900
800
18
1.6
525
3
◯
526
Example 25
2.50
0.53
Cr0.1
1250
900
800
23
1.4
525
3
◯
1232
Example 26
2.50
0.60
Mg0.1—Cr0.1
1250
900
800
15
1.7
525
3
X
487
Example 27
2.50
0.52
Sn0.3—Zn0.3
1250
900
800
23
2.3
525
3
X
663
Example 28
2.50
0.57
Mn0.2
1250
900
800
22
1.3
525
3
◯
792
Example 29
2.50
0.55
Cr0.1—Co0.1
1250
900
800
15
1.5
525
3
◯
1132
Example 30
2.50
0.50
Fe0.1—P0.03
1250
900
800
14
1.6
525
3
◯
713
Maximum
Maximum
Precipitate
Density
Density
Small
Size Ratio
Large
Small
Ratio
Ratio
Evaluation
Par-
Between
Particle
Particle
between
between
Elec-
ticle
Large
Number
Number
Fields of
Fields of
0.2%
trical
Diam-
Particle and
Density
Density
Vision of
Vision of
Tension
Yield
conduc-
Bending Workability
eter
Small
(piece/
(piece/
Large
Small
Strength
Strength
tivity
GW
BW
(nm)
Particle
μm 2 )
μm 2 )
Particle
Particle
(MPa)
(MPa)
(% IACS)
(MBR/t)
(MBR/t)
Example 24
27
19.5
0.31
8
1.7
1.1
728
723
45
1.0
0.8
Example 25
53
23.2
0.23
21
2.1
1.5
740
740
44
1.0
0.6
Example 26
94
5.2
0.29
639
1.9
1.2
636
638
45
0.0
0.0
Example 27
63
10.5
0.57
1015
1.6
1.1
725
728
40
0.1
0.0
Example 28
47
16.8
1.62
25
1.6
1.5
736
733
38
0.8
0.6
Example 29
70
16.2
1.77
18
2.6
1.3
798
797
37
0.6
0.6
Example 30
75
8.5
0.83
31
2.4
1.1
768
768
38
0.8
0.9
[0000]
TABLE 3
Alloy
Cold
Precipitate
Composition
Preparation Condition
Working
Large
Small
First
Melting/
Releasing
Solution
Size
Aging
After
Par-
Par-
Additive
Holding
Treatment
Treatment
Size
Ratio of
Condition
Aging (Per-
ticle
ticle
Element
Temper-
Temper-
Temper-
of
Neigh-
Temper-
formed: ◯,
Diam-
Diam-
(wt %)
ature
ature
ature
Grain
boring
ature
Time
Not Per-
eter
eter
Ni
Si
(°C.)
(° C.)
(° C.)
(μm)
Grain
(° C.)
(h)
formed: X)
(nm)
(nm)
Comparative
2.50
2.10
1250
950
Not Examined Because of Breaking during Hot Rolling
Example 1
Comparative
7.00
0.36
1310
950
Not Examined Because of Breaking during Hot Rolling
Example 2
Comparative
2.50
0.54
1260
950
550
3
3.5
525
5
X
3257
38
Example 3
Comparative
2.50
0.54
1260
950
1050
82
4.3
525
3
X
678
52
Example 4
Comparative
2.50
0.54
1260
950
850
22
1.3
550° C., 450° C. ×
X
942
5
Example 5
5 h (twice)
Comparative
2.50
0.54
1260
950
850
16
1.5
700
10
X
458
—
Example 6
Comparative
2.50
0.54
1260
950
850
18
1.7
400
168
◯
—
284
Example 7
Comparative
2.50
0.54
1260
950
800
14
1.1
600
0.0027
◯
—
—
Example 8
Comparative
2.50
0.54
1260
950
800
16
2.5
Rolling Between
X
347
23
Example 9
Solutionizing and Aging
60%
525
5
Comparative
2.50
0.54
1260
950
800
16
2.5
Rolling Between
X
481
41
Example 10
Solutionizing and Aging
30%
525
5
Comparative
2.50
0.54
1260
950
800
16
2.5
Rolling Between
X
568
16
Example 11
Solutionizing and Aging
90%
525
5
Comparative
2.50
0.54
1260
950
800
20
1.4
550
2
◯
334
—
Example 12
Cold Rolling
After Aging
70%
Comparative
2.50
0.50
1150
900
800
21
1.1
475
5
X
5683
59
Example 13
Comparative
2.50
0.50
1350
900
800
16
1.1
600
5
X
4324
49
Example 14
Comparative
2.50
0.50
1260
1000
950
34
1.1
600
5
X
670
78
Example 15
Comparative
2.50
0.50
1260
700
800
8
1.1
600
5
X
2951
55
Example 16
Comparative
2.50
0.50
1260
900
700
6
1.1
600
5
X
3214
51
Example 17
Comparative
2.50
0.50
1260
900
950
48
3.9
600
5
X
812
55
Example 18
Maximum
Maximum
Precipitate
Density
Density
Size Ratio
Large
Small
Ratio
Ratio
Evaluation
Between
Particle
Particle
between
between
Elec-
Large
Number
Number
Fields of
Fields of
0.2%
trical
Particle and
Density
Density
Vision of
Vision of
Tension
Yield
conduc-
Bending Workability
Small
(piece/
(piece/
Large
Small
Strength
Strength
tivity
GW
BW
Particle
μm 2 )
μm 2 )
Particle
Particle
(MPa)
(MPa)
(% IACS)
(MBR/t)
(MBR/t)
Comparative
Not Examined Because of Breaking during Hot Rolling
Example 1
Comparative
Not Examined Because of Breaking during Hot Rolling
Example 2
Comparative
65.7
0.01
4
15.0
2.3
567
843
50
1.0
1.0
Example 3
Comparative
13.0
0.001
1012
1.1
1.2
584
533
48
1.5
1.5
Example 4
Comparative
168.4
0.60
0.4
1.8
8.2
668
631
45
1.0
0.0
Example 5
Comparative
—
0.80
—
1.6
—
642
611
53
1.2
1.0
Example 6
Comparative
—
—
1552
—
1.2
712
554
48
1.1
1.0
Example 7
Comparative
—
—
—
—
—
678
544
35
0.0
0.0
Example 8
Comparative
13.0
2.50
304
1.4
2.3
684
635
51
1.8
1.8
Example 9
Comparative
11.7
2.10
321
1.8
2.1
657
611
49
1.6
1.5
Example 10
Comparative
35.5
2.70
287
1.2
2.5
731
681
52
2.0
2.5
Example 11
Comparative
—
1.28
—
2.1
—
824
781
37
1.2
5.4
Example 12
Comparative
96.3
3.8
354
6.2
1.3
651
631
30
1.5
1.3
Example 13
Comparative
88.2
3.9
389
6.8
1.1
624
591
40
1.6
1.5
Example 14
Comparative
8.6
0.01
618
1.2
1.4
638
601
39
1.2
1.1
Example 15
Comparative
53.7
4.8
289
11
2.5
668
622
37
1.3
1.2
Example 16
Comparative
63.0
2.3
411
9
3.8
670
635
42
1.5
1.3
Example 17
Comparative
14.8
0.4
876
1.4
1.9
634
600
40
1.6
1.4
Example 18
“— represents that particles in this range were not observed”
[0000]
TABLE 4
Alloy
Preparation Condition
Cold
Precipitate
Composition
Ratio
Working
Large
Small
First
Melting/
Releasing
Solution
Thickness
Aging
After
Par-
Par-
Additive
Holding
Treatment
Treatment
Size of
Direction
Condition
Aging (Per-
ticle
ticle
Element
Temper-
Temper-
Temper-
Crystal
of Neigh-
Temper-
formed: ◯,
Diam-
Diam-
(wt%)
ature
ature
ature
Rate
Grain
boring
ature
Time
Not Per-
eter
eter
Ni
Si
(°C.)
(° C.)
(° C.)
(° C.)
(μm)
Grain
(° C.)
(h)
formed: X)
(nm)
(nm)
Example 31
2.50
0.52
1250
900
850
16
22
1.5
525
4
◯
784
87
Example 32
2.50
0.52
1250
900
850
16
22
1.5
525
4
X
656
87
Comparative
2.50
0.52
1250
900
Not
—
38
5.2
525
4
X
2145
64
Example 19
provided
Comparative
2.50
0.52
1250
900
850
5
45
4.3
525
4
X
618
80
Example 20
Example 33
3.50
0.73
1250
950
950
23
15
1.1
525
4
X
551
83
Comparative
3.50
0.73
1250
950
950
8
24
3.8
525
4
X
356
76
Example 21
Precipitate
Maximum
Maximum
Density
Density
Size Ratio
Large
Small
Ratio
Ratio
Evaluation
Par-
Between
Particle
Particle
between
between
Elec-
ticle
Content
Large
Number
Number
Fields of
Fields of
0.2%
trical
Diam-
of
Particle and
Density
Density
Vision of
Vision of
Tension
Yield
conduc-
Bending Workability
eter
Ni—Si
Small
(piece/
(piece/
Large
Small
Strength
Strength
tivity
GW
BW
(nm)
(mass %)
Particle
μm 2 )
μm 2 )
Particle
Particle
(MPa)
(MPa)
(% IACS)
(MBR/t)
(MBR/t)
Example 31
23
89
34.1
13
0.4
3.1
1.2
790
765
45
0.8
1.0
Example 32
35
87
7.8
452
0.1
2.1
1.1
811
793
42
0.9
1.1
Comparative
51
73
42.1
512
6.1
21.0
11.0
745
701
41
1.5
1.2
Example 19
Comparative
58
91
10.7
668
5.2
13.0
2.5
765
725
47
1.6
1.3
Example 20
Example 33
12
85
45.5
312
0.1
4.1
2.0
1023
987
35
0.8
1.0
Comparative
30
83
8.4
806
5.4
16.0
2.7
890
835
38
1.3
1.2
Example 21
indicates data missing or illegible when filed
[0093] It is understood that strength, electrical conductivity and bending workability are well-balanced in the copper alloy corresponding to Examples of the invention indicated in Tables 1 and 2.
[0094] In Comparative Example 1, since Si was not in the scope of the composition, the ratio between Ni and Si was not appropriate, so breaking occurred during hot rolling due to coarse grains.
[0095] In Comparative Example 2, since Ni was not in the scope of the composition, Ni was in an excess state. Therefore, hot workability decreased, and breaking occurred during hot rolling.
[0096] In Comparative Example 3, since a solution treatment temperature was low, coarse particles remained. Therefore, electrical conductivity became high, but strength became low since the number density of small particles decreased. In addition, fracture occurred from a coarse particle as an origination at the time of bending.
[0097] In Comparative Example 4, since the solution treatment temperature is high, grains sizes became large so that large particles decreased while small particles increased. Therefore, strength increased but electrical conductivity decreased. Since grains were large at the time of the solution treatment, bendability decreased by the breaking of grain boundaries at the time of bending.
[0098] Comparative Example 5 corresponds to copper alloy described in Japanese Patent No. 3797736. Since aging was performed twice, the sizes of the small particles precipitated at a second aging were small, and the number density significantly decreased. The ratio between large particles and small particles was appropriate, but the number density of small particles became low, so that strength decreased.
[0099] In Comparative Example 6, since an aging temperature was high, coarse precipitates increased. Therefore, the density of small particles decreased, so that strength decreased. In addition, it was supposed that electrical conductivity became high, but since the aging temperature was high, so that the electrical conductivity decreased by re-solid solubilization. Fracture occurred from a coarse particle as an origination at the time of bending.
[0100] In Comparative Example 7, since aging time was too long, the size of small particles became too large, so that the number density of the small particles became small. Therefore, strength decreased.
[0101] In Comparative Example 8, since aging time was too short, there were no precipitate particles and the strength decreased.
[0102] In Comparative Examples 9 to 11, cold rolling was performed between a solution treatment and aging, and the degrees of working were 60, 30, and 90%, respectively. Therefore, the precipitates of large particles were facilitated, and the numbers of large particles increased. Accordingly, the numbers of small particles decreased. Though electrical conductivity was high, bending workability was bad. In addition, defects such as bad plating occurred.
[0103] In Comparative Example 12, the degree of working of cold rolling after aging was high. In addition, strength was high, but electrical conductivity was low, and the largest characteristic was bad bending workability in a bad way.
[0104] In Comparative Example 13, since a melting/holding temperature was too low, the size of large particles became large, and the ratio of an average particle size of large particles to small particles became large, so that strength decreased.
[0105] In Comparative Example 14, since a melting/holding temperature was too high, the size of large particles became large, and the ratio of an average particle size of large particles to small particles became large, so that strength decreased.
[0106] In Comparative Example 15, since a temperature of the reheating treatment was too high, grains became too large. Accordingly, the balance between large particles and small particles collapsed. Since the grains became coarse, the number of large particles decreased. Since the grains were coarse, strength was low and also electrical conductivity significantly decreased.
[0107] In Comparative Example 16, a reheating treatment temperature was too low, the size of large particles became large, and a ratio of an average particle size of large particles to small particles became large, so that strength decreased.
[0108] In Comparative Example 17, since a solution treatment temperature was low, the size of large particles became large, and a ratio of an average particle size of large particles to small particles became large, so that strength decreased.
[0109] In Comparative Example 18, a temperature of a solution treatment was high, and grains became coarse. Ni and Si were sufficiently solid-solubilized by solution treatment, but balance of precipitates of large particles and small particles collapsed due to coarse grains.
[0110] Comparative Example 19 corresponds to copper alloy described in International Publication No. 2008/032738. Since a melting/holding temperature and a temperature of reheating treatment remained constant without appropriately changing the temperatures according to Ni concentration, and further a solution treatment after hot rolling was not performed, sizes of large particles became large and bending workability was bad.
[0111] In Comparative Example 20, a cooling rate after a solution treatment was slow and precipitation was carried out during cooling, so that grains became coarse. Therefore, particles that had previously precipitated out became coarse particles during aging treatment. Accordingly, bending fractures occurred due to large particles.
[0112] In Comparative Example 21, a cooling rate after a solution treatment was slow, and precipitation way carried out during cooling. Especially, since Ni concentration was high, and flux pinning of precipitates occurred at the same time, grains became uneven.
|
The distribution of Ni—Si compound grains is controlled to thereby improve the properties of Corson alloys. The copper alloy for electronic materials comprises 0.4 to 6.0% mass of Ni and 0.1 to 1.4% by mass of Si, with the balance being Cu and unavoidable impurities.
The copper alloy comprising:
small particles of Ni—Si compound having a particle size of equal to or greater than 0.01 μm and smaller than 0.3 μm; and large particles of Ni—Si compound having a particle size of equal to of greater than 0.3 μm and smaller than 1.5 μm.
The number density of the small particles is 1 to 2000 pieces/μm 2 and the number density of the large particles is 0.05 to 2 pieces/μm 2 .
| 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains generally to systems for sensing or indicating an abnormal condition of a vehicular tire and is more particularly directed to such systems using radio frequency transmissions for signaling.
2. Description of the Prior Art
In the prior art numerous devices and apparatus have been suggested for sensing or indicating an abnormal condition in a vehicular tire. These include low pressure devices that indicate underinflation and minimum pressure devices that indicate a substantially complete loss of air or a flat.
One method of sensing an abnormal tire condition has been to provide a fluid pressure sensitive switch inside the tire and attached to either the wheel rim or tire sidewall. As the abnormal condition, such as a drop or loss of fluid pressure, develops the switch will operate to provide a warning signal. This warning signal can subsequently be communicated to a receiver monitor close to the operator of the vehicle to alert him of the condition.
Problems incurred with the fluid pressure sensitive switches are numerous in that they are mechanical and need adjustment and are not as reliable as one may prefer. For example, the opening communicating the air pressure to the device may become clogged or the spring actuator may become rusted because of moisture entering the device. The fluid pressure sensitive switch is not rugged enough to provide totally reliable service in the exposed locations that vehicle tires must operate in.
This is especially true for those fluid pressure devices which attach to the valve stems of the vehicle where no protection whatsoever is afforded. Another problem inherent with the valve stem operated pressure sensitive device is the provision of an additional place from which to leak air. Thus, they may contribute to the very condition the apparatus was attached to warn against.
The signals from the pressure operated switches have, in the past, been communicated to a centrally located monitor by either radio wave or contacting wires. If contacting wires are used, the problem of transmitting a signal from a rotating device presents itself. This has been accomplished laboriously in the past with slip rings or the like. On the other hand and if radio waves are used, there are the difficulties of powering the transmitter and not interferring with other communication facilities that may be nearby. Many of the transmitter indicators include batteries that have a limited operational cycle and require replacement at certain intervals.
A further problem having to do with previous indicators is that they are not particularly well adapted to the recent developments concerning "run-flat" tires. The new run-flat tires generally provide a small inner insert having a load bearing surface on which a vehicle may be driven for a reasonable time and speed while the tire is deflated. The new "run-flat" designs therefore, eliminate the need for spare vehicle tires but increase the difficulty of determining when a tire has lost its pressure.
It would be advantageous to provide a deflated tire condition indicating apparatus overcoming the problems faced in the prior art and which could also be easily integrated with a "run-flat" insert.
SUMMARY OF THE INVENTION
The invention provides a self-contained and self powered abnormal tire condition sensing system for a tire. The tire condition sensing system comprises a transmitting assembly with an energy generating transducer for powering a wheel module circuit that transmits a radio frequency abnormal condition signal to a receiver located in proximity to the operator of the vehicle. The radio frequency transmission eliminates the need for a direct physical connection between the transmitting assembly and receiver, thereby solving the problem of communicating information from a revolving source, i.e., a tire. Further, the reliability of the system is enhanced as the unit is mounted within the tire insert and has no external connections to the harsh external environment a tire must operate in. Another advantage of the system is that modification of the tire, wheel, or chassis is unnecessary. The system is installed when the "run-flat" insert is mounted on the wheel and the receiver is placed within the operator compartment.
The transducer converts the mechanical compression of the tire insert caused by a deflated tire condition into electrical energy. This production of energy, which is an indication of the deflated tire condition, eliminates the need for an external or peripheral power source such as a battery. The system thus obviates the problem of servicing the transmitting assembly to replace parts with a limited shelf life. Additionally, false signals are eliminated as the system will not communicate with the receiver unless an abnormal condition exists to generate the energy needed to produce the signal.
A charge storage release circuit included in the transmitting assembly of the invention produces a pulsed abnormal condition signal. The charge storage portion of the circuit stores the electrical energy produced by the transducer until a predetermined quantity of power is stored. The release portion of the circuit then operates to power the wheel module circuit to transmit for a short length of time. This intermittent operation allows a smaller transducer to be used and causes less hindrance to surrounding communication facilities than would a continuous operation.
Therefore, it is a general object of the invention to provide an improved abnormal tire condition indicating system.
It is another object of the invention to provide an abnormal tire condition indicating system which is easily integrated into a wide variety of wheel assemblies including those which have a "run-flat" insert.
It is an additional object of the invention to provide a radio frequency abnormal tire condition indicating system.
Still further, it is an object of the invention to provide a radio frequency signaling system with an intermittent operation.
These and other objects, features, and advantages of the invention will be more fully understood and appreciated upon reference to the following detailed description taken in conjunction with the appended drawings wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a pictorial schematic in partial cross-section of a vehicle incorporating an abnormal tire condition indicating system constructed in accordance with the invention;
FIG. 2 is a pictorial elevational view in partial cross-section of a vehicular wheel having a transmitting assembly for the system of FIG. 1;
FIG. 3 is an enlarged fragmented elevational view in cross section of the transmitting assembly of FIG. 2;
FIG. 4 is a system block diagram for the electronic portion of the transmitting assembly illustrated in FIG. 3; and
FIG. 5 is a detailed schematic view of the electronic portion of the transmitting assembly illustrated in FIG. 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to FIG. 1, there is shown a vehicle having a plurality of pneumatic tires 10 that are inflatable with a fluid such as air. The tires 10 are generally mounted on wheel assemblies 12 which support a chassis structure 14 that is illustrated in phantom in the drawing.
Associated with each tire 10 is a transmitting assembly 30 that is self contained, in the embodiment shown, within a "run-flat" insert 26 of each tire. However, assembly 30 is equally adaptable to use in more conventional tire and wheel assemblies as will be readily appreciated by those skilled in the art. Each transmitting assembly 30 utilizes a radio frequency transmission to communicate with a receiving antenna 18 and a receiver 16. The receiver is adapted to decode the transmissions of the transmitting assemblies 30 and to provide a warning, either audible or visible, to the operator of the vehicle that an abnormal condition, deflation of a tire, has occurred. The invention provides this warning without using connecting wires or cables that are difficult and expensive to install.
The receiver may be of conventional design including amplifiers and frequency selective circuitry. It is possible in some instances to use the vehicle's radio antenna for the receiving antenna 18 or an external antenna of suitable design may be employed.
It should also be understood that the utility of the device should not be confined to a passenger vehicle as shown in FIG. 1 but is applicable to the other uses of pneumatic tires including trucks, buses, airplanes, and the like.
FIG. 2 illustrates the mounting of the transmitting assembly within the tire 10. There illustrated in cross-section is the tire casing 20 and a "run-flat" insert 26 of generally smaller but similar shape to the casing 20 mounted upon a wheel rim 22. The "run-flat" insert 26 allows the vehicle to be driven without serious handicaps to safety or equipment on a load bearing surface 24 for a reasonable distance and time. When the tire 10 becomes deflated and the vehicle is being supported on the load bearing surface 24, the transmitting assembly 30, mounted between the surface 24 and the wheel rim 22, will signal the receiver 16 of the fact via transmitting antenna 28. The transmitting antenna 28 preferably is a submultiple of the wavelength of the transmitting frequency, i.e., 1/4, 1/2 wavelength and follows the contour of the insert. The transmitting assembly 30 and antenna 28 are shown molded integrally with the insert 26. This protects the assembly 30 and antenna 28 from the exposure to road contaminants and other hazards.
The mounting of the transmitting assembly 30 is shown to better advantage in an enlarged fragmentary view in FIG. 3. The size of the transmitting assembly in relation to the insert has been exaggerated to clearly indicate its operation. The transmitting assembly 30 comprises an energy producing transducer generally designated 50 having a circular wafer of piezoelectric ceramic material 42 bonded to a metallic disk 44. When the transducer is flexed or deformed a voltage is generated between the wafer 42 and disk 44. Preferably, transducer 50 is comprised of a commercially available piezoelectric generator. As the specifics of this generator do not themselves form a part of the present invention, further elaboration thereon is deemed unnecessary. Additionally, associated with the transducer 50 is an elastomeric button 40 which is formed from some durable rubber material or the like.
The transmitting assembly 30 further comprises a generally cylindrical mounting member 34 that fits into a molded cylindrical cavity 32 of the insert 26 and is held in position by a key 36. Preferably the cavity 32 is formed with a slight taper to allow easy molding and insertion of the transmitting assembly. The mounting member may be formed of metal or plastic of a light weight to lessen any tire imbalance.
The elastomeric button 40, piezoelectric wafer 42, and metallic disk 44 form a combination which rests on the bottom of cavity 32 and also slides partially into a recessed portion 45 and rests on a shoulder 48 of the mounting member 34. The recessed portion 45 is shaped to allow the wafer and disk to deform but not beyond their elastic limit. A curved portion 49 of the recess limits movement of the combination so maximum voltage may be generated without producing a destructive flexure of the combination. The transducer may then produce a voltage of approximately 80 volts from a flexure in the order of 0.015 inches. The duration of the energy generated is determined by the speed of the vehicle during the operation of the circuit but is on the order of millisec pulses with a positive and a negative polarity.
The mounting member 34 further includes a cylindrical chamber 47 which contains a wheel module circuit 46. The wheel module circuit contains the transmitting circuitry necessary to generate an abnormal condition signal to the receiver 16 and may be electrically interconnected with the transducer 50 by appropriate lead wires. It is seen that the transmitting assembly is entirely self-contained and takes a minimal amount of space. The portion of cavity 32 which is not filled by the transmitting assembly 30 is occupied by a filler plug 38 which allows the button 40 to remain in contact with the bottom of the cavity 32.
When an abnormal condition occurs and the operator is driving on a deflated or overloaded tire where the tire profile deflection is greater than an acceptable maximum deflection when supporting a vehicle, the load bearing surface 24 of the "run-flat" insert 26 will be carrying the weight of the vehicle. As the wheel rim 22 revolves and the portion of the insert 26 containing the transmitting assembly 30 is compressed, the button 40 will deform the wafer 42 and disk 44. This deformation will cause a voltage to be generated to the wheel module circuit that is one polarity while the transducer 50 is deformed and the opposite as it is released. The energy is generated for every revolution of the insert 26 and used to power the transmitting circuitry.
The wheel module circuitry 46 is further illustrated in FIG. 4 and comprises a rectifier 52, a charge storage release circuit 54, a modulator 56, and a transmitter 58.
The energy produced by the transducer 50 is rectified by the rectifier 52 and stored in the charge storage portion of the circuit 54. When sufficient charge or power has accumulated to power the modulator 56 and transmitter 58, the release portion of the circuit 54 turns the power on. The abnormal tire indication transmission then takes place via antenna 28 until the stored energy in circuit 54 has been used. The cycle is repeated at periodic intervals as additional revolutions of the wheel rim 22 cause additional voltage pulses to be generated by transducer 50 to thereby provide more energy for charging storage release circuit 54. This intermittent activity is advantageous in that it is not as disruptive to other communications as a solid or continuous signal would be and as mentioned above significantly eliminates false signaling.
With attention directed to the more detailed schematic of FIG. 5, there is illustrated the transducer 50 connected to the rectifier 52 comprising diodes 60,62,64, and 66 that form a full wave bridge. The full wave bridge configuration is to take advantage of the full voltage energy output by the transducer including its positive and negative peaks. The energy pulses from the rotation of the wheel are thusly converted into pulses of direct current that are stored in a capacitor 74 which is connected to the rectifier 52 through a diode 68. The capacitor 74 which is the charge storage portion of the charge storage-release circuit 54 will continually increase in voltage to a point where enough energy has been stored to operate the modulator 56 and the transmitter 58. To provide for a milliwatt output of the transmitter the capacitor is in the range of 12 volts and 50 μ fd. in capacity. It is understood if more or less power is to be stored the values will change accordingly.
The voltage on the capacitor 74 is continually monitored by the release portion of the charge storage release circuit 54 which comprises a switching device 72 preferably a SCR or the like, a diode 68, and a triggering device preferably a zener diode 70 or the like. In operation the zener diode 70 will remain non conductive until the capacitor 74 exceeds the reverse breakdown voltage characteristic of the zener diode. At that time the zener diode 70 will conduct and transmit a trigger signal to the gate of the switching device, SCR 72, to turn the device on. The operation of the SCR will supply power from the capacitor 74 to the modulator 56 and the transmitter 58 via the cathode of the SCR along power supply line 79.
A transmission will continue until the voltage on the capacitor 74 drops sufficiently to turn the SCR 72 off and begin the charging cycle once again.
The modulator 56 can encompass any circuitry for generating a characteristic modulation tone and is shown preferably to comprise a astable multivibrator with the collector of a NPN transistor 82 connected to a load resistor 76. The load resistor 76 is connected to the power line 79 at its other terminal. Likewise a second half of the multivibrator comprises NPN transistor 90 having a collector connection to a load resistor 86 which is connected at the opposite terminal to the power line 79.
The transistors 82,90 each have an associated timing circuit comprising a resistor 84, a capacitor 88 and a resistor 78, a capacitor 80, respectively, connected to their base terminals. The frequency of the modulation tone is determined by the RC time constants of these two circuits and can be different for individual tires.
The modulation signal is capacitively coupled to the transmitter 58 by a capacitor 92 connected at one terminal to the collector of transistor 90 and at the other to the base of transistor 97.
The transmitter 58 comprises a radio frequency type oscillator for generating a carrier suitable for frequency modulation. Preferably the oscillator is comprised of NPN transistor 97 having a tank circuit with inductor 102 and a capacitor 100 connected to the collector of the transistor 97. The antenna is connected to the inductor 102 at a tap. The tank circuit determines the carrier frequency of the transmitter. A resistor 96 connected between the base of transistor 97 and ground assists in biasing the oscillator. A capacitor 104 further provides a feedback loop for the oscillator and is connected between the emitter and collector of the transistor 97. A resistor 106 is connected between the emitter of transistor 97 and ground.
A voltage divider including a resistor 94 connected between power supply line 79 and one terminal of a resistor 96, which is connected to ground at the other, provides the biasing network for the base of the transistor 97 and is connected to the center point of the divider. A capacitor 98 is additionally connected between the center point of the divider and ground for the purpose of filtering.
The transmitter is designed to produce a milliwatts output in the radio frequency band which can be in the 50-100 Megahertz range. The transmitting distance should be kept within 50 feet to insure that interference will be kept to a minimum.
While the preferred embodiment of the invention have been disclosed with reference to a "run-flat" type of tire, it will be understood that various modifications obvious to one skilled in the art can be made thereto without departing from the spirit and scope of the invention as covered by the appended claims. For example, transmitting assembly 30 could be mounted within the tire by any number of convenient means for use in more conventional tires and wheel assemblies which do not include the "run-flat" insert. In such alternative arrangements, transducer 50 would be activated by an abnormal condition where the profile deflection is greater than an acceptable maximum amount due to tire under inflation, overloading or the like. Operation of the subject new system would then be the same as described in detail hereinabove.
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A self powered tire condition indicator system is disclosed. The system comprises a plurality of wheel mounted transmitting assemblies which communicate by a radio frequency transmission to a receiver located within the operator compartment of a vehicle. Each of the transmitting assemblies generates its own transmitting power by converting the mechanical compression of a flat tire into electrical energy. The electrical energy is used to generate an intermittent characteristic tone associated with a deflated tire condition by the frequency modulation of a carrier.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority benefit of Taiwan application serial no. 91102579, filed Feb. 15, 2002.
BACKGROUND OF THE INVENTION
[0002] 1. Field of Invention
[0003] The present invention relates to a semiconductor transport device. More particularly, the present invention relates to a vacuum suction memory for holding a silicon wafer.
[0004] 2. Description of Related Art
[0005] Wafer transport systems use a variety of mechanisms for transport, the most common and widely used method of which is creating a vacuum to suck up a silicon wafer. The vacuum suction method is used, for example, in a chemical-mechanical polishing device to hold a silicon wafer.
[0006] [0006]FIG. 1 is simplified and localized cross-sectional view of a conventional chemical-mechanical polishing device. As shown in FIG. 1, the chemical-mechanical polishing device includes a polishing head 100 and a polishing table 110 . A polishing pad 120 covers the polishing table 110 . The polishing head 100 further includes a gripping pan 102 having an elastic membrane 106 therein. When the polishing head 100 presses upon a silicon wafer 108 , the downward pressure produced by the polishing head 100 on the wafer 108 is evenly spread out so that the wafer 108 can be polished smoothly.
[0007] However, at the end of a chemical-mechanical polishing operation, an external robotic arm is often used to unload the wafer 108 from the polishing table 110 and then transfer the wafer 108 elsewhere. To smooth the process and reduce operating cost, the polishing head 100 often incorporates a vacuum system. In other words, the gripping pan 102 structure is frequently modified to include a set of internal gaseous pipelines. In addition, a multiple-hole panel is inserted between the gripping pan 102 and the membrane 106 such that the membrane 106 also encloses the bottom section of the multiple-hole panel. After a chemical-mechanical polishing operation, a vacuum system may be triggered to create a vacuum state inside the polishing head 100 through the set of internal gaseous pipelines. Hence, the membrane 106 originally pressed against the wafer 108 now attaches to the wafer 108 through suction. Thereafter, the polishing head 100 may move to carry the wafer 108 away. On releasing the vacuum inside the polishing head 100 , suction between the membrane 106 and the wafer 108 disappears and the wafer 108 drops off from the polishing head 100 .
[0008] [0008]FIG. 2 is a schematic top view of a conventional multiple-hole panel inside a vacuum-suction polishing head. As shown in FIG. 2, the multiple-hole panel 200 has a shape that corresponds to a silicon wafer. Hence, the multiple-hole panel 200 is circular and contains a number of holes 202 . At the end of a polishing operation, the polishing head is turned into a vacuum state. Through differential pressure acting via the holes 202 , the elastic membrane 106 contracts into the hole 202 resulting in a suction pressure on the wafer.
[0009] However, the conventional technique has some drawbacks in real applications. The polishing head must return to normal pressure after a polishing operation so that the wafer attached to the membrane can drop off. Due to considerable suction between the membrane and the wafer, the wafer may not unload normally. In other words, the wafer is still attached to the membrane after the polishing head has returned to a normal pressure. Eventually, the wafer may be damaged due to subsequent mishandling.
[0010] In addition, because there is no membrane between the multiple-hole panel for sucking up the wafer and the wafer, the process of creating a suction vacuum also carries some micro-particles from the surrounding atmosphere towards the wafer leading to wafer contamination.
SUMMARY OF THE INVENTION
[0011] Accordingly, one object of the present invention is to provide a membrane for vacuum suction of a silicon wafer such that excessive suction pressure between the membrane and the wafer that may lead to unloading failure is prevented.
[0012] A second object of this invention is to provide a membrane for vacuum suction of a silicon wafer such that time and labor for processing unloading failure is reduced.
[0013] A third object of this invention is to provide a membrane for vacuum suction of a silicon wafer such that contamination of the wafer is prevented.
[0014] To achieve these and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, the invention provides a device having a membrane therein typically incorporated into a polishing head for sucking up a silicon wafer. The device includes a flat main body and a plurality of minute protrusions such as micro-particles on the surface of the flat main body. The minute protrusions are positioned over corresponding holes of a polishing head suction panel.
[0015] The minute protrusions on the vacuum suction membrane according to this invention are able to reduce suction pressure between the wafer and the membrane after the removal of suction. Hence, the design is able to minimize wafer damage due to unloading failure.
[0016] The membrane for vacuum suction of a silicon wafer according to this invention is quite effective in unloading a wafer. Thus, time and labor required to process failure in wafer unloading is minimized and yield of the wafer is increased.
[0017] Furthermore, the provision of a membrane between the wafer suction panel and the wafer cuts off all deposition of contaminant particles from surrounding air in the process of creating a vacuum.
[0018] It is to be understood that both the foregoing general description and the following detailed description are exemplary, and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings,
[0020] [0020]FIG. 1 is simplified and localized cross-sectional view of a conventional chemical-mechanical polishing device;
[0021] [0021]FIG. 2 is a schematic top view of a conventional multiple-hole panel inside a vacuum suction polishing head;
[0022] [0022]FIG. 3A is a schematic cross-sectional view of a multiple-hole panel and a membrane that encloses the bottom section of the multiple-hole panel according to one preferred embodiment of this invention;
[0023] [0023]FIG. 3B is a schematic cross-sectional view showing the configuration of the system in FIG. 3A after creating a suction pressure; and
[0024] [0024]FIG. 4 is a local magnification of a portion IV shown in FIG. 3B.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.
[0026] This invention provides a membrane for vacuum suction of silicon wafers that can be incorporated with a chemical-mechanical polishing device. The membrane serves as a film for enclosing a multiple-hole panel inside a polishing head. However, the membrane can also be applied to various other vacuum suction devices for transferring or holding wafers.
[0027] The chemical-mechanical polishing device used as an example in the description includes a polishing head and a polishing table. The polishing head is connected to a vacuum system. The polishing head further includes a gripping pan for stationing a wafer. Details inside the gripping panel are shown in FIGS. 3A, 3B and 4 .
[0028] [0028]FIG. 3A is a schematic cross-sectional view of a multiple-hole panel and a membrane that encloses the bottom section of the multiple-hole panel according to one preferred embodiment of this invention. As shown in FIG. 3A, inside the gripping panel (not shown in the figure) of the polishing head is a multiple-hole panel 300 having a plurality of holes 302 therein. A membrane 304 fabricated according to this invention wraps around the bottom section of the multiple-hole panel 300 . The membrane 304 includes a flat main body 305 and a plurality of minute spiny protrusions 306 on the surface of the flat main body 305 . Both the flat main body 305 and the spiny protrusions 306 are made from an identical material. The spiny protrusions 306 may have a particle shape, for example. The protrusions 306 are positioned on the membrane 304 over corresponding holes 302 of the multiple-hole panel 300 , for example. For a membrane having a diameter of about 300 mm, each protrusion 306 has a diameter of about 2 mm and a height of about 2 mm. However, the protrusions 306 may have other shapes, dimensions or density on the membrane in order to produce a device having an optimal wafer suction/unloading capability. For example, the quantity of protrusions 306 on the membrane 304 may vary according to the size of holes 302 in the multiple-hole panel 300 . In other words, total quantity of protrusions in an area over a larger hole may be greater than total quantity of protrusions in an area over a smaller hole.
[0029] When the polishing head is conducting a polishing operation, the multiple-hole panel 300 presses downward against the wafer. At the end of the polishing operation, the vacuum system is triggered to turn the interior of the polishing head into a vacuum state so that the polishing head can be used as a tool for moving the wafer elsewhere. How the vacuum system of this invention is able to suck up a wafer is explained in greater detail with reference to FIG. 3B.
[0030] [0030]FIG. 3B is a schematic cross-sectional view showing the configuration of the system in FIG. 3A after creating a suction pressure. As shown in FIG. 3B, air within the polishing head is evacuated in step 308 to create a partial vacuum so that the multiple-hole panel 300 has a pressure differential between the interior and the exterior. Consequently, the portion of membrane 304 positioned directly over the holes 302 cave upward towards the upper section of the multiple-hole panel 300 . Originally, the membrane 304 is pressed tightly against the wafer, but now the membrane 304 attaches to the wafer through suction. Because the membrane 304 has a plurality of minute protrusions 306 on the surface, suction pressure between the membrane 304 and the wafer is slightly lowered when the wafer is attached. Details of how the membrane 304 functions over the hole 302 are further explained using FIG. 4.
[0031] [0031]FIG. 4 is a local magnification of a portion IV shown in FIG. 3B. When a vacuum state is created inside the polishing head, the membrane region over the holes 304 caves upward towards the upper section of the multiple-hole panel 300 . Thus, the membrane 304 around the holes produces an upward suction.
[0032] A comparison between the membrane of this invention and a conventional design can be made here. In a conventional design, a suction-like counteraction is often created trying to remove the downward pressure on the wafer during the polishing operation. Thus, the counteraction provides a suction force between the membrane and the wafer even before a vacuum suction is created. Hence, when the wafer is carried under vacuum suction, the suction between the wafer and the membrane at the bottom section of the multiple-hole panel exceeds the desired suction considerably. Such an excessive suction often results in a failure to unload the wafer from the polishing head even when the vacuum state is canceled. The failure of disengagement between the polishing head and the wafer may lead to defective polishing when the wafer undergoes a float polishing operation inside a float polisher, for example.
[0033] On the contrary, the membrane fabricated according to this invention has protrusions around the holes of the multiple-hole panel. Since the protrusions cancel most of the suction due to counteraction after removing the pressure on the wafer, there is no excess counteraction before the creation of a vacuum suction between the wafer and the membrane. Once the vacuum state in the polishing head is relieved, suction between the wafer and the membrane immediately disappears and the wafer unloads from the membrane smoothly. Consequently, the probability of wafer unloading failure is greatly reduced.
[0034] In addition, if this invention is applied to other vacuum suction transport or wafer holding systems, the presence of a membrane between the multiple-hold panel and the wafer prevents any deposition of contaminants on the wafer when the vacuum is created.
[0035] It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.
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A membrane for vacuum suction of a silicon water typically used inside a polishing head. The membrane has a flat main body and a plurality of protrusions each having a particle-like profile over the surface of the flat main body. The protrusions are formed in positions that correspond to the holes of a supporting multiple-hole panel. The protrusions on the flat main body lower the suction pressure between the wafer and the membrane somewhat so that wafer unloading failure is minimized.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of the present invention relates to a door latch for an electrical equipment enclosure generally, and more particularly to a door latch which can prevent the door of an electrical equipment enclosure from being forced open during a short circuit over current condition without requiring bolts within the latch, of which the following is a specification, reference being had to the drawings accompanying and forming a part of the same.
2. Description of the Related Art
In conventional electrical distribution and control systems, electrical switching devices are often enclosed in a housing having an openable cover or door. Conventional electrical equipment enclosures such as those containing, for example, a motor starter, electric switch, or circuit breaker require durable latches to prevent the enclosure door from blowing open under the arc gas pressure generated upon occurrence of a short-circuit overcurrent condition within any of the enclosed electric equipment.
In FIG. 1 , a conventional switch device enclosure 100 is having a switching device (not shown), such as a circuit breaker or switch installed therein. A hinged cover or door 104 is openable via at least one hinge 133 to provide access to the interior of enclosure 100 . When closed, the door 104 prevents direct operative access to the enclosed switch (not shown). An operating handle 102 mounted external to the enclosure 100 and movable in the directions indicated by arrow 119 is configured to drive a mechanism (not shown), which in turn acts to toggle the switch (not shown) from a power ON position to a power OFF position. Labels having text such as “ON” and “OFF”, are positioned on enclosure 100 to correspond to operating handle 102 positions that likewise correspond to, and thus indicate, the state of the enclosed switch (not shown). The door 104 is retained in a closed position by at least one releasable door-latching mechanism 128 ( FIG. 2A ) having a releasable pawl or latch member 108 ( FIG. 2A ) comprising a tab 118 extending therefrom.
Referring to FIG. 2A , a cut-away side view of the interior of the enclosure of FIG. 1 is shown in the vicinity of the latch mechanism 128 . A conventional latch member 108 is rotatably mounted to enclosure 100 by a rivet or pin 138 which provides an axis of rotation A 1 for latch 108 . A center line C L1 through the center axis of rotation pin 138 and generally orthogonal to the surface of door 104 is shown in FIG. 2A for reference. Latch member 108 comprises a tab 118 having a latching surface 119 configured to latchably cooperate with a latching portion 134 the outer surface of door 104 . When enclosure door 104 is closed, an aperture or slot 114 disposed in the door 104 is configured to allow tab 118 to protrude through to the exterior of enclosure 100 . To secure the door 104 in a closed position, a bias spring 120 is anchored between latch member 108 and enclosure 100 and disposed to apply a bias force F 1 in a first latching direction D 1 to maintain at least a portion of latching surface 119 proximal to a latching portion 134 of the outer surface of door 104 . Generally, a small air gap 137 is provided between latching surface 119 and latching portion 134 . The latching portion 134 of the outer surface of door 104 is conventionally disposed, with respect to the centerline C L1 of the axis of rotation A 1 , in first latching direction D 1 . In this way, the latching surface 119 of tab 118 interferes with the surface of door 104 to prevent inadvertant opening of door 104 .
To allow the door 104 to open, the latch member 108 is unlatched by manually applying a force F 2 to latch member 108 in a second de-latching direction D 2 generally opposite to the first latching direction D 1 , sufficient to cause latch member 108 to rotate in a second de-latching direction D 2 around the axis of rotation A 1 and allow tab 118 to pass through slot 114 .
Latch member 108 is provided with an aperture 112 configured to receive a locking member (not shown) such as the hasp of a lock (not shown) for locking the cover 104 closed.
As shown in FIG. 2B , in the event of a high-pressure condition in enclosure 100 , for example, if the switching device (not shown) in the enclosure 100 experiences a short circuit fault, a relatively high instantaneous pressure is generated inside the enclosure 100 . Under such a high internal pressure, a resultant expansive force vector F e is applied generally orthogonal to the enclosure door 104 which causes the door 104 to deflect or move in an outward direction. The door 104 , at latching portion 134 , in turn contacts the latching surface 119 of tab 118 , thus applying the expansive force vector F e to tab 118 . The latching surface 119 of tab 118 is conventionally configured to create a moment arm of length R 1 in the first latching direction D 1 , between the centerline C L1 of the axis of rotation A 1 and the latching surface 119 of tab 118 . It will be appreciated that, in the event of a high expansive force F e applied to the latching surface 119 in a direction generally orthogonal to the interior of enclosure door 104 , a rotational force, or torque, T R1 , is developed in a second de-latching direction D 2 , is applied to latch member 108 having a magnitude that is the product of the expansive force F e and moment arm R 1 , such that T R1 =F e ×R 1 . The rotational force T R1 biases the latch 108 in the second de-latching direction D 2 , and, if of sufficient magnitude, for example greater than the force applied by bias spring 120 , results in the rotation of latch 108 .
As shown in FIG. 2C , and as discussed above, in the event of a high-pressure condition in enclosure 100 , the conventional latch 108 may unlatch or move out of position, and allow the door 104 to open, thus releasing hot gasses and debris.
BRIEF SUMMARY OF THE INVENTION
In view of the foregoing, there is a need to provide a durable latch that is relatively simple in construction, using a minimum number of parts that prevents the enclosure door from opening during a short circuit fault. It would be desirable to provide a simple latch for an electrical equipment enclosure that increases the latching force exerted on the door in the event of a short circuit fault.
In an embodiment, an enclosure for mounting a switching device. The enclosure comprises a simple latch assembly that is configured to prevent opening of the enclosure in the event of high pressure conditions inside the enclosure.
In another embodiment, a latch for an enclosure having a door is provided. The latch comprises a moveable member operable in response to high pressure conditions inside the enclosure, and configured to prevent opening of the enclosure in the event of high pressure conditions inside the enclosure.
Other features and advantages of the disclosure will become apparent by reference to the following description taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Although specific features of the invention are shown in some drawings and not in others, this is for convenience only as one or more of the features of any drawing may be combined with any or all of the other features of one or more of the remaining drawings in accordance with one or more embodiments of the invention.
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate a presently preferred embodiment of the invention, in which:
FIG. 1 illustrates a perspective view of a prior art enclosure having a door secured by a conventional latch;
FIG. 2A illustrates a side view of the prior art latch of FIG. 1 under a low-pressure condition;
FIG. 2B illustrates the forces applied to the prior art latch of FIG. 2A under a high-pressure condition;
FIG. 2C illustrates the prior art latch of FIG. 2B in an unlatched state;
FIG. 3 illustrates a perspective view of an embodiment of an enclosure of the present invention;
FIG. 4A illustrates a side view of an embodiment under a low-pressure condition;
FIG. 4B illustrates the forces applied to the embodiment of FIG. 4A under a high-pressure condition; and
FIG. 4C illustrates embodiment of FIG. 4B in a fully latched state under the high-pressure condition of FIG. 4B .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As used herein, an element or function recited in the singular and proceeded with the word “a” or “an” should be understood as not excluding plural said elements or functions, unless such exclusion is explicitly recited. Furthermore, references to “one embodiment” of the claimed invention should not be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.
In FIG. 3 , a housing 300 configured to enclose a conventional switching device such as a conventional circuit breaker (not shown), installed therein is shown. A cover or door 304 having a first interior surface 354 and a second exterior surface 366 is openable to provide access to the interior of the housing 300 . The door 304 is retained in a closed position by at least one releasable door-latching mechanism 328 having a biased releasable pawl or latch member 308 having a tab 318 extending therefrom.
As shown in FIG. 4A , a conventional latch member 308 is rotatably mounted to enclosure 300 by a rivet or pin 338 which provides an axis of rotation A 2 for latch 308 . A center line C L2 through the center axis of rotation pin 338 and generally orthogonal to the surface of door 304 is shown in FIG. 3A for reference. Latch member 308 comprises a tab 318 having a latching surface 319 configured to latchably cooperate with a latching portion 334 the outer surface of door 304 . When enclosure door 304 is closed, an aperture or slot 314 disposed in the door 304 is configured to allow tab 318 to protrude through to the exterior of enclosure 300 . To secure the door 304 in a closed position, a bias spring 320 is anchored between latch member 308 and enclosure 300 and disposed to apply a bias force F 1 in a first latching direction D 1 to maintain at least a portion of latching surface 319 proximal to a latching portion 334 of the outer surface of door 304 . The latching portion 334 of the outer surface of door 304 is disposed, with respect to the centerline C L2 of the axis of rotation A 2 , in a second de-latching direction D 2 generally opposite to the first latching direction D 1 . In this way, the latching surface 319 interferes with the opening of door 304 .
To allow the door 304 to open, the latch member 308 is unlatched by manually applying a force F 2 in the second de-latching direction D 2 , sufficient to overcome the biasing force of spring 320 . The unlatching force F 2 rotates latch member 308 in the second de-latching direction D 2 around the axis of rotation A 2 and allows tab 318 to pass through slot 314 .
As shown in FIG. 4B , in the event of a high-pressure condition in enclosure 300 , if the switching device (not shown) in the enclosure 300 experiences a short circuit fault, a relatively high instantaneous pressure is generated inside the enclosure 300 . Under such high internal pressure, an expansive force vector F e is applied generally orthogonal to the enclosure door 304 which causes the door 304 to deflect or move in an outward direction. The door 304 , at latching portion 334 , in turn contacts the latching surface 319 of tab 318 , thus applying force vector F e to tab 318 . The latching surface 319 of tab 318 is configured to create a moment arm of length R 2 in the second de-latching direction D 2 , between the centerline C L2 of the axis of rotation A 2 and the latching surface 319 of tab 318 . In the event of a high expansive force F e applied to the latching surface 319 in a direction generally orthogonal to the interior of enclosure door 304 , a rotational force T R2 , is developed in the first latching direction D 1 , is applied to latch member 308 having a magnitude that is the product of the expansive force F e and moment arm R 2 , such that T R2 =F e ×R 2 . In this way, in the event of a high pressure condition, latch 308 acts to retain the door in a closed position
With respect to the above description, it should be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, form function and manner of operation, assembly and use, are deemed readily apparent and illustrated in the drawings and described in the specification are intended to be encompassed only by the scope of appended claims.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
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A latch for an electrical device enclosure, wherein the latch comprises a moveable member operable in response to high pressure conditions inside the enclosure, and is configured to prevent opening of the enclosure in the event of high pressure conditions inside the enclosure.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of application Ser. No. 09/874,839 filed Jun. 5, 2001, which is a continuation of application Ser. No. 09/679,831 filed Oct. 5, 2000, now issued as U.S. Pat. No. 6,252,093, which is a divisional of U.S. patent application Ser. No. 09/242,091, filed on Jan. 6, 2000, now issued as U.S. Pat. No. 6,160,184, which was a U.S. National Stage Filing under 35 U.S.C. 371 of PCT/US 97/13644, filed Aug. 5, 1997, which is a continuation-in-part of U.S. patent application Ser. No. 08/689,461, filed Aug. 8, 1996, now issued as U.S. Pat. No. 5,723,632, the specifications of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Natural products from plants and microorganisms have proven to be a major source of active anticancer agents and lead compounds for cancer chemotherapy. Mushrooms of the class Basidiomycetes are an exception. Although they occur widely and some are well known to contain a variety of highly poisonous substances, only Omphalotus illudens (jack o'lantern mushroom) is known to produce promising anticancer compounds. These are the sesquiterpenes illudin S and illudin M. The illudins are extremely cytotoxic compounds but have a low therapeutic index particularly in solid tumor systems. However, modification of their structures has yielded several analogs, which possess a greatly improved therapeutic index. Remarkable efficacy has been observed in tests on mouse xenografts of leukemias and various solid tumors.
[0003] First and second generation analogs, for example, dehydroilludin M and acylfulvene, have been described (WO 91/04754). A promising compound is a third generation analog hydroxymethylacylfulvene (HMAF). In tests with MV 522 metastatic lung carcinoma xenografts in nude mice, complete tumor regression was observed in all animals. HMAF also exhibited outstanding activity against breast (MX-1), colon (HT-29) and skin cancers.
[0004] The structures of illudin S and illudin M were first published in 1963 (McMorris et al., J Am. Chem. Soc. 85:831 (1963)). Until recently only one total synthesis of these compounds had been reported (Matsumoto et al., Tetrahedron Lett. 1171 (1970)). This synthesis involved Michael addition of a cycylopropane intermediate to an appropriately substituted cyclopentenone. The resulting product was then transformed into an intermediate which could undergo aldol condensation to form illudin's six-membered ring. A number of further reactions were required to complete the synthesis.
[0005] Padwa et al., ( J. Am. Chem. Soc. 116: 2667 (1994)), have published a synthetic approach to the illudin skeleton using a dipolar cycloaddition reaction of a cyclic carbonyl ylide dipole with cyclopentenone to construct the six-membered ring. Kinder and Bair ( J. Org. Chem. 59:6955 (1994)), have also employed the Padwa methodology to synthesize illudin M. However, these syntheses are long and not well suited for making acylfulvenes on a large scale.
[0006] Thus, a continuing need exists for improved methods for synthesizing acylfulvenes.
SUMMARY OF THE INVENTION
[0007] The present invention provides a method of synthesizing compounds of formula (I):
[0008] wherein R and R′ are independently (C 1 -C 4 )alkyl, preferably methyl. According to the invention, a method is provided of synthesizing a compound of formula (V), a preferred intermediate in the synthesis of compounds of formula (I),:
[0009] comprising the steps of coupling a cyclopentanone of formula (II):
[0010] wherein R 4 is —O—C(R 9 ) 2 O(R 9 ), wherein R 9 is (C 1 -C 4 )alkyl, preferably methyl; with a cyclic carbonyl ylide dipole of formula (III):
[0011] to form a compound of formula (IV):
[0012] and treating compound (IV) with base to form a ketone of formula (V).
[0013] The present method further may further comprise the steps of
[0014] dihydroxylating the ketone to yield a compound of formula (VI):
[0015] and treating the compound of formula (VI) with a removable 1,2-diol protecting reagent to yield an intermediate of formula (VII):
[0016] wherein X is a removable 1,2-diol protecting group. Protecting groups may be introduced by forming a cyclic acetal by treatment with an aldehyde or ketone such as acetone, formaldehyde, acetaldehyde or benzaldehyde. For example, an isopropylidene derivative (acetonide) may be introduced by reaction with acetone. Preferably, the isopropylidene group is introduced by acid-catalyzed exchange with 2,2-dimethoxypropane.
[0017] The method further comprises the steps of treating compound (VII) with RMgCl, where R is (C 1 -C 4 )alkyl, to yield a Grignard product of formula VIII:
[0018] and cleaving the oxybridge to yield a diol of formula (IX):
[0019] The method further comprises the step of removing the diol protecting group to yield a tetraol of formula (X):
[0020] The tetraol is then converted to an orthoester of formula (XI):
[0021] wherein R″ is (C 2 -C 3 )alkyl; and the cis hydroxyls are eliminated to yield a dienone of formula (XII):
[0022] The method further comprises the steps of reducing the compound of formula (XII) to convert the ketone to an alcohol, under conditions which dehydrate the resulting alcohol to yield a fulvene of formula (XIII):
[0023] The fulvene of formula (XIII) is then oxidized to yield a compound of formula (I):
[0024] The present invention also provides a method of synthesizing a compound of formula (XVII):
[0025] wherein R 1 is OH, R 2 is H, and R′ is (C 1 -C 4 )alkyl, preferably methyl.
[0026] According to the present invention, a method is provided of synthesizing a diketone of formula (XIII), a preferred intermediate in the synthesis of compounds of formula (XVII),:
[0027] comprising the steps of
[0028] (a) cleaving the oxybridge in the compound of formula (XIV):
[0029] to yield a diketone of formula (XIII).
[0030] The method further comprises the steps of
[0031] (b) protecting the hydroxyl group in the compound of formula (XIII) with a removable hydroxyl protecting group X; and
[0032] (c) introducing a double bond in the five-membered ring to yield a compound of the formula (XV):
[0033] wherein R′ 1 and R′ 2 together are keto; and
[0034] X is a removable hydroxyl protecting group. Removable hydroxyl protecting groups may be introduced by reaction with a suitable reagent, such as a reagent of the formula ((C 1 -C 4 )alkyl) 3 SiCl, including triethylsilyl (TES) chloride, trimethylsilyl (TMS) chloride, t-butyldimethylsilyl (TBDMS) chloride, dimethyl (1,2,2-trimethylpropyl)silyl chloride, or tris(isopropyl)silyl; and methoxymethyl chloride, β-methoxyethoxymethyl chloride, and isobutylene.
[0035] The method further comprises the steps of
[0036] (d) reducing both keto groups to yield hydroxy groups under conditions that yield a compound of formula (XVI):
[0037] (e) eliminating the cyclopentenol hydroxyl group; and
[0038] (f) oxidizing the cyclohexanol hydroxyl group and removing hydroxyl protecting group X to yield a compound of formula (XVII):
[0039] wherein R 1 is OH and R 2 is H.
[0040] The method additionally comprises the step of
[0041] (g) following step (d), treating the alcohol with mesyl chloride in the presence of a base to produce a mesylate of the formula (XVIII):
[0042] wherein R″ 1 is —OX, R″ 2 is absent and R is H.
[0043] The present invention further provides a method of synthesizing compounds of the formula (XXIII):
[0044] wherein R′ 1 and R′ 2 together are ethylenedioxy, and R′ is (C 1 -C 4 )alkyl, preferably methyl.
[0045] According to the present method, the carbonyl group of the compound of formula (XIII) is converted to an acetal group to yield a compound of formula (XIX):
[0046] The method further comprises the steps of
[0047] (b) protecting the hydroxyl group in the compound of formula (XIX) with a removable hydroxyl protecting group X; and
[0048] (c) introducing a double bond in the five-membered ring to yield a compound of the formula (XX):
[0049] wherein X is a removable hydroxyl protecting group.
[0050] The method further comprises the steps of
[0051] (d) reducing the keto group to yield a hydroxy group under conditions that yield a compound of formula (XXI):
[0052] (e) eliminating the cyclopentenol hydroxyl group;
[0053] (f) removing hydroxyl protecting group X to yield a compound of formula (XXII):
[0054] and
[0055] (g) oxidizing the cyclohexanol hydroxyl group to yield a compound of formula (XXIII):
[0056] The method further comprises the step of
[0057] (h) following step (d), treating the alcohol with mesyl chloride to produce a mesylate of the formula (XXIV):
[0058] With respect to both mesylates of formulas (XVIII) and (XXIV), the mesylates are relatively unstable and convert to fulvenes upon standing. Removal of the protecting group X and oxidation yield compounds of formulas (XVII) and (XXIII), respectively.
[0059] The invention also provides novel compounds of formula I-XXIV, all of which are useful as intermediates in the synthesis of 6-substituted acylfulvene analogs (6-substituted acylfulvenes) as disclosed, for example, in Kelner et al., U.S. Pat. No. 5,523,490, or which have antitumor or cytotoxic activity per se.
BRIEF DESCRIPTION OF THE DRAWINGS
[0060] [0060]FIG. 1 is a schematic representation of the synthesis of a compound of Formula (I), specifically compound 26 .
[0061] [0061]FIG. 2 is a schematic representation of the synthesis of compound of Formula (XV), specifically compound 35 .
[0062] [0062]FIG. 3 is a schematic representation of the synthesis of compound of Formula (XV), specifically compound 42 .
DETAILED DESCRIPTION OF THE INVENTION
[0063] An illudin analog of formula (I), where R and R′ are methyl (compound 26 ), can be synthesized by utilizing FIG. 1. The numbers following the named compounds refer to the numbered compounds of Schemes I, II and III. The starting compound ( 14 ) is readily prepared from furfural and methylmagnesium chloride followed by acid catalyzed rearrangement (Piancatelli et al., Tetrahedron Lett. 3555 (1976)). Protection of the hydroxyl in 14 by forming the acetal derivative 15 , for example, followed by reaction with ylide 5 gives the adduct 16 (84% yield). Mild base treatment (KOH—MeOH, room temp., 1 h) of 16 affords the unsaturated ketone 17 (95%). Dihydroxylation of 17 with OsO 4 , NMO in THF (room temp., 24 h) gives the cis-dihydroxy product 18 which is converted to the acetonide 19 with dimethoxy propane and p- TsOH (87% for the two steps). Regioselective reaction of 19 with methylmagnesium chloride (in THF, −78° C.) affords the Grignard product 20 . Treatment of 20 with 10% KOH—MeOH at 80° C. for 2 h cleaves the oxybridge giving the diol 21 (75% for the two steps). The structure ( 21 ) has been confirmed by X-ray crystallographic analysis which indicates trans relationship of the two hydroxyls.
[0064] Hydrolysis of the acetonide with Dowex resin (H + form) in MeOH at room temperature for 12 h affords the tetraol 22 in 95% yield. Conversion of 22 to the orthoester 23 by treatment with trimethylorthoformate and p-TsOH at room temperature followed by heating 23 at 190° C. under reduced pressure results in elimination of the cis hydroxyls yielding the dienone. The yields in this reaction are rather low but can be improved by adding acetic anhydride. A good yield of the monoacetate and diacetate ( 24 a, b ) is obtained. Reduction of the ketone with NaBH 4 —CeCl 3 gives the corresponding alcohol which is unstable and is converted to the fulvene on standing. The acetate groups are removed by treatment with lithium aluminum hydride and the resulting fulvene 25 is oxidized with the Dess-Martin reagent to ± acylfulvene 26 . The overall yield for the last four steps is approximately 30%.
[0065] An acylfulvene analog of formula (XV) where R′ 1 and R′ 2 together are ethylenedioxy (compound 35 ), may be synthesized as shown in FIG. 2. The oxybridge in the intermediate 7 is cleaved with K 2 CO 3 in isopropanol at room temperature giving the diketone 27 (82%). Regioselective acetal formation (ethylene glycol, p-TsOH, C 6 H 6 , room temperature) gives in quantitative yield the monoacetal 28 . Protection of the hydroxyl as the triethyl silyl ether (triethylsilylchloride, pyridine, 60° C.) is quantitative. A double bond is introduced into compound 29 , by treatment with benzene seleninic anhydride in chlorobenzene at 95° C., yielding cross conjugated ketone 30 (78%). Reduction of 30 (NaBH 4 , CeCl 3 . 7 H 2 O in MeOH) gives alcohol 31 . This compound on treatment with methane sulfonyl chloride and triethylamine gives the fulvene 33 (via the unstable mesylate 32 ). Removal of the silyl protecting group (p-TsOH, acetone-water 1:1) gives the alcohol 34 , which upon oxidation with pyridinium dichromate in dichloromethane affords the acylfulvene 35 (60% yield for four steps).
[0066] Another analog of formula (XVII) where R 1 is OH and R 2 is H (compound 42 ) can be made from intermediate 27 . As shown in FIG. 3, compound 27 is converted to the triethylsilyl (TES) ether 36 . A double bond is then introduced in the five membered ring by reaction with phenylseleninic anhydride giving 37 in good yield. Reduction of the diketone with sodium borohydride-ceric chloride gives the corresponding alcohols accompanied by rearrangement of the TES group, resulting in compound 38 . Treatment of the latter with triethylamine and mesylchloride gives the unstable mesylate 39 which directly yields the fulvene 40 . Oxidation of 40 with Dess-Martin reagent and removal of the silyl protecting group gives ± acylfulvene analog 42 .
[0067] The compounds of formulas (I), (XVII) and ((XXIII) and intermdiates thereof are useful as antineoplastic agents, i.e., to inhibit tumor cell growth in vitro or in vivo, in mammalian hosts, such as humans or domestic animals, and are particularly effective against solid tumors and multi-drug resistant tumors. These compounds may be particularly useful for the treatment of solid tumors for which relatively few treatments are available. Such tumors include epidermoid and myeloid tumors, acute (AML) or chronic (CML), as well as lung, ovarian, breast and colon carcinoma. The compounds can also be used against endometrial tumors, bladder cancer, pancreatic cancer, lymphoma, Hodgkin's disease, prostate cancer, sarcomas and testicular cancer as well as against tumors of the central nervous system, such as brain tumors, neuroblastomas and hematopoietic cell cancers such as B-cell leukemia/lymphomas, myelomas, T-cell leukemia/lymphomas, and small cell leukemia/lymphomas. These leukemia/lymphomas could be either acute (ALL) or chronic (CLL).
[0068] The compounds may also be incorporated in a pharmaceutical composition, such as pharmaceutical unit dosage form, comprising an effective anti-neoplastic amount of one or more of the illudin analogs in combination with a pharmaceutically acceptable carrier.
[0069] The methods of the present invention may also be adapted to make pharmaceutically acceptable salts of compounds of formula (I), (XVII) or (XXIII). Pharmaceutically acceptable salts include, where applicable, salts such as amine acid addition salts and the mono-, di- and triphosphates of free hydroxyl groups. Amine salts include salts of inorganic and organic acids, including hydrochlorides, sulfates, phosphates, citrates, tartarates, malates, maleates, bicarbonates, and the like. Alkali metal amine or ammonium salts can be formed by reacting hydroxyaryl groups with metal hydroxides, amines or ammonium.
[0070] The compounds can be formulated as pharmaceutical compositions and administered to a mammalian host, such as a human cancer patient, in a variety of forms adapted to the chosen route of administration, i.e., orally or parenterally, by intravenous, intraperitoneal, intramuscular or subcutaneous routes.
[0071] The subject can be any mammal having a susceptible cancer, i.e., a malignant cell population or tumor. The analogs are effective on human tumors in vivo as well as on human tumor cell lines in vitro.
[0072] Thus, the compounds may be orally administered, for example, in combination with a pharmaceutically acceptable vehicle such as an inert diluent or an assimilable edible carrier. They may be enclosed in hard or soft shell gelatin capsules, may be compressed into tablets, or may be incorporated directly with the food of the patient's diet. For oral therapeutic administration, the active compound may be combined with one or more excipients and used in the form of ingestible tablets, buccal tablets, troches, capsules, elixirs, suspensions, syrups, wafers, and the like. Such compositions and preparations should contain at least 0.1% of active compound. The percentage of the compositions and preparations may, of course, be varied and may conveniently be between 2 to about 60% of the weight of a given unit dosage form. The amount of active compound in such therapeutically useful compositions is such that an effective dosage level will be obtained.
[0073] The tablets, troches, pills, capsules and the like may also contain the following: A binder such as gum tragacanth, acacia, corn starch or gelatin; excipients such as dicalcium phosphate; a disintegrating agent such as corn starch, potato starch, alginic acid and the like; a lubricant such as magnesium stearate; and a sweetening agent such as sucrose, lactose, or saccharin or a flavoring agent such as peppermint, oil of wintergreen, or cherry flavoring may be added. When the unit dosage form is a capsule, it may contain, in addition to materials of the above type, a liquid carrier, such as a vegetable oil or a polyethylene glycol. Various other materials may be present as coatings or to otherwise modify the physical form of the solid unit dosage form. For instance, tablets, pills, or capsules may be coated with gelatin, wax, shellac or sugar and the like. A syrup or elixir may contain the active compound, sucrose as a sweetening agent, methyl and propylparabens as preservatives, a dye and flavoring such as cherry or orange flavor. Of course, any material used in preparing any unit dosage form should be pharmaceutically acceptable and substantially non-toxic in the amounts employed. In addition, the active compound may be incorporated into sustained-release preparations and devices.
[0074] The active compound may also be administered intravenously or intraperitoneally by infusion or injection. Solutions of the active compound can be prepared in water, optionally mixed with a nontoxic surfactant. Dispersions can also be prepared in glycerol, liquid polyethylene glycols, triacetin, and mixtures thereof and in oils. Under ordinary conditions of storage and use, these preparations contain a preservative to prevent the growth of microorganisms.
[0075] The pharmaceutical dosage forms suitable for injection or infusion use can include sterile aqueous solutions or dispersions or sterile powders comprising the active ingredient which are adapted for the extemporaneous preparation of sterile injectable of infusible solutions or dispersions. In all cases, the ultimate dosage form must be sterile, fluid and stable under the conditions of manufacture and storage. The liquid carrier or vehicle can be a solvent or liquid dispersion medium comprising, for example, water, ethanol, a polyol (for example, glycerol, propylene glycol, liquid polyethylene glycols, and the like), vegetable oils, nontoxic glyceryl esters, and suitable mixtures thereof. The proper fluidity can be maintained, for example, by the formation of liposomes, by the maintenance of the required particle size in the case of dispersion or by the use of surfactants. The prevention of the action of microorganisms can be brought about by various antibacterial and antifungal agents, or example, parabens, chlorobutanol, phenol, sorbic acid, thimerosal, and the like. In many cases, it will be preferable to include isotonic agents, for example, sugars, buffers or sodium chloride. Prolonged absorption of the injectable compositions can be brought about by the use in the compositions of agents delaying absorption, for example, aluminum monostearate and gelatin. Sterile injectable solutions are prepared by incorporating the active compound in the required amount in the appropriate solvent with various of the other ingredients enumerated above, as required, followed by filter sterilization. In the case of sterile powders for the preparation of sterile injectable solutions, the preferred methods of preparation are vacuum drying and the freeze drying techniques, which yield a powder of the active ingredient plus any additional desired ingredient present in the previously sterile-filtered solutions.
[0076] Useful dosages of compounds made according to the present methods can be determined by correlating the compounds' in vitro activity, and in vivo activity in animal models, such as murine or dog models as taught for illudin analogs such as those of U.S. Pat. Nos. 5,439,936 and 5,523,490, to activity in higher mammals, such as children and adult humans as taught, e.g., in Borch et al. (U.S. Pat. No. 4,938,949).
[0077] The therapeutically effective amount of analog necessarily varies with the subject and the tumor to be treated. However, it has been found that relatively high doses of the analogs can be administered due to the decreased toxicity compared to illudin S and M. A therapeutic amount between 30 to 112,000 μg per kg of body weight is especially effective for intravenous administration while 300 to 112,000 μg per kg of body weight is effective if administered intraperitoneally. As one skilled in the art would recognize, the amount can be varied depending on the method of administration.
[0078] The invention will be further described by reference to the following detailed examples.
EXAMPLES
Example I
[0079] Synthesis of Compound 36
[0080] General. Solvents were dried and distilled prior to use. THF and diethyl ether were distilled from sodium-benzophenone, CH 2 Cl 2 and triethylamine from CaH 2 , Melting points are uncorrected. 1H- and 13C-NMR spectra were measured at 300 MHz and 75 MHz, respectively. High resolution mass spectra were determined at 70 ev (EI) by the Mass Spectrometry Service Laboratory at the University of Minnesota. Column chromatography was performed on silica gel ( Davisil 230-425 mesh, Fisher Scientific ). In some cases, a small amount of triethylamine was used to neutralize the silica gel.
[0081] Compound 15 . To a solution of 14 (0.448 g, 4 mmol) in 2-methoxypropene (1.55 ml, 16.2 mmol), a drop of POCl 3 was added under Ar. The solution was stirred at 25° C. for 12 hours and quenched by 3 drops of Et 3 N. The volatile components were removed in vacuo and the product 15 was obtained as a brown liquid which crystallized below 0° C. (0.69 g, 94.3%). 1 H NMR (CDCl 3 ): δ 7.43(dd, 1H), 6.17(d, 1H), 4.58(br s, 1H), 3.26(s, 3H), 2.26(m, 1H), 1.41(s, 3H), 1.40(s, 3H), 1.22(d, 3H).
[0082] Compound 16 . To a mixture of 15 (5.02 g, 27.3 mmol), rhodium acetate (145 mg, 0.33 mmol), DMF(500 uL) in CH 2 Cl 2 (50 mL), a solution of 4 (6.0 g, 39.5 mmol) in CH 2 Cl 2 (50 mL) was added dropwise within 10 minutes at 40° C. The orange-red solution was refluxed at 40° C. for 1.5 hours and the solvent was removed in vacuo. Chromatography (Hexane/EtOAc, 10:2) gave product 16 as white crystals (7.10 g, 84.5%). m.p.:142-144° C.; 1 H NMR (CDCl 3 ): δ 4.98(s, 1H), 4.13(dd, 1H), 3.28(s, 3H), 2.82(t, 1H), 2.63(d, 1H), 2.54(m, 1H), 1.43(s, 3H), 1.42(s, 3H), 1.18(s, 3H), 1.08(d, 3H), 1.29(m, 1H), 1.03-1.16(m, 2H), 0.72(m, 1H); 13 C NMR (CDCl 3 ): δ 213.3, 212.1, 101.2, 87.4, 81.8, 73.8, 59.4, 50.4, 49.7, 45.8, 39.0, 26.0, 25.1, 14.1, 13.7, 12.4, 11.4. IR (film, cm −1 ): 2985, 1738, 1389, 1339, 1173, 1080, 1052, 991, 859, 827; HRMS calcd. for C 17 H 24 O 5 : 308.1624, found: 308.1625
[0083] Compound 17 . The solution of 16 (594.3 mg, 1.93 mmol) in 5% KOH—MeOH (35 ml) was stirred at room temperature for 1 hour. The generated red solution was then neutralized and extracted with EtOAc. The combined organic phase was washed with sat. brine (20 ml×2) and dried over Na 2 SO 4 . Chromatography (Hexanes/EtOAc, 10:3)gave the product 17 as white crystals (390.9 mg, 93%).m.p.: 108.5-109.4° C.; 1 H NMR (CDCl 3 ): δ 7.15(d, 1H), 4.24(s, 1H), 3.21(br s, 1H), 2.55(d, 1H), 1.75(s, 3H), 1.23(s, 3H), 1.25(m, 1H), 1.10( m, 1H), 0.97(m, 1H), 0.74(m, 1H); 13 C NMR (CDCl 3 ): δ 211.77, 205.86, 154.23, 145.86, 86.05, 80.93, 54.68, 45.82, 37.56, 14.05, 13.22, 11.58, 10.22; IR (film, cm −1 ): 1754, 1703, 1639, 1389, 1339, 997; HRMS calcd. for C 13 H 14 O 3 : 218.0943, found: 218.0941
[0084] Compound 19 . To a solution of 17 (349.4 mg, 1.60 mmol), NMO (355 mg) in THF (17.7 ml) and H 2 O (0.5 ml), was added OsO 4 -THF solution (2.5 wt %, 3.5 ml). After stirred at 25° C. for 21 hrs, the reaction was quenched by aqueous Na 2 SO 3 solution. The reaction mixture was extracted with EtOAc. The organic phase was washed with sat. NaCl solution, dried over Na 2 SO 4 and concentrated. The crude diol product 18 was used for next step without further purification. A small amount of 18 was purified by chromatography. 1 H NMR (CDCl 3 ): δ 4.60(s, 1H), 3.95(t, 1H), 3.01(d, 1H), 2.94(d, 1H), 2.88(s, 1H), 2.81(dd, 1H), 1.36(s, 3H), 1.28(s, 3H), 1.33(m, 1H), 1.18(m, 1H), 1.06(m, 1H), 0.75(m, 1H)
[0085] The crude diol 18 was reacted with 2,2-dimethoxypropane (0.8 ml, 4 eq.) in CH 3 CN (8.0 ml) in the presence of a trace of pTsOH. After being stirred at 25° C. for 10 hrs, the mixture was diluted with CH 2 Cl 2 and washed with sat. NaHCO 3 solution and brine. Chromatography (Hexanes/EtOAc, 10:2) gave the product 19 as white crystals (308.5 mg, 87.3%). m.p.: 178.5-179.5° C.; 1 H NMR (CDCl 3 ): δ 4.58(s, 1H), 4.36(s, 1H), 2.89(q, 2H), 1.42(s, 3H), 1.34(s, 3H), 1.31(s, 3H), 1.20(s, 3H), 1.28(m, 1H), 1.16(m, 1 H), 1.05(m, 1H), 0.69-0.76(m, 1H); 13 C NMR (CDCl 3 ): δ 215.53, 210.05, 110.66, 87.96, 86.44, 85.03, 83.34, 57.36, 45.37, 38.49, 27.17, 25.96, 16.92, 14. 19, 13.57, 12.32; IR (film, cm −1 ): 2986, 1746, 1372, 1338, 1247, 1216, 1158, 1082; HRMS calcd. for C 16 H 20 O 5 : 292.1311, found: 292.1315
[0086] Compound 21 . To the solution of 19 (289.5 mg, 0.99 mmol) in THF (25 ml) at -78° C., was added MeMgCl-THF solution (3.0M, 830 μl, 2.5 eq) slowly. After 2.5 hrs, the solution was warmed to 0° C. and quenched with sat. NH 4 Cl solution. The solution was extracted with EtOAc and the organic phase was washed with brine solution. Concentration of dried organic solution gave the crude compound 20 . 1 H NMR (CDCl 3 ): δ 4.29(s, 1H), 4.23(s, 1H), 3.45(d, 1H), 2.78(d, 1H), 1.39(s, 3H), 1.35(s, 3H), 1.33(s, 3H), 1.24(s, 3H), 1.01(s, 3H), 0.77(m, 1H), 0.67(m, 1H), 0.52(m, 1H), 0.20(m, 1H); IR (film, cm −1 ): 3492, 2984, 2934, 1743, 1454, 1373, 1257, 1210, 1159, 1082; HRMS calcd. for C 17 H 24 O 5 : 308.1624, found: 308.1629.
[0087] The crude compound 20 was dissolved in 10% KOH—MeOH solution. The red mixture was heated at 80° C. for 2 hrs then partitioned between H 2 O and CH 2 Cl 2 . The organic layer was washed with brine then dried over Na 2 SO 4 . Chromatography (Hexanes/EtOAc, 10:15) gave the product 21 as white crystals (228.0mg, 75%) (inseparable mixture of isomers shown by 1 H NMR). m.p.: 162.0-164.0° C.; 1 H NMR (CDCl 3 ): δ 4.52(d, 1H), 3.88(dd, 1H), 3.38(m, 1H), 2.33(d, 1H), 2.18(s, 1H), 1.81(d, 3H), 1.42(s, 3H), 1.38(s, 3H), 1.07 (s, 3H), 0.97-1.18(m, 4H); 13 C NMR (CDCl 3 ): δ 201.52, 152.89, 126.44, 112.96, 85.95, 81.34, 73.14, 72.31, 44.44, 29.41, 28.71, 28.22, 22.82, 21.07, 14.11, 12.58, 7.58; IR (film, cm −1 ): 3455, 2987, 2935, 1694, 1599, 1445, 1373, 1240, 1212, 1092, 1048; HRMS calcd. for C 17 H 24 O 5 : 308.1624, found: 308.1624
[0088] Compound 22 . The compound 21 (60.9 mg, 0.20 mmol) was stirred with Dowex 50w-x16 resin (2.96 g) in MeOH (5.0 ml) at r.t. for 22 hrs. The resin was filtered away and the filtrate was washed with sat. NaHCO 3 , sat. NaCl and dried over Na 2 SO 4 . Chromatography (CH 2 Cl 2 /MeOH, 10:1) gave the product as white crystals (49.5 mg, 93%). m.p.:149.0-151.0° C.; 1 H NMR (CD 3 OD): δ 3.83(d, 1H), 3.81(s, 1H), 3.25(m, 1H), 1.90(d, 3H), 1.25(s, 3H), 1.07(s, 3H), 0.99-1.11(m, 4H); 13 C NMR (CD 3 OD): δ 202.95, 156.24, 127.16, 76.44, 74.38, 74.12, 71.69, 44.52, 30.07, 23.14, 20.03, 14.56, 13.30, 8.20; HRMS calcd. for C 14 H 20 O 5 : 268.1311, found: 268.1312.
[0089] Compound 24 a and 24 b. To the solution of 22 (40.2 mg, 0.15 mmol) and pTsOH (3.0 mg) in THF (3.0 ml), was added HC(OCH 3 ) 3 (130 μl 8 eq.) at 25° C. After 2 hrs, sat. NaHCO 3 solution was added and the mixture was extracted with EtOAc. The combined organic phase was washed with brine and dried over Na 2 SO 4 . Concentration of the filtrate gave the ortho ester 23 (46.3 mg, 100%) as the intermediate for next reaction.
[0090] The ortho ester 23 (35.7 mg, 0.12 mmol) in Ac 2 O (2.0 ml) was heated at 150° C. for 1 hr. To the cooled reaction solution was added sat. NaHCO 3 solution and extracted with EtOAc. The organic phase was washed with brine and dried over Na 2 SO 4 . Chromatography (Hexanes/EtOAc, 10:3 to 10:7) gave the products 24 a and 24 b as white crystals in 57.3% (18.2 mg) and 9.8% (3.6 mg) respectively.
[0091] Product 24 a : m.p.: 119-121° C.; 1 H NMR (CDCl 3 ): δ 6.98(s, 1H), 5.25(d, 1H), 3.92(br s, 1H), 1.95(s, 3H), 1.92(s, 3H), 1.80(t, 3H), 0.94-1.42(m, 4H); 13 C NMR (CDCl 3 ): δ 195.59, 170.87, 147.53, 145.85, 145.25, 128.16, 74.16, 72.64, 41.02, 30.30, 22.93, 20.89, 13.48, 11.19, 11.00, 7.70; IR (film, cm −1 ): 3431, 2982, 2914, 1735, 1671, 1613, 1437, 1374, 1237, 1222, 1086, 1027; HRMS calcd. for C 16 H 20 O 4 : 276.1362, found: 276.1363.
[0092] Product 24 b : m.p.: 189.3-191.2° C.; 1 H NMR (CDCl 3 ): δ 6.95(s, 1H), 6.12(d, 1H), 3.49(br s, 1H), 2.00(s, 3H), 1.97(s, 3H), 1.92(s, 3H), 1.79(s, 3H), 1.30(s, 3H), 0.92-1.27(m, 4H); 13 C NMR (CDCl 3 ): δ 195.35, 170.17, 170.35, 146.76, 146.00, 145.47, 127.95, 83.75, 70.53, 41.12, 29.27, 22.38, 20.78, 17.23, 12.35, 11.39, 10.95, 9.11.
[0093] Compound 26 Acylfulvene from 24 a. To the clear solution of 24 a (2.3 mg, 8.8 umol), CeCl 3 .7H 2 O (24.9 mg, 8.0 eq) in Methanol (78 μl) and THF (155 μl) at 0° C., excess of NaBH 4 was added in one portion. After 15 minutes at 0° C., the suspension was stirred at 25° C. for 30 minutes. At 0° C., the mixture was quenched with 5% HCl solution and Sat.NH4Cl solution and extracted with CH 2 Cl 2 . The organic phase was washed with H 2 O and dried over MgSO 4 . Concentration and chromatography (Hexanes/EtOAc, 10:5) gave the product as yellow solid (1.8 mg, 84%). 1 H NMR (CDCl3): δ 6.06(s, 1H), 6.01(s, 1H), 5.84(s, 1H), 2.21(s, 3H), 2.04(s, 3H), 1.81(s, 3H), 1.15(s, 3H), 0.62-1.44(m, 4H);
[0094] The yellow compound was then dissolved in absolute ethanol (100 ul) and a trace of KCN was added. The solution was stirred overnight at 25° C. and TLC showed the compound 25 was the exclusive product. The solution was diluted with ether and washed with sat.brine and dried over Na 2 SO 4 .
[0095] After concentration, the crude diol 25 was oxidized by Dess-Martin reagent (11.8 mg) in CH 2 Cl 2 solution (1.2 ml). After being stirred at 25° C. for 1 hour, the reaction solution was diluted with ether and quenched with the mixture of aqueous sodium bicarbonate and sodium bisulfite. The organic phase was washed with sat. NaHCO 3 and sat. NaCl solution and dried over NaSO 4 . Concentration and chromatography (Hexanes/EtOAc, 10:1) gave product 26 Acylfulvene as a yellow gum (1.1 mg, 47% from 24 a ). 1 H NMR (CDCl 3 ): δ 7.16(s, 1H), 6.43(t, 1H), 2.15(s, 3H), 2.00(s, 3H), 1.38(s, 3H), 0.70-1.55(m, 4H);IR (film, cm −1 ): 3464, 2922, 2851, 1723, 1664, 1610, 1487, 1441, 1355, 1327, 1264, 1095, 1031; HRMS calcd. for C 14 H 16 O 2 : 217.1229(M+H + ), found: 217.1224(M+H + ).
[0096] Compound 26 Acylfulvene from 24 b. To the clear solution of 24 b (4.1 mg, 0.013 mmol), CeCl 3 .7H 2 O (39.5 mg, 0.11 mmol) in Methanol (100 ul) and THF(200 ul) at 0° C., excess of NaBH 4 was added in one portion. After 1 hour at 0° C., the suspension was stirred at 25° C. for 15 minutes. At 0° C., the mixture was quenched with 5% HCl solution and Sat.NH4Cl solution and extracted with CH 2 Cl 2 . The organic phase was washed with H 2 O and dried over MgSO 4 . Concentration and chromatography (Hexanes/EtOAc, 10:3) gave the product as yellow solid (3.9 mg, 100%). 1 H NMR (CDCl 3 ): δ 6.24(s, 1H), 6.18(s, 1H), 6.02(d, 1H), 2.06(s, 3H), 2.03(s, 3H), 1.89(s, 3H), 1.82(s, 3H), 1.50(s, 3H), 1.39(m, 1H), 0.99-1.07(m, 3H);
[0097] The yellow solid (3.0 mg, 0.01 mmol) was redissolved in ether (0.6 ml) and added to the reaction vial with LiAlH 4 (12 mg, 0.31 mmol) in ether (0.4 ml) at 0° C. The suspension was stirred at 0° C. for 30 minutes and warmed up to 25° C. for 20 minutes. The reaction was quenched with acetone then 5% HCl solution and sat. NH 4 Cl solution were added. The mixture was extracted with ether. The combined ether phase was washed with sat. NaCl solution and dried over NaSO 4 . Remove of solvent gave the crude diol 25 .
[0098] The crude diol 25 was oxidized by Dess-Martin reagent (70 mg) in CH 2 Cl 2 solution (1.5 ml). After being stirred at 25° C. for 1 hour, the reaction solution was diluted with ether and quenched with the mixture of aqueous sodium bicarbonate and sodium bisulfite. The organic phase was washed with sat. NaCO 3 and sat. NaCl solution and dried over NaSO 4 . Concentration and chromatography (Hexanes/EtOAc, 10:1) gave product 26 Acylfulvene as a yellow gum (0.7 mg, 33% from 24 b ). 1 H NMR (CDCl 3 ): δ 7.16(s, 1H), 6.43(t, 1H), 2.15(s, 3H), 2.00(s, 3H), 1.38(s, 3H), 0.70-1.55(m, 4H); IR (film, cm −1 ):3464, 2922, 2851, 1723, 1664, 1610, 1487, 1441, 1355, 1327, 1264, 1095, 1031; HRMS calcd. for C 14 H 16 O 2 : 217.1229 (M+H + ), found: 217.1224 (M+H + )
Example II
[0099] Synthesis of Compound 35
[0100] General. Melting points are uncorrected. 1 H and 13 C NMR spectra were measured at 300 and 75 MHz. High resolution mass spectra were determined at the University of Minnesota Mass Spectrometry Service Laboratory. All chromatography used silica gel (Davisil 230-425 mesh, Fisher Scientific) and solvent was ethyl acetate and hexanes. Analytical TLC was carried out on Whatman 4420 222 silica gel plates. Reactions were routinely monitored by TLC. Yield was calculated after recycling starting materials.
[0101] Compound 7 . Compound 7 was made following literature as a white solid: mp 134-6° C.; IR (KBr) 2993, 2952, 1757, 1743, 1454 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.74 (m, 1H), 1.03 (m, 1H), 1.13 (m, 1H), 1.25 (s, 3H), 1.32 (m, 1H), 2.08 (m, 2H), 2.27 (m, 2H), 2.54 (d, J=7.5 Hz, 1H), 2.92(m, 1H), 4.45 (s, 1H); 13 C NMR (CDCl 3 ) δ 216.6, 211.4, 87.7, 87.4, 57.6, 41.3, 39.2, 38.3, 25.1, 14.1, 13.4, 11.9; MS m/z 206 (M + ), 177, 149, 124; HRMS for C 12 H 14 O 3 calcd 206.0943, found 206.0941.
[0102] Compound 27 . To a stirred solution of 7 (2.83 g, 13.7 mmol) and 2-propanol (500 ml) was added K 2 CO 3 (8 g, 58.0 mmol) at 25° C. The mixture was stirred for 7 days, then partitioned between EtOAc and water. The organic extract was washed with saturated NH 4 Cl and dried over MgSO 4 . Then the crude product was concentrated and chromatographed to give 1.88 g of 7 and 0.78 g of 27 (82.1%). 27 is a white solid: mp 183-5° C.; IR (KBr) 3369, 2995, 1696, 1616, 1407, 1367, 1226 cm −1 ; 1 H NMR (CDCl 3 ) δ 1.24 (m, 1H), 1.38 (m, 1H), 1.68 (m, 1H), 1.88 (m, 1H), 2.00 (s, 3H), 2.16 (m, 2H), 2.46 (m, 2H), 3.21 (m, 1H), 4.06 (d, J=2.7 Hz, 1H); 13 C NMR (CDCl 3 ) δ206.1, 204.8, 147.5, 128.0, 72.0, 42.2, 39.5, 32.1, 21.7, 19.4, 18.6, 11.7; MS m/z 206 (M + ), 177, 150, 147; HRMS for C 12 H 14 O 3 calcd 206.0943, found 206.0944.
[0103] Compound 28 . p-Tolunesulfonic acid (12 mg, 0.063 mmol) was added to a stirred solution of 27 (107 mg, 0.519 mmol) and ethylene glycol (3.04 g, 49 mmol) in benzene (10 ml) at 25° C. which was then stirred for 24 h. The mixture was partitioned between EtOAc and saturated NaHCO 3 . The combined organic layers were washed with saline, dried over MgSO 4 and concentrated to an oil which was chromatographed to give 5 mg of 27 and 118 mg of 28 (95.3%) as colorless oil: IR (KBr) 3469, 2952, 2892, 1757, 1690, 1616, 1374, 1159, 1085 cm −1 ; 1 H NMR (CDCl 3 ) δ 1.00 (m, 3H), 1.36 (m, 1H), 1.88 (d, J=2.7 Hz, 3H), 1.96 (m, 2H), 2.36 (m, 2H), 3.19 (t, J=3.9 Hz, 1H), 3.78 (t, J=3.9 Hz, 1H), 4.00 (m, 4H); 13 C NMR (CDCl 3 ) δ 205.4, 148.3, 128.3, 108.9, 67.9, 65.6, 64.5, 41.9, 39.3, 26.8, 20.8, 12.8, 11.5, 6.22; MS m/z 250 (M + ), 221, 193, 177; HRMS for C 14 H 18 O 4 calcd 250.1205, found 250.1201.
[0104] Compound 29 . To a stirred solution of 28 (8.0 mg, 0.032 mmol) and pyridine (0.5 ml) was added TESCl (0.1 ml, 0.25 mmol) under N 2 . The reaction mixture was stirred at 60° C. for 30 min and then concentrated to an oil. The crude product was purified by chromatography to give 13 mg of 29 (quantitative) as a colorless oil: IR (KBr) 2959, 2885, 1710, 1610, 1454, 1414, 1381, 1219 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.62 (q, J=7.8 Hz, 6H), 0.94 (m, 11H), 1.28 (m, 1H), 1.83 (m, 1H), 1.87 (d, J=2.4 Hz, 3H), 2.35 (m, 2H), 3.13 (m, 2H), 3.75 (d, J=3.3 Hz, 1H), 4.01 (m, 4H); 13 C (CDCl 3 ) δ 205.6, 148.8, 128.8, 109.5, 69.1, 65.3, 64.7, 43.3, 39.5, 27.4, 21.5, 12.9, 11.6, 6.8, 6.5, 4.8; MS m/z 364 (M + ), 336, 291, 219, 161; HRMS for C 20 H 32 O 4 Si calcd 364.2070, found 364.2070.
[0105] Compound 30 . A solution of 29 (13 mg, 0.0357 mmol) and phenylseleninic anhydride (13 mg, 0.0361 mmol) in chlorobenzene (0.5 ml) was stirred at 95° C. for 0.5 h under N 2 . The solution was then concentrated and chromatographed to give 4.9 mg of 29 and 7.0 mg of 30 (78.2%) as colorless oil: IR (KBr) 2959, 2878, 1716, 1683, 1622, 1454, 1381, 1213 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.54 (q, J=6.3 Hz, 6H), 0.89 (m, 10H), 1.27 (m, 2H), 1.57 (m, 1H), 1.93 (m, 3H), 3.79 (s, 1H), 4.00 (m, 4H), 6.30 (dd, J=2.4, 6 Hz, 1H), 7.28 (dd, J=2.1, 6Hz, 1H); 13 C NMR(CDCl 3 ) δ 195.9, 154.7, 146.9, 137.7, 127.5, 109.5, 69.2, 65.5, 64.6, 47.4, 28.0, 12.8, 11.1, 7.1, 6.7, 5.0; MS m/z 362 (M + ), 333, 289, 187, 159, 87; HRMS for C 20 H 30 O 4 Si calcd 362.1913, found 362.1919.
[0106] Compound 34 . To the solution of 30 (20 mg, 0.055 mmol) and CeCl 3 .7H 2 O (35 mg, 0.094 mmol) in MeOH (1 ml) was added NaBH 4 (excess). The mixture was stirred for 15 min at 25° C. and then more NaBH 4 was added. After 15 min of stirring the mixture was partitioned between Et 2 O and saturated NH 4 Cl. The ether extract was dried over MgSO 4 and concentrated to give crude product 31 as pale yellow oil.
[0107] To the solution of the above crude product 31 in CH 2 Cl 2 (1 ml) was added Et 3 N (20 ml, 0.143 mmol) and MsCl (20 ml, 0.258 mmol) respectively at 25° C. It was stirred for 5 min. Then the mixture was partitioned between Et 2 O and saturated NaHCO 3 . The ether extract was washed by saline and dried over MgSO 4 . After concentration, it was chromatographed to give 33 and 34 as yellow gum.
[0108] To the solution of the above compound 33 in acetone (2 ml) and water (1 ml) was added some p-TsOH at room temperature. The mixture was set aside for 5 min and partitioned between Et 2 O and saturated NaHCO 3 . Then the ether extract was washed by saline and dried by MgSO 4 . After concentration and chromatography, it was mixed with the above product 34 to give 10.5 mg of 34 as yellow gum: IR (KBr) 3456, 2912, 2885, 1730, 1636, 1441, 1367 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.75 (m, 1H), 1.10 (m, 2H), 1.24 (m, 1H), 1.88 (s, 3H), 2.34 (d, J=6.9 Hz, 1H), 3.95 (m, 2H), 4.06 (m, 2H), 4.68 (d, J=5.7 Hz, 1H), 6.34 (m, 1H), 6.42 (m, 2H); 13 C NMR (CDCl 3 ) d 152.0, 139.8, 134.6, 130.5, 125.3, 117.9, 111.9, 71.3, 67.0, 66.1, 31.5, 16.4, 9.5, 6.6; MS m/z 232 (M + ), 215, 189, 160, 145; HRMS for C 14 H 16 O 3 calcd 232.1099, found 232.1093.
[0109] Compound 35 . A solution of 34 (7.3 mg, 31 mmol) and pyridinium dichromate (26 mg, 69 mmol) in CH 2 Cl 2 (1 ml) was stirred for 1h at 25° C. The mixture was diluted by Et 2 O and then filtered. The concentrated crude product was chromatographed to give 5.2 mg of 35 (71.9%) as yellow crystal: mp 138-140° C.; IR (KBr) 2959, 2892, 1683, 1616, 1549, 1441, 1360 cm −1 ; 1H NMR (CDCl 3 ) δ 1.14 (m, 2H), 1.35 (m, 2H), 2.06 (s, 3H), 4.02 (m, 2H), 4.16 (m, 2H), 6.63 (dd, J=2.4, 4.8 Hz, 1H), 6.76 (d, J=4.8 Hz, 1H), 7.39 (s, 1H); 13 C NMR (CDCl 3 ) δ 187.6, 159.6, 140.3, 135.4, 131.0, 127.9, 124.8, 106.2, 66.0, 33.4, 16.9, 12.9; MS m/z 230 (M + ), 202, 158; HRMS for C 14 H 14 O 3 calcd 230.0942, found 230.0948; UV γmax (methanol) 230 nm (e 6543), 330 (e 3484).
Example III
[0110] Synthesis of Compound 42
[0111] Compound 36 . To a solution of 27 (Example II) (37 mg, 0.18 mmol) in pyridine (3 ml) was added TESCl (0.25 ml, 0.624 mmol). The mixture was stirred at 60° C. for 0.5 h under N 2 . After concentration and chromatography, it gave 50 mg of 36 (87%) as colorless oil: IR (KBr) 2952, 2872, 1703, 1622, 1461, 1414, 1226 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.58 (q, J=7.8 Hz, 6H), 0.97 (m, 10H), 1.25 (m, 2H), 1.58 (m, 1H), 1.85 (m, 2H), 1.98 (s, 3H), 2.42 (m, 2H), 3.09 (b, 1H), 4.01 (d, J=3 Hz, 1H); 13 C NMR (CDCl 3 ) δ 206.0, 205.0, 147.0, 128.6, 72.6, 43.0, 39.6, 32.1, 21.4, 19.6, 18.0, 11.5, 6.5, 4.5; MS m/z 320 (M + ), 291, 259, HRMS for C 18 H 28 O 3 Si calcd 320.1808, found 320.1803.
[0112] Compound 37 . The solution of 36 (278 mg, 0.869 mmol) and phenylseleninic anhydride (320 mg, 0.889 mmol) in chlorobenzene (2.5 ml) was stirred at 95° C. for 0.5 h under N 2 . The mixture was then concentrated and chromatographed to give 58.7 mg of 36 and 131.2 mg of 37 (60.2%) as colorless gum: IR(KBr) 2952, 2878, 1730, 1690, 1636, 1454, 1240cm −1 ; 1 H NMR (CDCl 3 ) δ 0.52 (q, J=7.8 Hz, 6H), 0.85 (t, J=7.8 Hz, 9H), 1.20 (m, 1H), 1.36 (m, 1H), 1.69 (m, 1H), 1.82 (m, 1H), 2.06 (s, 3H), 3.58 (s, 1H), 4.26 (d, J=2.4 Hz, 1H), 6.45 (dd, J=2.1, 6 Hz, 1H), 7.33 (dd, J=2.1, 6 Hz, 1H); 13 C NMR (CDCl 3 ) δ 205.9, 195.3, 153.2, 144.3, 139.4, 127.7, 72.1, 47.3, 32.4, 20.1, 19.7, 11.4, 6.4, 4.4; MS m/z 318 (M + ), 289, 261; HRMS for C 18 H 26 O 3 Si calcd 318.1651, found 318.1658.
[0113] Compound 40 . To a solution of 37 (9.5 mg, 0.0299 mmol), CeCl 3 .7H 2 O (58.5 mg, 0.157 mmol) in MeOH (0.3 ml) was added NaBH 4 (excess) at 25° C. It was stirred for 30 min. Then the mixture was partitioned between Et 2 O and saturated NH 4 Cl. The ether extract was dried by MgSO 4 and concentrated to give crude product 38 as pale yellow oil.
[0114] To the solution of above 38 in CH 2 Cl 2 (0.2 ml) was added Et 3 N (5 ml, 0.036 mmol) and MsCl (5 ml, 0.965 mmol) at 25° C. The mixture was stirred for 5 min and then separated between Et 2 O and saturated NaHCO 3 . Then the ether extract was washed by saline and dried by MgSO 4 . After concentration, it was chromatographed to give 8.2 mg of 40 (90.3%) as yellow gum: IR (KBr) 3557, 3449, 2946, 2878, 1716, 1643, 1461, 1112 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.66 (q, J=7.8 Hz, 6H), 0.87 (m, 2H), 0.98 (t, J=7.8 Hz, 9H), 1.26 (m, 2H), 1.86 (s, 3H), 2.55 (d, J=3.9 Hz, 1H), 3.24 (s, 1H), 4.94 (d, J=2.1 Hz, 1H), 6.35 (m, 2H), 6.46 (m, 1H); 13 C NMR (CDCl 3 ) δ 148.9, 140.0, 130.4, 117.8, 117.5, 77.0, 68.6, 61.9, 16.1,11.6, 7.8, 6.8, 5.0; MS m/z 304 (M + ), 287, 275; HRMS for C 18 H 28 O 2 Si calcd 304.1859, found 304.1860.
[0115] Compound 41 . A solution of 40 (1.2 mg, 3.95 mmol) and Dess-Martin reagent (2.2 mg, 5.19 mmol) in CH 2 Cl 2 (0.2 ml) was stirred for 30 min at 25° C. The mixture was separated between Et 2 O and 10% Na 2 SO 3 . Then the ether extract was washed by saline and dried by MgSO 4 . After concentration, it was chromatographed to give 1.1 mg of 41 (92.3%) as yellow gum: IR (KBr) 2952, 2872, 1690, 1610, 1549, 1354, 1132 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.71 (q, J=7.8 Hz, 6H), 0.85 (m, 1H), 0.97 (t, J=7.8 Hz, 9H), 1.21 (m, 2H), 1.45 (m, 1H), 2.08 (s, 3H), 4.50 (s, 1H), 6.66 (dd, J=2.4, 4.8 Hz, 1H), 6.72 (d, J=5.1 Hz, 1H), 7.25 (s, 1H); 13 C NMR (CDCl 3 ) δ 193.3, 161.2, 140.7, 131.8, 131.2, 128.3, 122.8, 32.9, 17.1, 12.5, 10.3, 6.9, 5.2; MS m/z 302 (M + ), 273, 245; HRMS for C 18 H 26 O 2 Si calcd 302.1702, found 302.1710; UV γmax 227nm (e 15612), 323nm (e 10720).
[0116] Compound 42 . To a solution of 41 (9.0 mg, 0.0298 mmol) in acetone (0.8 ml) and H 2 O (0.4 ml) was added some p-TsOH. The mixture was stirred for 30 min. Then it was partitioned between Et 2 O and saturated NaHCO 3 . The ether extract was washed by saline and dried by MgSO 4 After concentration, it was chromatographed to give quantitative 42 as yellow gum: IR (KBr) 3449, 3013, 2925, 1663, 1609, 1441, 1367, 1260 cm −1 ; 1 H NMR (CDCl 3 ) δ 0.81 (m, 1H), 1.25 (m, 1H), 1.36 (m, 1H), 1.44 (m, 1H), 2.12 (s, 3H), 3.82 (d, J=2.4 Hz, 1H), 4.55 (d, J=2.1 Hz, 1H), 6.70 (dd, J=2.7, 5.1 Hz, 1H), 6.81 (t, 1H), 7.32 (s, 1H); 13 C NMR (CDCl 3 ) δ 194.2, 162.2, 140.9, 132.7, 131.4, 126.5, 124.1, 74.6, 32.8, 17.0, 12.7, 10.3; MS m/z 188 (M + ), 160, 145; HRMS for C 12 H 12 O 2 calcd 188.0837, found 188.0840; UV γmax (methanol) 227 nm (e 13626), 323nm (e 7474).
[0117] The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.
|
The present invention provides a method of synthesizing compounds of formula (I) or (II):
wherein R 1 is hydrogen, R′ is (C 1 -C 4 )alkyl and X is a hydroxyl protecting group.
| 2 |
This is a continuation-in-part application of application Ser. No. 09/462,282, filed Mar. 16, 2000, now abandoned entitled DIRECT SMELTING PROCESS which entered the national phase on Jan. 5, 2000, which is a national phase application of PCT/AU99/00583 filed on Jul. 1, 1999.
The present invention relates to a process for producing molten metal (which term includes metal alloys), in particular although by no means exclusively iron, from metalliferous feed material, such as ores, partly reduced ores and metal-containing waste streams, in a metallurgical vessel containing a molten bath.
The present invention relates particularly to a molten metal bath-based direct smelting process for producing molten metal from a metalliferous feed material.
BACKGROUND OF THE INVENTION
The most widely used process for producing molten metal is based on the use of a blast furnace. Solid material is charged into the top of the furnace and molten iron is tapped from the hearth. The solid material includes iron ore (in sinter, lump or pellet form), coke, and fluxes and forms a permeable burden that moves downwardly. Preheated air, which may be oxygen enriched, is injected into the bottom of the furnace and moves upwardly through the permeable bed and generates carbon monoxide and heat by combustion of coke. The result of these reactions is to produce molten iron and slag.
A process that produces iron by reduction of iron ore below the melting point of the iron produced is generally classified as a “direct reduction process” and the product is referred to as DRI.
The FIOR (Fluid Iron Ore Reduction) process is an example of direct reduction process. The process reduces iron ore fines as the fines are gravity-fed through each reactor in a series of fluid bed reactors. The fines are reduced by compressed reducing gas that enters the bottom of the lowest reactor in the series and flows counter-current to the downward movement of fines.
Other direct reduction processes include moving shaft furnace-based processes, static shaft furnace-based processes, rotary hearth-based processes, rotary kiln-based processes, and retort-based processes.
The COREX process produces molten iron directly from coal without the blast furnace requirement of coke. The process includes 2-stage operation in which:
(a) DRI is produced in a shaft furnace from a permeable bed of iron ore (in lump or pellet form), coal and fluxes; and
(b) the DRI is then charged without cooling into a connected melter gasifier.
Partial combustion of coal in the fluidised bed of the melter gasifier produces reducing gas for the shaft furnace.
Another known group of processes for producing molten iron is based on cyclone converters in which iron ore is melted by combustion of oxygen and reducing gas in an upper melting cyclone and is smelted in a lower smelter containing a bath of molten iron. The lower smelter generates the reducing gas for the upper melting cyclone.
A process that produces molten metal directly from ores is generally referred to as a “direct smelting process”.
One known group of direct smelting processes is based on the use of electric furnaces as the major source of energy for the smelting reactions.
Another known direct smelting process, which is generally referred to as the Romelt process, is based on the use of a large volume, highly agitated slag bath as the medium for smelting top-charged metal oxides to metal and for post-combusting gaseous reaction products and transferring the heat as required to continue smelting metal oxides. The Romelt process includes injection of oxygen enriched air or oxygen into the slag via a lower row of tuyeres to provide slag agitation and injection of oxygen into the slag via an upper row of tuyeres to promote post-combustion. In the Romelt process the metal layer is not an important reaction medium.
Another known group of direct smelting processes that are slag-based is generally described as “deep slag” processes. These processes, such as DIOS and AISI processes, are based on forming a deep layer of slag with 3 regions, namely: an upper region for post-combusting reaction gases with injected oxygen; a lower region for smelting metal oxides to metal; and an intermediate region which separates the upper and lower regions. As with the Romelt process, the metal layer below the slag layer is not an important reaction medium.
Another known direct smelting process which relies on a molten metal layer as a reaction medium, and is generally referred to as the HIsmelt process, is described in International application PCT/AU96/00197 (WO 96/31627) in the name of the applicant.
The HIsmelt process as described in the International application comprises:
(a) forming a bath of molten iron and slag in a vessel;
(b) injecting into the bath:
(i) metalliferous feed material, typically metal oxides; and
(ii) a solid carbonaceous material, typically coal, which acts as a reductant of the metal oxides and a source of energy; and
(c) smelting the metalliferous feed material to metal in the metal layer.
The HIsmelt process also comprises post-combusting reaction gases , such as CO and H 2 , released from the bath in the space above the bath with oxygen-containing gas and transferring the heat generated by the post-combustion to the bath to contribute to the thermal energy required to smelt the metalliferous feed materials.
The HIsmelt process also comprises forming a transition zone above the nominal quiescent surface of the bath in which there is a favourable mass of ascending and thereafter descending droplets or splashes or streams of molten metal and/or slag which provide an effective medium to transfer to the bath the thermal energy generated by post-combusting reaction gases above the bath.
The HIsmelt process as described in the International application is characterised by forming the transition zone by injecting a carrier gas and metalliferous feed material and/or solid carbonaceous material and/or other solid material into the bath through a section of the side of the vessel that is in contact with the bath and/or from above the bath so that the carrier gas and the solid material penetrate the bath and cause molten metal and/or slag to be projected into the space above the surface of the bath.
The HIsmelt process as described in the International application is an improvement over earlier forms of the HIsmelt process which form the transition zone by bottom injection of gas and/or carbonaceous material into the bath which causes droplets and splashes and streams of molten metal and slag to be projected from the bath.
SUMMARY OF THE INVENTION
This applicant has carried out extensive pilot plant work on the HIsmelt process and has made a series of significant findings in relation to the process.
In general terms, the present invention provides a direct smelting process for producing metals from a metalliferous feed material which includes the steps of:
(a) forming a molten bath having a metal layer and a slag layer on the metal layer in a metallurgical vessel;
(b) injecting metalliferous feed material and solid carbonaceous material into the metal layer via a plurality of lances/tuyeres;
(c) smelting metalliferous material to metal in the metal layer;
(d) causing molten material to be projected as splashes, droplets, and streams into a space above a nominal quiescent surface of the molten bath to form a transition zone; and
(e) injecting an oxygen-containing gas into the vessel via one or more than one lance/tuyere to post-combust reaction gases released from the molten bath, whereby the ascending and thereafter descending splashes, droplets and streams of molten material in the transition zone facilitate heat transfer to the molten bath, and whereby the transition zone minimises heat loss from the vessel via the side walls in contact with the transition zone;
and includes the step of controlling the process by maintaining a high slag inventory.
The invention further provides a direct smelting process for producing metals from a metalliferous feed material which includes the steps of:
(a) forming a molten bath having a metal layer and a slag layer on the metal layer in a metallurgical vessel having side walls, said slag layer providing a high inventory in the vessel;
(b) injecting metalliferous feed material and solid carbonaceous material into the metal layer via a plurality of lances/tuyeres;
(c) smelting metalliferous material to metal in the metal layer;
(d) generating a gas flow from the metal layer at a flow rate of at least 0.04 Nm 3 /s/m 2 of the metal layer area at the interface between the metal layer and the slag layer (under quiescent conditions), which gas flow causes molten material to be projected as splashes, droplets, and streams into a space above a nominal quiescent surface of the molten bath to form a transition zone, the molten material and particularly the slag of the transition zone continuously splashing the side walls and reducing heat loss via the side walls; and
(e) injecting an oxygen-containing gas into the vessel via one or more than one lance/tuyere to post-combust reaction gases released from the molten bath, whereby the ascending and thereafter descending splashes, droplets and streams of molten material in the transition zone facilitate heat transfer to the molten bath, and whereby the transition zone minimises heat loss from the vessel via the side walls in contact with the transition zone.
The above-described gas flow rate from the metal layer of at least 0.04 Nm 3 /s/m 2 area of the metal layer is a substantially higher bath-derived gas flow rate than the rate recommended to successfully operate the Romelt, DIOS, and AISI processes as described above and is a significant difference between the process of the present invention and these known direct smelting processes.
The term “smelting” is understood herein to mean thermal processing wherein chemical reactions that reduce the metalliferous feed material take place to produce liquid metal.
The term “quiescent surface” in the context of the molten bath is understood to mean the surface of the molten bath under process conditions in which there is no gas/solids injection and therefore no bath agitation.
The space above the nominal quiescent surface of the molten bath is hereinafter referred to as the “top space”.
A significant outcome of the pilot plant work is that it is important to maintain high levels of slag in the vessel (and more particularly in the transition zone) and to generate sufficient gas flow from the metal layer such that the side walls are continuously splashed by molten material, particularly slag, in the transition zone in order to control heat losses from the vessel. The importance of slag to the HIsmelt process is a significant departure from previous work on the HIsmelt process. In the previous work the amount of slag was not considered to be as important to the process.
Preferably the gas flow rate is at least 0.2 Nm 3 /s/m 2 of the metal layer area.
Preferably the gas flow rate is less than 2 Nm 3 /s/m 2 .
The gas flow from the metal layer may be caused by any one or more of a number of factors. For example, gas flow may be generated at least in part as a result of injection of metalliferous feed material and solid carbonaceous material into the metal layer. By way of further example, the gas flow may be generated at least in part as a result of injection of a carrier gas into the metal layer with injected metalliferous feed material and/or solid carbonaceous material. By way of further example, gas flow may be generated at least in part as a result of bottom and/or side wall injection of a gas into the metal layer.
Preferably the gas flow rate of at least 0.04 Nm 3 /s/m 2 of the metal layer area forms a metal-rich transition zone above the metal layer and a slag-rich transition zone above the metal-rich transition zone.
The concept of a “high slag inventory” may be understood in the context of the depth of the slag layer in the vessel.
Preferably the process includes maintaining the high slag inventory by controlling the slag layer to be 0.5 to 4 meters deep under stable operating conditions.
More preferably the process includes maintaining the high slag inventory by controlling the slag layer to be 1.5 to 2.5 meters deep under stable operating conditions.
It is preferred particularly that the process includes maintaining the high slag inventory by controlling the slag layer to be at least 1.5 meters deep under stable operating conditions.
The concept of a “high slag inventory” may also be understood in the context of the amount of slag compared to the amount of metal in the vessel.
Preferably, when the process is operating under stable conditions, the process includes maintaining the high slag inventory by controlling the weight ratio of metal:slag to be between 4:1 and 1:2.
More preferably the process includes maintaining the high slag inventory by controlling the weight ratio of metal:slag to be between 3:1 and 1:1.
It is preferred particularly that the process includes maintaining the high slag inventory by controlling the metal:slag weight ratio to be between 3:1 and 2:1.
The amount of slag in the vessel, ie the slag inventory, has a direct impact on the amount of slag that is in the transition zone.
The relatively low heat transfer characteristics of slag compared to metal is important in the context of minimising heat loss from the transition zone to the side walls and from the vessel via the side walls of the vessel.
By appropriate process control, slag in the transition zone can form a layer or layers on the side walls that adds resistance to heat loss from the side walls.
Therefore, by changing the slag inventory it is possible to increase or decrease the amount of slag in the transition zone and on the side walls and therefore control the heat loss via the side walls of the vessel.
The slag may form a “wet” layer or a “dry” layer on the side walls. A “wet” layer comprises a frozen layer that adheres to the side walls, a semi-solid (mush) layer, and an outer liquid film. A “dry” layer is one in which substantially all of the slag is frozen.
The amount of slag in the vessel also provides a measure of control over the extent of post combustion.
Specifically, if the slag inventory is too low there will be increased exposure of metal in the transition zone and therefore increased oxidation of metal and dissolved carbon in metal and the potential for reduced post-combustion and consequential decreased post combustion, notwithstanding the positive effect that metal in the transition zone has on heat transfer to the metal layer.
In addition, if the slag inventory is too high the one or more than one oxygen-containing gas injection lance/tuyere will be buried in the transition zone and this minimises movement of top space reaction gases to the end of the or each lance/tuyere and, as a consequence, reduces potential for post-combustion.
The amount of slag in the vessel, ie the slag inventory, measured in terms of the depth of the slag layer or the weight ratio of metal:slag, may be controlled by the tapping rates of metal and slag.
The production of slag in the vessel may be controlled by varying the feed rates of metalliferous feed material, carbonaceous material, and fluxes to the vessel and operating parameters such as oxygen-containing gas injection rates.
The process of the present invention is characterised by controlling heat transfer via the transition zone to the metal layer and controlling heat loss from the vessel via the transition zone.
As noted above, in particular the present invention is preferably characterised by controlling the process by maintaining a high slag inventory.
In addition, the present invention is more preferably characterised by controlling the process by means of the following process features, separately or in combination;
(a) locating the one or more than one oxygen-containing gas injection lance/tuyere and injecting the oxygen-containing gas at a flow rate so that:
(i) the oxygen-containing gas is injected towards the slag layer and penetrates the transition zone; and
(ii) the stream of oxygen-containing gas deflects the splashes, droplets and streams of molten material around a lower section of the or each lance/tuyere and a gas continuous space described as a “free space” forms around the end of the or each lance/tuyere;
(b) controlling heat loss from the vessel by splashing predominantly slag onto the side walls of the vessel in contact with the transition zone by adjusting one or more of:
(i) the amount of slag in the molten bath;
(ii) the injection flow rate of the oxygen-containing gas through the one or more than one oxygen-containing gas injection lance/tuyere; and
(iii) the flow rate of metalliferous feed material and carbonaceous material through the lances/tuyeres.
In situations where the metalliferous feed material is an iron-containing material, the present invention is also preferably characterised by controlling the process by controlling the level of dissolved carbon in molten iron to be at least 3 wt % and maintaining the slag in a strongly reducing condition leading to FeO levels of less than 6 wt %, more preferably less than 5 wt %, in the slag layer and in the transition zone.
Preferably, the metallurgical vessel includes:
(a) the above-described one or more than one lance/tuyere for injecting oxygen-containing gas and the lances/tuyeres for injecting solid materials, such as metalliferous material, carbonaceous material (typically coal) and fluxes, into the vessel;
(b) outlets for discharging molten metal and slag from the vessel; and
(c) one or more off-gas outlet.
In order to operate the process it is essential that the vessel contains a molten bath having a metal layer and a slag layer on the metal layer.
The term “metal layer” is understood herein to mean that region of the bath that is predominantly metal.
The term “slag layer” is understood herein to mean that region of the bath that is predominantly slag.
An important feature of the process of the present invention is that metalliferous material is smelted to metal at least predominantly in the metal layer of the molten bath.
In practice, there will be a proportion of the metalliferous material that is smelted to metal in other regions of the vessel, such as the slag layer. However, the objective of the process of the present invention, and an important difference between the process and prior art processes, is to maximise smelting of metalliferous material in the metal layer.
As a consequence of the above, the process includes injecting metalliferous material and carbonaceous material, which acts as a source of reductant and as a source of energy, into the metal layer.
One option is to inject metalliferous material and carbonaceous material via lances/tuyeres positioned above and extending downwardly towards the metal layer. Typically, the lances/tuyeres extend through side walls of the vessel and are angled inwardly and downwardly towards the surface of the metal layer.
Another option, although by no means not the only other option, is to inject metalliferous material and carbonaceous material via tuyeres in the bottom of the vessel or in side walls of the vessel that contact the metal layer.
The injection of metalliferous material and carbonaceous material may be through the same or separate lances/tuyeres.
Another important feature of the process of the present invention is that it causes molten material, typically in the form of splashes, droplets, and streams, to be projected upwardly from the molten bath into at least part of the top space above the quiescent surface of the bath to form the transition zone.
The transition zone is quite different to the slag layer. By way of explanation, under stable operating conditions of the process the slag layer comprises gas bubbles in a liquid continuous volume whereas the transition zone comprises splashes, droplets, and streams of molten material in a gas continuous volume.
Preferably the process includes causing molten material to be projected as splashes, droplets and streams into the top space above the transition zone.
Another important feature of the present invention is that it post-combusts reaction gases, such as carbon monoxide and hydrogen, generated in the molten bath, in the top space (including the transition zone) above the nominal quiescent surface of the bath and transfers the heat generated by the post-combustion to the metal layer to maintain the temperature of the molten bath—as is essential in view of endothermic reactions in that layer.
Preferably the oxygen-containing gas is air.
More preferably the air is pre-heated.
Typically, the air is preheated to 1200° C.
The air may be oxygen enriched.
Preferably the level of post-combustion is at least 40%, where post-combustion is defined as: [ CO 2 ] + [ H 2 O ] [ CO 2 ] + [ H 2 O ] + [ CO ] + [ H 2 ]
where:
[CO 2 ]=volume % of CO 2 in off-gas
[H 2 O]=volume % of H 2 O in off-gas
[CO]=volume % of CO in off-gas
[H 2 ]=volume % of H 2 in off-gas
The transition zone is important for 2 reasons.
Firstly, the ascending and thereafter descending splashes, droplets and streams of molten material are an effective means of transferring to the molten bath the heat generated by post-combustion of reaction gases in the top space above the quiescent surface of the bath.
Secondly, the molten material, and particularly the slag, in the transition zone is an effective means of minimising heat loss via the side walls of the vessel.
A fundamental difference between the process of the present invention and prior art processes is that in the process of the present invention the main smelting region is the metal layer and the main oxidation (ie heat generation) region is above and in the transition zone and these regions are spatially well separated and heat transfer is via physical movement of molten metal and slag between the two regions.
Preferably the transition zone is generated by injecting metalliferous material and carbonaceous material in a carrier gas through lances/tuyeres that extend downwardly towards the metal layer.
More preferably, as noted above, lances/tuyeres extend through the side walls of the vessel and are angled inwardly and downwardly towards the metal layer.
This injection of the solid material towards and thereafter into the metal layer has the following consequences:
(a) the momentum of the solid material/carrier gas causes the solid material and gas to penetrate the metal layer;
(b) the carbonaceous material, typically coal, is devolatilised and thereby produces gas in the metal layer;
(c) carbon predominantly dissolves into the metal and partially remains as solid;
(d) the metalliferous material is smelted to metal by carbon derived from injected carbon as described above in item (c) and the smelting reaction generates carbon monoxide gas; and
(e) the gases transported into the metal layer and generated via devolatilisation and smelting produce significant buoyancy uplift of molten metal, solid carbon and slag (which is drawn into the metal layer as a consequence of solid/gas injection) from the metal layer which results in upward movement of splashes, droplets and streams of molten metal and slag, and these splashes, droplets, and streams entrain further slag as they move through the slag layer.
Another important feature of the present invention is that the location and operating parameters of the one or more than one lance/tuyere that injects the oxygen-containing gas and the operating parameters that control the transition zone are selected so that:
(a) the oxygen-containing gas is injected towards the slag layer and penetrates the transition zone;
(b) the stream of oxygen-containing gas deflects the splashes, droplets and streams of molten material so that, in effect:
(i) the transition zone extends upwardly around the lower section of the one or more than one lance/tuyere; and
(ii) a gas continuous space described as a “free space” forms around the end of the one or more than one lance/tuyere.
The formation of the free space is an important feature because it makes it possible for reaction gases in the top space of the vessel to be drawn into the region of the end of the one or more than one oxygen-containing gas injection lance/tuyere and to be post-combusted in the region. In this context, the term “free space” is understood to mean a space which contains practically no metal and slag.
In addition, the above-described deflection of molten material shields to some degree the side walls of the vessel from the combustion zone generated at the end of the or each lance/tuyere. Also it provides a means for returning more energy back to the bath from gases post combusted in the top space.
Preferably the process includes injecting the oxygen-containing gas into the vessel in a swirling motion.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described further by way of example with reference to the accompanying drawing which is a vertical section through a metallurgical vessel illustrating in schematic form a preferred embodiment of the process of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following description is in the context of smelting iron ore to produce molten iron and it is understood that the present invention is not limited to this application and is applicable to any suitable metallic ores and/or concentrates—including partially reduced metallic ores and waste revert materials.
The vessel shown in the figure has a hearth that includes a base 3 and sides 55 formed from refractory bricks; side walls 5 which form a generally cylindrical barrel extending upwardly from the sides 55 of the hearth and which include an upper barrel section 51 and a lower barrel section 53 ; a roof 7 ; an outlet 9 for off-gases; a forehearth 57 for discharging molten metal continuously; and a tap-hole 61 for discharging molten slag.
In use, the vessel contains a molten bath of iron and slag which includes a layer 15 of molten metal and a layer 16 of molten slag on the metal layer 15 . The arrow marked by the numeral 17 indicates the position of the nominal quiescent surface of the metal layer 15 and the arrow marked by the numeral 19 indicates the position of nominal quiescent surface of the slag layer 16 . The term “quiescent surface” is understood to mean the surface when there is no injection of gas and solids into the vessel.
The vessel also includes 2 solids injection lances/tuyeres 11 extending downwardly and inwardly at an angle of 30-60° to the vertical through the side walls 5 and into the slag layer 16 . The position of the lances/tuyeres 11 is selected so that the lower ends are above the quiescent surface 17 of the metal layer 15 .
In use, iron ore, solid carbonaceous material (typically coal), and fluxes (typically lime and magnesia) entrained in a carrier gas (typically N 2 ) are injected into the metal layer 15 via the lances/tuyeres 11 . The momentum of the solid material/carrier gas causes the solid material and gas to penetrate the metal layer 15 . The coal is devolatilised and thereby produces gas in the metal layer 15 . Carbon partially dissolves into the metal and partially remains as solid carbon. The iron ore is smelted to metal and the smelting reaction generates carbon monoxide gas. The gases transported into the metal layer 15 and generated via devolatilisation and smelting produce significant buoyancy uplift of molten metal, solid carbon, and slag (drawn into the metal layer 15 as a consequence of solid/gas/injection) from the metal layer 15 which generates an upward movement of splashes, droplets and streams of molten metal and slag, and these splashes, and droplets, and streams entrain slag as they move through the slag layer 16 .
The buoyancy uplift of molten metal, solid carbon and slag causes substantial agitation in the metal layer 15 and the slag layer 16 , with the result that the slag layer 16 expands in volume and has a surface indicated by the arrow 30 . The extent of agitation is such that there is reasonably uniform temperature in the metal and the slag regions—typically, 1450-1550° C. with a temperature variation of the order of 30° in each region.
In addition, the upward movement of splashes, droplets and streams of molten material caused by the buoyancy uplift of molten metal, solid carbon, and slag extends into the top space 31 above the molten bath in the vessel and:
(a) forms a transition zone 23 ; and
(b) projects some molten material (predominantly slag) beyond the transition zone and onto the part of the upper barrel section 51 of the side walls 5 that is above the transition zone 23 and onto the roof 7 .
In general terms, the slag layer 16 is a liquid continuous volume, with gas bubbles therein, and the transition zone 23 is a gas continuous volume with splashes, droplets, and streams of molten metal and slag.
The vessel further includes a lance 13 for injecting an oxygen-containing gas (typically pre-heated oxygen enriched air) which is centrally located and extends vertically downwardly into the vessel. The position of the lance 13 and the gas flow rate through the lance 13 are selected so that the oxygen-containing gas penetrates the central region of the transition zone 23 and maintains an essentially metal/slag free space 25 around the end of the lance 13 . The lance 13 includes an assembly which causes the oxygen-containing gas to be injected in a swirling motion into the vessel.
The injection of the oxygen-containing gas via the lance 13 post-combusts reaction gases CO and H 2 in the transition zone 23 and in the free space 25 around the end of the lance 13 and generates high temperatures of the order of 2000° C. or higher in the gas space. The heat is transferred to the ascending and descending splashes droplets, and streams, of molten material in the region of gas injection and the heat is then partially transferred to the metal layer 15 when the metal/slag returns to the metal layer 15 .
The free space 25 is important to achieving high levels of post combustion because it enables entrainment of gases in the space above the transition zone 23 into the end region of the lance 13 and thereby increases exposure of available reaction gases to post combustion.
The combined effect of the position of the lance 13 , gas flow rate through the lance 13 , and upward movement of splashes, droplets and streams of molten material is to shape the transition zone 23 around the lower region of the lance 13 —generally identified by the numerals 27 . This shaped region provides a partial barrier to heat transfer by radiation to the side walls 5 .
Moreover, the ascending and descending droplets, splashes and streams of material is an effective means of transferring heat from the transition zone 23 to the molten bath with the result that the temperature of the transition zone 23 in the region of the side walls 5 is of the order of 1450° C.-1550° C.
The vessel is constructed with reference to the levels of the metal layer 15 , the slag layer 16 , and the transition zone 23 in the vessel when the process is operating and with reference to splashes, droplets and streams of molten metal and slag that are projected into the top space 31 above the transition zone 23 when the process is operating, so that:
(a) the hearth and the lower barrel section 53 of the side walls 5 that contact the metal/slag layers 15 / 16 are formed from bricks of refractory material (indicated by the cross-hatching in the figure);
(b) at least part of the lower barrel section 53 of the side walls 5 is backed by water cooled panels 8 ; and
(c) the upper barrel section 51 of the side walls 5 and the roof 7 that contact the transition zone 23 and the top space 31 are formed from water cooled panels 57 , 59 .
Each water cooled panel 8 , 57 , 59 in the upper section 10 of the side walls 5 has parallel upper and lower edges and parallel side edges and is curved so as to define a section of the cylindrical barrel. Each panel includes an inner water cooling pipe and an outer water cooling pipe. The pipes are formed into a serpentine configuration with horizontal sections interconnected by curved sections. Each pipe further includes a water inlet and a water outlet. The pipes are displaced vertically so that the horizontal sections of the outer pipe are not immediately behind the horizontal sections of the inner pipe when viewed from an exposed face of the panel, ie the face that is exposed to the interior of the vessel. Each panel further includes a rammed refractory material which fills the spaces between the adjacent horizontal sections of each pipe and between the pipes.
The water inlets and the water outlets of the pipes are connected to a water supply circuit (not shown) which circulates water at high flow rate through the pipes.
In use the operating conditions are controlled so that there is sufficient slag contacting the water cooled panels 57 , 59 and sufficient heat extraction from the panels to build-up and maintain a layer of slag on the panels. The slag layer forms an effective thermal barrier to heat loss via the transition zone and the remainder of the top space above the transition zone.
As indicated above, the applicant has identified the following process features in pilot plant work that, separately or in combination, provide effective control of the process.
(a) Controlling the slag inventory, ie the depth of the slag layer and/or the slag/metal ratio, to balance the positive effect of metal in the transition zone 23 on heat transfer with the negative effect of metal in the transition zone 23 on post combustion due to back reactions in the transition zone 23 . If the slag inventory is too low the exposure of metal to oxygen is too high and there is reduced potential for post combustion. On the other hand, if the slag inventory is too high the lance 13 will be buried in the transition zone 23 and there will be reduced entrainment of gas into the free space 25 and reduced potential for post combustion.
(b) Controlling the level of dissolved carbon in metal to be at least 3 wt % and maintaining the slag in a strongly reducing condition leading to FeO levels of less than 6 wt % in the slag layer 16 and in the transition zone 23 .
(c) Selecting the position of the lance 13 and controlling injection rates of oxygen-containing gas and solids via the lance 13 and lances/tuyeres 11 to maintain the essentially metal/slag free region around the end of the lance 13 and to form the transition zone 23 around the lower section of the lance 13 .
(d) Controlling heat loss from the vessel by splashing with slag the side walls of the vessel that are in contact with the transition zone 23 or are above the transition zone 23 by adjusting one or more of:
(i) the slag inventory; and
(ii) the injection flow rate through the lance 13 and the lances/tuyeres 11 .
The pilot plant work referred to above was carried out as a series of extended campaigns by the applicant at its pilot plant at Kwinana, Western Australia.
The pilot plant work was carried out with the vessel shown in the figure and described above and in accordance with the process conditions described above.
The pilot plant work evaluated the vessel and investigated the process under a wide range of different:
(a) feed materials;
(b) solids and gas injection rates;
(c) slag inventories—measured in terms of the depth of the slag layer and the slag:metal ratios;
(d) operating temperatures; and
(e) apparatus set-ups.
Table 1 below sets out relevant data during start-up and stable operating conditions for the pilot plant work.
START
STABLE
UP
OPERATION
Bath Temperature
(° C.)
1450
1450
Operating Pressure
(bar g)
0.5
0.5
HAB Air
(kNm 3 /h)
26.0
26.0
Oxygen in HAB
(%)
20.5
20.5
HAB Temperature
(C.)
1200
1200
DSO Ore
(t/h)
5.9
9.7
Coal
(t/h)
5.4
6.1
Calcined Flux
(t/h)
1.0
1.4
Ore Feed Temp
(C.)
25.0
25.0
Hot Metal
(t/h)
3.7
6.1
Slag
(t/h)
2.0
2.7
Post Combustion
(%)
60.0
60.0
Offgas Temperature
(C.)
1450
1450
Heat Transfer to Bath
(MW)
11.8
17.3
Heat Loss to Panels
(MW)
12.0
8.0
Coal Rate
(kg/thm)
1453
1003
Gas Flow Rate from
Nm 3 /h
6,200
8,600
Metal Layer
Mn 3 /s/m 2
0.34
0.47
The iron ore was sourced from Hamersley as a normal fine direct shipping ore and contained 64.6% iron, 4.21% SiO 2 , and 2.78% Al 2 O 3 on a dry basis.
An anthracite coal was used both as a reductant and a source of carbon and hydrogen to combust and supply energy to the process. The coal had a calorific value of 30.7 MJ/kg, an ash content of 10%, and a volatile level of 9.5%. Other characteristics included 79.82% total carbon, 1.8% H 2 O, 1.59% N 2 , 3.09% O 2 , and 3.09% H 2 .
The process was operated to maintain a slag basicity of 1.3 (CaO/SiO 2 ratio) using a combination of fluxes of lime and magnesia. The magnesia contributed MgO thereby reducing the corrosiveness of the slag to the refractory by maintaining appropriate levels of MgO in the slag.
Under start-up conditions the pilot plant operated with: a hot air blast rate of 26,000 Nm 3 /h at 1200° C.; a post combustion rate of 60% ((CO 2 +H 2 O)/(CO+H 2 +CO 2 +H 2 O)); and a feed rate of iron ore fines of 5.9 t/h, a feed rate of coal of 5.4 t/h and a feed rate of flux of 1.0 t/h, all injected as solids using N 2 as a carrier gas. There was little or no slag in the vessel and there was not sufficient opportunity to form a frozen slag layer on the side panels. As a consequence, the cooling water heat loss was relatively high at 12 MW. The pilot plant operated at a production rate of 3.7 t/h of hot metal (4.5 wt % C) and a coal rate of 1450 kg coal/t hot metal produced.
Under stable operating conditions, with control of slag inventory and a frozen slag layer on the water cooling panels forming the side walls, relatively low heat losses of 8 MW were experienced. The reduction of the heat lost to the water cooling system allowed an increased productivity to 6.1 t/h of hot metal. The increased productivity was obtained at the same hot air blast rate and post combustion as at start-up. Solid infection rates were 9.7 t/h of ore fines and 6.1 t/h of coal along with 1.4 t/h of flux. The improved productivity also improved the coal rate to 1000 kg coal/t hot metal achieved.
Many modifications may be made to the preferred embodiments of the process of the present invention as described above without departing from the spirit and scope of the present invention.
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A direct smelting process for producing metals from a metalliferous feed material is disclosed. The process includes forming a molten bath having a metal layer ( 15 ) and a slag layer ( 16 ) on the metal layer in a metallurgical vessel, injecting metalliferous feed material and solid carbonaceous material into the metal layer via a plurality of lances/tuyeres ( 11 ), and smelting metalliferous material to metal in the metal layer. The process also includes causing molten material to be projected as splashes, droplets, and streams into a top space above a nominal quiescent surface of the molten bath to form a transition zone ( 23 ). The process also includes injecting an oxygen-containing gas into the vessel via one or more than one lance/tuyere ( 13 ) to post-combust reaction gases released from the molten bath, whereby the ascending and thereafter descending splashes, droplets and streams of molten material in the transition zone facilitate heat transfer to the molten bath, and whereby the transition zone minimises heat loss from the vessel via the side walls in contact with the transition zone. The process is controlled by maintaining a high slag inventory and by reducing the heat loss from the vessel through the side walls being continuously splashed by the transition zone.
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BACKGROUND
International Publication Number WO95/10516, published Apr. 20, 1995 discloses compounds of the formula: ##STR5## wherein R can be heterocycloalkyl attached to the carbon of the --C(═Z)-- group by a heteroatom, substituted piperidiny or substituted piperidinylmethyl. The compounds are said to be useful for inhibiting farnesyl protein transferase.
SUMMARY OF THE INVENTION
Compounds of the present invention are represented by Formula I: ##STR6## or an N-oxide thereof, or a pharmaceutically acceptable salt or solvate thereof, wherein;
R and R 2 are independently selected from halo;
R 1 and R 3 are independently selected from the group consisting of H and halo, provided that at least one of R 1 and R 3 is H;
W is N, CH or C when the double bond is present at the C-11 position;
R 4 is --(CH 2 ) n --R 5 or ##STR7## R 5 is ##STR8## R 6 is R 5 or ##STR9## Z 1 and Z 2 are independently selected from the group consisting of ═O and ═S;
n is 1-6; and
n 1 is 0 or 1.
In the compounds of the invention, preferably R is Br, R 2 is halo and R 1 is halo; or R is Br, R 2 is halo and R 3 is halo; or R is Br, R 2 is halo and R 1 and R 3 are each H. R 2 is preferably Br or Cl. When R 1 or R 3 is halo, it is preferably Br or Cl. Z 1 is preferably ═O. Z 2 is preferably ═O. W is preferably CH. Preferred values for n are 1-3. R 5 and R 6 are preferably ##STR10## When R 4 is ##STR11## n 1 is preferably 1 and the resultant piperidinyl group is preferably joined to the methylene at the 4-position carbon ring member.
The compounds of this invention: (i) potently inhibit farnesyl protein transferase, but not geranylgeranyl protein transferase I, in vitro; (ii) block the phenotypic change induced by a form of transforming Ras which is a farnesyl acceptor but not by a form of transforming Ras engineered to be a geranylgeranyl acceptor; (iii) block intracellular processing of Ras which is a farnesyl acceptor but not of Ras engineered to be a geranylgeranyl acceptor; and (iv) block abnormal cell growth in culture induced by transforming Ras.
The compounds of this invention inhibit farnesyl protein transferase and the farnesylation of the oncogene protein Ras. This invention further provides a method of inhibiting ras farnesyl protein transferase, in mammals, especially humans, by the administration of an effective amount of the tricyclic compounds described above. The administration of the compounds of this invention to patients, to inhibit farnesyl protein transferase, is useful in the treatment of the cancers described below.
This invention provides a method for inhibiting or treating the abnormal growth of cells, including transformed cells, by administering an effective amount of a compound of this invention. Abnormal growth of cells refers to cell growth independent of normal regulatory mechanisms (e.g., loss of contact inhibition). This includes the abnormal growth of: (1) tumor cells (tumors) expressing an activated Ras oncogene; (2) tumor cells in which the Ras protein is activated as a result of oncogenic mutation in another gene; and (3) benign and malignant cells of other proliferative diseases in which aberrant Ras activation occurs.
This invention also provides a method for inhibiting or treating tumor growth by administering an effective amount of the tricyclic compounds, described herein, to a mammal (e.g., a human) in need of such treatment. In particular, this invention provides a method for inhibiting or treating the growth of tumors expressing an activated Ras oncogene by the administration of an effective amount of the above described compounds. Examples of tumors which may be inhibited or treated include, but are not limited to, breast cancer, prostate cancer, lung cancer (e.g., lung adenocarcinoma), pancreatic cancers (e.g., pancreatic carcinoma such as, for example, exocrine pancreatic carcinoma), colon cancers (e.g., colorectal carcinomas, such as, for example, colon adenocarcinoma and colon adenoma), myeloid leukemias (for example, acute myelogenous leukemia (AML)), thyroid follicular cancer, myelodysplastic syndrome (MDS), bladder carcinoma and epidermal carcinoma.
It is believed that this invention also provides a method for inhibiting or treating proliferative diseases, both benign and malignant, wherein Ras proteins are aberrantly activated as a result of oncogenic mutation in other genes--i.e., the Ras gene itself is not activated by mutation to an oncogenic form--with said inhibition or treatment being accomplished by the administration of an effective amount of the tricyclic compounds described herein, to a mammal (e.g., a human) in need of such treatment.
For example, the benign proliferative disorder neurofibromatosis, or tumors in which Ras is activated due to mutation or overexpression of tyrosine kinase oncogenes (e.g., neu, src, abl, Ick, and fyn), may be inhibited or treated by the tricyclic compounds described herein.
The tricyclic compounds useful in the methods of this invention inhibit or treat the abnormal growth of cells. Without wishing to be bound by theory, it is believed that these compounds may function through the inhibition of G-protein function, such as ras p21, by blocking G-protein isoprenylation, thus making them useful in the treatment of proliferative diseases such as tumor growth and cancer. Without wishing to be bound by theory, it is believed that these compounds inhibit ras farnesyl protein transferase, and thus show antiproliferative a ctivity against ras transformed cells.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the following terms are used as defined below unless otherwise indicated:
MH+ represents the molecular ion plus hydrogen of the molecule in the mass spectrum;
Bu represent s butyl; Et repres ents ethyl; Me represents methyl; Ph represents phenyl; and
halo represents fluoro, chloro, bromo and iodo.
The following solvents and reagents may be referred to herein by the abbreviations indicated: tetrahydrofuran (THF); ethanol (EtOH); methanol (MeOH); acetic acid (HOAc or AcOH); ethyl acetate (EtOAc); N,N-dimethylformamide (DMF); trifluoroacetic acid (TFA); trifluoroacetic anhydride (TFAA); 1-hydroxybenzotriazole (HOBT); m-chloroperbenzoic acid (MCPBA); triethylamine (Et 3 N); diethyl other (Et 2 O); ethyl chloroformate (CICO 2 Et); and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (DEC).
Rep resentative structures of Formula I with respect to W and the optional double bond are as follows: ##STR12##
Lines drawn into the ring systems indicate that the indicated bond may be attached to any of the substitutable ring carbon atoms.
Certain compounds of the invention may exist in different isomeric (e.g., enantiomers, diastereoisomers and atropisomers) forms. The invention contemplates all such isomers both in pure form and in admixture, including racemic mixtures. Enol forms are also included.
Certain tricyclic compounds will be acidic in nature, e.g. those compounds which possess a carboxyl or phenolic hydroxyl group. These compounds may form pharmaceutically acceptable salts. Examples of such salts may include sodium, potassium, calcium, aluminum, gold and silver salts. Also contemplated are salts formed with pharmaceutically acceptable amines such as ammonia, alkyl amines, hydroxyalkylamines, N-methylglucamine and the like.
Certain basic tricyclic compounds also form pharmaceutically acceptable salts, e.g., acid addition salts. For example, the pyrido-nitrogen atoms may form salts with strong acid, while compounds having basic substituents such as amino groups also form salts with weaker acids. Examples of suitable acids for salt formation are hydrochloric, sulfuric, phosphoric, acetic, citric, oxalic, malonic, salicylic, malic, fumaric, succinic, ascorbic, maleic, methanesulfonic and other mineral and carboxylic acids well known to those in the art. The salts are prepared by contacting the free base form with a sufficient amount of the desired acid to produce a salt in the conventional manner. The free base forms may be regenerated by treating the salt with a suitable dilute aqueous base solution such as dilute aqueous NaOH, potassium carbonate, ammonia and sodium bicarbonate. The free base forms differ from their respective salt forms somewhat in certain physical properties, such as solubility in polar solvents, but the acid and base salts are otherwise equivalent to their respective free base forms for purposes of the invention.
All such acid and base salts are intended to be pharmaceutically acceptable salts within the scope of the invention and all acid and base salts are considered equivalent to the free forms of the corresponding compounds for purposes of the invention.
Compounds of the invention may be made by the methods described in the examples below, and by using the methods described in WO 95/10516-- see, for example, the methods for preparing compounds of Formula 400.00.
Compounds of the invention wherein Z 1 and Z 2 are ═O can be prepared by reacting a compound of the formula II or III ##STR13## wherein all other substituents are as defined for Formula I, with an acid of the formula HOOC--(CH 2 ) n --NHR 7 , wherein n is as defined above and R 7 is an amino protecting group such as t-butoxycarbonyl (BOC). The reaction is carried out using standard amide coupling conditions, for example the reaction can be carried out at room temperature, in an inert solvent such as DMF, in the presence of a condensing agent such as 1-(3-dimethyl-aminopropyl)-3-ethyl-carbodiimide hydrochloride, a base such as N-methylmorpholine and an activating agent such as 1-hydroxybenzo-triazole. The R 7 protecting group is then removed, for example by treatment with trifluoroacetic acid, to obtain the corresponding amine of the formula IIA or IIIA: ##STR14##
To prepare compounds of formula I wherein R 5 or R 6 comprises a cyclic lactam, a compound of formula IIA or IIIA is reacted with 4-bromobutyryl chloride or 4-bromovaleryl chloride, followed by cyclization with a reagent such a NaH. Compounds of formula I wherein R 5 or R 6 comprises a cyclic urea are similarly prepared by reacting an amine of formula IIA or IIIA with 2-bromo ethyl isocyanate or 3-chloropropyl isocyanate, followed as before by cyclization with a reagent such as NaH.
Alternatively, an amine of formula IIA or IIIA can be reacted with lactam-substituted acetic acid under standard amide coupling conditions as described above.
When Z 1 , or Z 1 and Z 2 , represent sulfur, a compound of formula I wherein Z 1 , or Z 1 and Z 2 , is oxygen is reacted with P 2 S 5 , Lawesson's reagent, or another reagent capable of introducing sulfur in place of oxygen. The reaction may take place at elevated temperature in pyridine, toluene or other suitable solvents. For compounds wherein Z 1 and Z 2 are different, the conversion form oxygen to sulfur can be effected before the starting materials (i.e., compounds of formula IIIA and the alkanoyl chloride or isocyanate) are reacted.
Compounds of formula I comprising a pyridyl N-oxide in ring I of the tricyclic portion can be prepared by procedures well known in the art. For example, the compound of formula II can be reacted with MCPBA in a suitable organic solvent, e.g., CH 2 Cl 2 (usually anhydrous). at a suitable temperature, to obtain an N-oxide of formula IIa ##STR15## Generally, the organic solvent solution of formula II is cooled to about 0° C. before the MCPBA is added. The reaction is then allowed to warm to room temperature during the reaction period. The desired product can be recovered by standard separation means, for example, the reaction mixture can be washed with an aqueous solution of a suitable base, e.g., saturated NaHCO 3 or NaOH (e.g., 1N NaOH), and then dried over anhydrous MgSO 4 . The solution containing the product can be concentrated in vacuo, and the product can be purified by standard means, e.g., by chromatography using silica gel (e.g., flash column chromatography).
Compounds of formula II are prepared by methods known in the art, for example by methods disclosed in WO 95/10516, in U.S. Pat. No. 5,151,423 and those described below. Compounds of formula II wherein the C-3 postion of the pyridine ring in the tricyclic structure is substituted by bromo can also be prepared by a procedure comprising the following steps:
(a) reacting an amide of the formula ##STR16## wherein R 11a is Br, R 5a is hydrogen and R 6a is C 1 -C 6 alkyl, aryl or heteroaryl; R 5a is C 1 -C 6 alkyl, aryl or heteroaryl and R 6a is hydrogen; R 5a and R 6a are independently selected from the group consisting of C 1 -C 6 alkyl and aryl; or R 5a and R 6a , together with the nitrogen to which they are attached, form a ring comprising 4 to 6 carbon atoms or comprising 3 to 5 carbon atoms and one hetero moiety selected from the group consisting of --O-- and --NR 9a --, wherein R 9a is H, C 1 -C 6 alkyl or phenyl; with a compound of the formula ##STR17## wherein R 1a , R 2a , R 3a and R 4a are are independently selected from the group consisting of hydrogen and halo and R 7a is Cl or Br, in the presence of a strong base to obtain a compound of the formula ##STR18## (b) reacting a compound of step (a) with (i) POCl 3 to obtain a cyano compound of the formula ##STR19## (ii) DIBALH to obtain an adlehyde of the formula ##STR20## (c) reacting the cyano compound or the aldehyde with a piperidine derivative of the formula ##STR21## wherein L is a leaving group selected from the group consisting of Cl and Br, to obtain an aldehyde or an alcohol of the formula below, respectively: ##STR22## (d)(i) cyclizing the aldehyde with CF 3 SO 3 H to obtain a compound of formula II wherein the dotted line represents a double bond; or
(d)(ii) cyclizing the alcohol with polyphosphoric acid to obtain a compound of formula II wherein the dotted line represents a single bond.
Methods for preparing compounds of formula II disclosed in WO 95/10516, U.S. Pat. No. 5,151,423 and described below employ a tricyclic ketone intermediate. Such intermediates of the formula ##STR23## wherein R 11b , R 1a , R 2a , R 3a and R 4a are independently selected from the group consisting of hydrogen and halo, can be prepared by the following process comprising:
(a) reacting a compound of the formula ##STR24## (i) with an amine of the formula NHR 5a R 6a , wherein R 5a and R 6a are as defined in the process above; in the presence of a palladium catalyst and carbon monoxide to obtain an amide of the formula: ##STR25## (ii) with an alcohol of the formula R 10a OH, wherein R 10a is C 1 -C 6 lower alkyl or C 3 -C 6 cycloalkyl, in the presence of a palladium catalyst and carbon monoxide to obtain the ester of the formula ##STR26## followed by reacting the ester with an amine of formula NHR 5a R 6a to obtain the amide;
(b) reacting the amide with an iodo-substituted benzyl compound of the formula ##STR27## wherein R 1a , R 2a , R 3a , R 4a and R 7a are as defined above, in the presence of a strong base to obtain a compound of the formula ##STR28## (c) cyclizing a compound of step (b) with a reagent of the formula R 8a MgL, wherein R 8a is C 1 -C 8 alkyl, aryl or heteroaryl and L is Br or Cl, provided that prior to cyclization, compounds wherein R 5a or R 6a is hydrogen are reacted with a suitable N-protecting group.
(+)-Isomers of compounds of formula II wherein X is CH can be prepared with high enantioselectivity by using a process comprising enzyme catalyzed transesterification. Preferably, a racemic compound of formula II, wherein X is C, the double bond is present and R 3 is not H, is reacted with an enzyme such as Toyobo LIP-300 and an acylating agent such as trifluoroethly isobutyrate; the resultant (+)-amide is then hydrolyzed, for example by refluxing with an acid such as H 2 SO 4 , to obtain the corresponding optically enriched (+)-isomer wherein X is CH and R 3 is not H. Alternatively, a racemic compound of formula II, wherein X is C, the double bond is present and R 3 is not H, is first reduced to the corresponding racemic compound of formula II wherein X is CH and then treated with the enzyme (Toyobo LIP-300) and acylating agent as described above to obtain the (+)-amide, which is hydrolyzed to obtain the optically enriched (+)-isomer.
Compounds of formula III can be prepared from compounds of formula II by procedures known in the art, for example by reacting 1 -N-t-butoxy-carbonylpiperidinyl-4-acetic acid with the compound of formula II under the standard amide coupling conditions described above.
Compounds useful in this invention are exemplified by the following preparative examples, which should not be construed to limit the scope of the disclosure. Alternative mechanistic pathways and analogous structures within the scope of the invention may be apparent to those skilled in the art.
PREPARATIVE EXAMPLE 1 ##STR29## Step A: ##STR30##
Combine 25.86 g (55.9 mmol) of 4-(8-chloro-3-bromo-5,6-dihydro-11 H-benzo 5,6!cyclohepta 1,2-b!pyridin-11-ylidene)-1-piperidine-1-carboxylic acid ethyl ester and 250 mL of concentrated H 2 SO 4 at -5° C., then add 4.8 g (56.4 mmol) of NaNO 3 and stir for 2 hours. Pour the mixture into 600 g of ice and basify with concentrated NH 4 OH (aqueous). Filter the mixture, wash with 300 mL of water, then extract with 500 mL of CH 2 Cl 2 . Wash the extract with 200 mL of water, dry over MgSO 4 , then filter and concentrate in vacuo to a residue. Chromatograph the residue (silica gel, 10% EtOAc/CH 2 Cl 2 ) to give 24.4 g (86% yield) of the product. m.p.=165°-167° C., Mass Spec.: MH+=506, 508 (Cl).
elemental analysis: calculated--C,52.13; H, 4.17; N, 8.29; found--C, 52.18; H, 4.51; N,8.16
Step B: ##STR31##
Combine 20 g (40.5 mmol) of the product of Step A and 200 mL of concentrated H 2 SO 4 at 20° C., then cool the mixture to 0° C. Add 7.12 g (24.89 mmol) of 1,3-dibromo-5,5-dimethyl-hydantoin to the mixture and stir for 3 hours at 20° C. Cool to 0° C., add an additional 1.0 g (3.5 mmol) of the dibromohydantoin and stir at 20° C. for 2 hours. Pour the mixture into 400 g of ice, basify with concentrated NH 4 OH (aqueous) at 0° C., and collect the resulting solid by filtration. Wash the solid with 300 mL of water, slurry in 200 mL of acetone and filter to provide 19.79 g (85.6% yield) of the product. m.p=236°-237° C., Mass Spec.: MH+=586 (Cl).
elemental analysis: calculated--C, 45.11; H, 3.44; N, 7.17; found--C, 44.95; H, 3.57; N, 7.16
Step C: ##STR32## Combine 25 g (447 mmol) of Fe filings, 10 g (90 mmol) of CaCl 2 and a suspension of 20 g (34.19 mmol) of the product of Step B in 700 mL of 90:10 EtOH/water at 50° C. Heat the mixture at reflux overnight, filter through Celite® and wash the filter cake with 2×200 mL of hot EtOH. Combine the filtrate and washes, and concentrate in vacuo to a residue. Extract the residue with 600 mL of CH 2 Cl 2 , wash with 300 mL of water and dry over MgSO 4 . Filter and concentrate in vacuo to a residue, then chromatograph (silica gel, 30% EtOAc/CH 2 Cl 2 ) to give 11.4 g (60% yield) of the product. m.p.=211°-212° C., Mass Spec.: MH+=556 (Cl).
elemental analysis: calculated--C, 47.55; H, 3.99; N, 7.56 found--C, 47.45; H, 4.31; N, 7.49
Step D: ##STR33##
Slowly add (in portions) 20 g (35.9 mmol) of the product of Step C to a solution of 8 g (116 mmol) of NaNO 2 in 120 mL of concentrated HCl (aqueous) at -10° C. Stir the resulting mixture at 0° C. for 2 hours, then slowly add (dropwise) 150 mL (1.44 mole) of 50% H 3 PO 2 at 0° C. over a 1 hour period. Stir at 0° C. for 3 hours, then pour into 600 g of ice and basify with concentrated NH 4 OH (aqueous). Extract with 2×300 mL of CH 2 Cl 2 , dry the extracts over MgSO 4 , then filter and concentrate in vacuo to a residue. Chromatograph the residue (silica gel, 25% EtOAc/ hexanes) to give 13.67 g (70% yield) of the product. m.p.=163°-165° C., Mass Spec.: MH+=541 (Cl).
elemental analysis: calculated--C, 48.97; H, 4.05; N, 5.22; found--C, 48.86; H, 3.91; N, 5.18
Step E: ##STR34##
Combine 6.8 g (12.59 mmol) of the product of Step D and 100 mL of concentrated HCl (aqueous) and stir at 85° C. overnight. Cool the mixture, pour it into 300 g of ice and basify with concentrated NH 4 OH (aqueous). Extract with 2×300 mL of CH 2 Cl 2 , then dry the extracts over MgSO 4 . Filter, concentrate in vacuo to a residue, then chromatograph (silica gel, 10% MeOH/EtOAc+2% NH 4 OH (aq.)) to give 5.4 g (92% yield) of the title compound. m.p.=172°-174° C., Mass Spec.: MH+=469 (FAB).
elemental analysis: calculated--C, 48.69; H, 3.65; N, 5.97 ; found--C, 48.83; H, 3.80; N, 5.97
PREPARATIVE EXAMPLE 2 ##STR35## Step A: ##STR36##
Hydrolyze 2.42 g of 4-(8-chloro-3-bromo-5,6-dihydro-11H-benzo 5,6!cyclohepta 1,2-b!pyridin-11-ylidene)-1-piperidine-1-carboxylic acid ethyl ester by dissolving in concentrated HCl and heating to about 100° C. for @ 16 hours. Cool the mixture, the neutralize with 1M NaOH (aqueous). Extract with CH 2 Cl 2 , dry the extracts over MgSO 4 , filter and concentrate in vacuo to give 1.39 g (69% yield) of the product.
Step B: ##STR37##
Combine 1 g (2.48 mmol) of the product of Step A and 25 mL of dry toluene, add 2.5 mL of 1M DIBAL in toluene and heat the mixture at reflux. After 0.5 hours, add another 2.5 mL of 1M DIBAL in toluene and heat at reflux for 1 hour. (The reaction is monitored by TLC using 50% MeOH/CH 2 Cl 2 +NH 4 OH (aqueous).) Cool the mixture to room temperature, add 50 mL of 1N HCl (aqueous) and stir for 5 min. Add 100 mL of 1N NaOH (aqueous), then extract with EtOAc (3×150 mL). Dry the extracts over MgSO 4 , filter and concentrate in vacuo to give 1.1 g of the title compound.
PREPARATIVE EXAMPLE 3 ##STR38## Step A: ##STR39##
Combine 16.6 g (0.03 mole) of the product of Preparative Example 1, Step D, with a 3:1 solution of CH 3 CN and water (212.65 mL CH 3 CN and 70.8 mL of water) and stir the resulting slurry overnight at room temperature. Add 32.833 g (0.153 mole) of NalO 4 and then 0.31 g (2.30 mmol) of RuO 2 and stir at room temperature give 1.39 g (69% yield) of the product. (The addition of RuO 2 is accompanied by an exothermic reaction and the temperature climbs from 20° to 30° C.) Stir the mixture for 1.3 hrs. (temperature returned to 25° C. after about 30 min.), then filter to remove the solids and wash the solids with CH 2 Cl 2 . Concentrate the filtrate in vacuo to a residue and dissolve the residue in CH 2 Cl 2 . Filter to remove insoluble solids and wash the solids with CH 2 Cl 2 . Wash the filtrate with water, concentrate to a volume of about 200 mL and wash with bleach, then with water. Extract with 6N HCl (aqueous). Cool the aqueous extract to 0° C. and slowly add 50% NaOH (aqueous) to adjust to pH=4 while keeping the temperature <30° C. Extract twice with CH 2 Cl 2 , dry over MgSO 4 and concentrate in vacuo to a residue. Slurry the residue in 20 mL of EtOH and cool to 0° C. Collect the resulting solids by filtration and dry the solids in vacuo to give 7.95 g of the product. 1 H NMR (CDCl 3 , 200 MHz): 8.7 (s, 1H); 7.85 (m, 6H); 7.5 (d, 2H); 3.45 (m, 2H); 3.15 (m, 2H).
Step B: ##STR40##
Combine 21.58 g (53.75 mmol) of the product of Step A and 500 mL of an anhydrous 1:1 mixture of EtOH and toluene, add 1.43 g (37.8 mmol) of NaBH 4 and heat the mixture at reflux for 10 min. Cool the mixture to 0° C., add 100 mL of water, then adjust to pH≈4-5 with 1M HCl (aqueous) while keeping the temperature <10° C. Add 250 mL of EtOAc and separate the layers. Wash the organic layer with brine (3×50 mL) then dry over Na 2 SO 4 . Concentrate in vacuo to a residue (24.01 g) and chromatograph the residue (silica gel, 30% hexane/CH 2 Cl 2 ) to give the product. Impure fractions were purified by rechromatography. A total of 18.57 g of the product was obtained. 1 H NMR (DMSO-d 6 , 400 MHz): 8.5 (s, 1H); 7.9 (s, 1H); 7.5 (d of d, 2H); 6.2 (s, 1H); 6.1 (s, 1H); 3.5 (m, 1H); 3.4 (m, 1H); 3.2 (m, 2H).
Step C: ##STR41##
Combine 18.57 g (46.02 mmol) of the product of Step B and 500 mL of CHCl 3 , then add 6.70 mL (91.2 mmol) of SOCl 2 , and stir the mixture at room temperature for 4 hrs. Add a solution of 35.6 g (0.413 mole) of piperazine in 800 mL of THF over a period of 5 min. and stir the mixture for 1 hr. at room temperature. Heat the mixture at reflux overnight, then cool to room temperature and dilute the mixture with 1 L of CH 2 Cl 2 . Wash with water (5×200 mL), and extract the aqueous wash with CHCl 3 (3×100 mL). Combine all of the organic solutions, wash with brine (3×200 mL) and dry over MgSO 4 . Concentrate in vacuo to a residue and chromatograph (silica gel, gradient of 5%, 7.5%, 10% MeOH/CH 2 Cl 2 +NH 4 OH) to give 18.49 g of the title compound as a racemic mixture.
Step D--Separation of Enantiomers: ##STR42##
The racemic title compound of Step C is separated by preparative chiral chromatography (Chiralpack AD, 5 cm×50 cm column, flow rate 100 mL/min., 20% iPrOH/hexane+0.2% diethylamine), to give 9.14 g of the (+)-isomer and 9.30 g of the (-)-isomer.
Physical chemical data for (+)-isomer: m.p.=74.5°-77.5° C.; Mass Spec. MH+=471.9; a! D 25 =+97.4° (8.48 mg/2 mL MeOH).
Physical chemical data for (-)-isomer: m.p.=82.9°-84.5° C.; Mass Spec. MH+=471.8; a! D 25 =-97.4° (8.32 mg/2 mL MeOH).
PREPARATIVE EXAMPLE 4 ##STR43## Step A: ##STR44##
Combine 15 g (38.5 mmol) of 4-(8-chloro-3-bromo-5,6-dihydro-11H-benzo 5,6!cyclohepta 1 ,2-b!pyridin-11-ylidene)-1-piperidine-1-carboxylic acid ethyl ester and 150 mL of conc. H 2 SO 4 at -5° C., then add 3.89 g (38.5 mmol) of KNO 3 and stir for 4 h. Pour the mixture into 3 L of ice and basify with 50% NaOH (aqueous). Extract with CH 2 Cl 2 , dry over MgSO 4 , then filter and concentrate in vacuo to a residue. Recrystallize the residue from acetone to give 6.69 g of the product. 1 H NMR (CDCl 3 , 200 MHz): 8.5 (s, 1H); 7.75 (s, 1H); 7.6 (s, 1H); 7.35 (s, 1H); 4.15 (q, 2H); 3.8 (m, 2H); 3.5-3.1 (m, 4H); 3.0-2.8 (m, 2H); 2.6-2.2 (m, 4H); 1.25 (t, 3H).
Step B: ##STR45##
Combine 6.69 g (13.1 mmol) of the product of Step A and 100 mL of 85% EtOH/water, add 0.66 g (5.9 mmol) of CaCl 2 and 6.56 g (117.9 mmol) of Fe and heat the mixture at reflux overnight. Filter the hot reaction mixture through celite® and rinse the filter cake with hot EtOH. Concentrate the filtrate in vacuo to give 7.72 g of the product. Mass Spec.: MH+=478.0
Step C: ##STR46##
Combine 7.70 g of the product of Step B and 35 mL of HOAc, then add 45 mL of a solution of Br 2 in HOAc and stir the mixture at room temperature overnight. Add 300 mL of 1N NaOH (aqueous), then 75 mL of 50% NaOH (aqueous) and extract with EtOAc. Dry the extract over MgSO 4 and concentrate in vacuo to a residue. Chromatograph the residue (silica gel, 20%-30% EtOAc/hexane) to give 3.47 g of the product (along with another 1.28 g of partially purified product).
Mass Spec.: MH+=555.9. 1 H NMR (CDCl 3 , 300 MHz): 8.5 (s, 1H); 7.5 (s, 1H); 7.15 (s, 1H); 4.5 (s, 2H); 4.15 (m, 3H); 3.8 (br s, 2H); 3.4-3.1 (m, 4H); 9-2.75 (m, 1H); 2.7-2.5 (m, 2H); 2.4-2.2 (m, 2H); 1.25 (m, 3H).
Step D: ##STR47##
Combine 0.557 g (5.4 mmol) of t-butyinitrite and 3 mL of DMF, and heat the mixture at to 60°-70° C. Slowly add (dropwise) a mixture of 2.00 g (3.6 mmol) of the product of Step C and 4 mL of DMF, then cool the mixture to room temperature. Add another 0.64 mL of t-butylnitrite at 40° C. and reheat the mixture to 60°-70° C. for 0.5 hrs. Cool to room temperature and pour the mixture into 150 mL of water. Extract with CH 2 Cl 2 , dry over MgSO 4 and concentrate in vacuo to a residue. Chromatograph the residue (silica gel, 10%-20% EtOAc/hexane) to give 0.74 g of the product. Mass Spec.: MH+=541.0. 1 H NMR (CDCl3, 200 MHz): 8.52 (s, 1H); 7.5 (d, 2H); 7.2 (s, 1H); 4.15 (q, 2H); 3.9-3.7 (m, 2H); 3.5-3.1 (m, 4H); 3.0-2.5 (m, 2H); 2.4-2.2 (m, 2H); 2.1-1.9 (m, 2H); 1.26 (t, 3H).
Step E: ##STR48##
Combine 0.70 g (1.4 mmol) of the product of Step D and 8 mL of concentrated HCl (aqueous) and heat the mixture at reflux overnight. Add 30 mL of 1N NaOH (aqueous), then 5 mL of 50% NaOH (aqueous) and extract with CH 2 Cl 2 . Dry the extract over MgSO 4 and concentrate in vacuo to give 0.59 g of the title compound. Mass Spec.: M+=468.7. m.p.=123.9°-124.2° C.
PREPARATIVE EXAMPLE 5 ##STR49## Step A: ##STR50##
Prepare a solution of 8.1 g of the title compound from Preparative Example 4 in toluene and add 17.3 mL of a 1M solution of DIBAL in toluene. Heat the mixture at reflux and slowly add (dropwise) another 21 mL of 1M DIBAL/toluene solution over a period of 40 min. Cool the reaction mixture to about 0° C. and add 700 mL of 1M HCl (aqueous). Separate and discard the organic phase. Wash the aqueous phase with CH 2 Cl 2 , discard the extract, then basify the aqueous phase by adding 50% NaOH (aqueous). Extract with CH 2 Cl 2 , dry the extract over MgSO 4 and concentrate in vacuo to give 7.30 g of the title compound, which is a racemic mixture of enantiomers.
Step B--Separation of Enantiomers: ##STR51##
The racemic title compound of Step A is separated by preparative chiral chromatography (Chiralpack AD, 5 cm×50 cm column, using 20% iPrOH/hexane+0.2% diethylamine), to give the (+)-isomer and the (-)-isomer of the title compound.
Physical chemical data for (+)-isomer: m.p.=148.8° C.; Mass Spec. MH+=469; a! D 25 =+65.6° (mg/2 mL MeOH).
Physical chemical data for (-)-isomer: m.p.=112° C.; Mass Spec. MH+=469; a! D 25 =-65.2° (mg/2 mL MeOH).
PREPARATIVE EXAMPLE 6 ##STR52## Step A: ##STR53##
Combine 40.0 g (0.124 mole) of the starting ketone and 200 mL of H 2 SO 4 and cool to 0° C. Slowly add 13.78 g (0.136 mole) of KNO 3 over a period of 1.5 hrs., then warm to room temperature and stir overnight. Work up the reaction using substantially the same procedure as described for Preparative Example 1, Step A. Chromatograph (silica gel, 20%, 30%, 40%, 50% EtOAc/hexane, then 100% EtOAc) to give 28 g of the 9-nitro product, along with a smaller quantity of the 7-nitro product and 19 g of a mixture of the 7-nitro and 9-nitro compounds.
Step B: ##STR54##
React 28 g (76.2 mmol) of the 9-nitro product of Step A, 400 mL of 85% EtOH/water, 3.8 g (34.3 mmol) of CaCl 2 and 38.28 g (0.685 mole) of Fe using substantially the same procedure as described for Preparative Example 1, Step C, to give 24 g of the product
Step C: ##STR55##
Combine 13 g (38.5 mmol) of the product of Step B, 140 mL of HOAc and slowly add a solution of 2.95 mL (57.8 mmol) of Br 2 in 10 mL of HOAc over a period of 20 min. Stir the reaction mixture at room temperature, then concentrate in vacuo to a residue. Add CH 2 Cl 2 and water, then adjust to pH=8-9 with 50% NaOH (aqueous). Wash the organic phase with water, then brine and dry over Na 2 SO 4 . Concentrate in vacuo to give 11.3 g of the product.
Step D: ##STR56##
Cool 100 mL of concentrated HCl (aqueous) to 0° C., then add 5.61 g (81.4 mmol) of NaNO 2 and stir for 10 min. Slowly add (in portions) 11.3 g (27.1 mmol) of the product of Step C and stir the mixture at 0°-3° C. for 2.25 hrs. Slowly add (dropwise) 180 mL of 50% H 3 PO 2 (aqueous) and allow the mixture to stand at 0° C. overnight. Slowly add (dropwise) 150 mL of 50% NaOH over 30 min., to adjust to pH=9, then extract with CH 2 Cl 2 . Wash the extract with water, then brine and dry over Na 2 SO 4 . Concentrate in vacuo to a residue and chromatograph (silica gel, 2% EtOAc/CH 2 Cl 2 ) to give 8.6 g of the product.
Step E: ##STR57##
Combine 8.6 g (21.4 mmol) of the product of Step D and 300 mL of MeOH and cool to 0°-2° C. Add 1.21 g (32.1 mmol) of NaBH 4 and stir at ˜0° C. for 1 hr. Add another 0.121 g (3.21 mmol) of NaBH 4 , stir for 2 hr. at 0° C., then let stand overnight at 0° C. Concentrate in vacuo to a residue then partition the residue between CH 2 Cl 2 and water. Separate the organic phase and concentrate in vacuo (50° C.) to give 8.2 g of the product.
Step F: ##STR58##
Combine 8.2 g (20.3 mmol) of the product of Step E and 160 mL of CH 2 Cl 2 , cool to 0° C., then slowly add (dropwise) 14.8 mL (203 mmol) of SOCl 2 over a 30 min. period. Warm the mixture to room temperature and stir for 4.5 hrs., then concentrate in vacuo to a residue, add CH 2 Cl 2 and wash with 1N NaOH (aqueous) then brine and dry over Na 2 SO 4 . Concentrate in vacuo to a residue, then add dry THF and 8.7 g (101 mmol) of piperazine and stir at room temperature overnight. Concentrate in vacuo to a residue, add CH 2 Cl 2 , and wash with 0.25N NaOH (aqueous), water, then brine. Dry over Na 2 SO 4 and concentrate in vacuo to give 9.46 g of the crude product. Chromatograph (silica gel, 5% MeOH/CH 2 Cl 2 +NH 3 ) to give 3.59 g of the title compound, as a racemate. 1 H NMR (CDCl 3 , 200 MHz): 8.43 (d, 1H); 7.55 (d, 1H); 7.45 (d, 1H); 7.11 (d, 1H) 5.31 (s, 1H); 4.86-4.65 (m, 1H); 3.57-3.40 (m, 1H); 2.98-2.55 (m, 6H); 2.45-2.20 (m, 5H).
Step G--Separation of Enantiomers: ##STR59##
The racemic title compound from Step F (5.7 g) is chromatographed as described for Preparative Example 3, Step D, using 30% iPrOH/hexane+0.2% diethylamine, to give 2.88 g of the R-(+)-isomer and 2.77 g of the S-(-)-isomer of the title compound.
Physical chemical data for the R-(+)-isomer: Mass Spec. MH+=470; a! D 25 =+12.1° (10.9 mg/2 mL MeOH).
Physical chemical data for the S-(-)-isomer: Mass Spec. MH+=470; a! D 25 =-13.2° (11.51 mg/2 mL MeOH).
PREPARATIVE EXAMPLE 7 ##STR60## Step A: ##STR61##
Combine 13 g (33.3 mmol) of the title compound from Preparative Example 1, Step D, and 300 mL of toluene at 20° C., then add 32.5 mL (32.5 mmol) of a 1M solution of DIBAL in toluene. Heat the mixture at reflux for 1 hr., cool to 20° C., add another 32.5 mL of 1M DIBAL solution and heat at reflux for 1 hr. Cool the mixture to 20° C. and pour it into a mixture of 400 g of ice, 500 mL of EtOAc and 300 mL of 10% NaOH (aqueous). Extract the aqueous layer with CH 2 Cl 2 (3×200 mL), dry the organic layers over MgSO 4 , then concentrate in vacuo to a residue. Chromatograph (silica gel, 12% MeOH/CH 2 Cl 2 +4% NH 4 OH) to give 10.4 g of the title compound as a racemate. Mass Spec.: MH+=469 (FAB). partial 1 H NMR (CDCl 3 , 400 MHz): 8.38 (s, 1H); 7.57 (s, 1H); 7.27 (d, 1H); 7.06 (d, 1H); 3.95 (d, 1H).
Step B--Separation of Enantiomers: ##STR62##
The racemic title compound of Step A is separated by preparative chiral chromatography (Chiralpack AD, 5 cm×50 cm column, using 5% iPrOH/hexane+0.2% diethylamine), to give the (+)-isomer and the (-)-isomer of the title compound.
Physical chemical data for (+)-isomer: Mass Spec. MH+=470.9 (FAB); a! D 25 =+43.5° (c=0.402, EtOH); partial 1 H NMR (CDCl 3 , 400 MHz): 8.38 (s, 1H); 7.57 (s, 1H); 7.27 (d, 1H); 7.05 (d, 1H); 3.95 (d, 1H).
Physical chemical data for (-)-isomer: Mass Spec. MH+=470.9 (FAB); a! D 25 =-41.8° (c=0.328 EtOH); partial 1 H NMR (CDCl 3 , 400 MHz): 8.38 (s, 1H); 7.57 (s, 1H); 7.27 (d, 1 H); 7.05 (d, 1 H); 3.95 (d, 1 H).
PREPARATIVE EXAMPLE 8 ##STR63##
Treat 4-(8-chloro-3-bromo-5,6-dihydro-11H-benzo 5,6!cyclohepta- 1,2b!pyridin-11-ylidene)-1-piperidine-1-carboxylic acid ethyl ester via substantially the same procedure as described in Preparative Example 3, Steps A-D, to give as the product of Step C, the racemic title compound, and as the products of Step D the R-(+)-isomer and S-(-)-isomer of the title compound.
Physical chemical data for the R-(+)-isomer: 13 C NMR (CDCl 3 ): 155.8 (C); 146.4 (CH); 140.5 (CH); 140.2 (C); 136.2 (C); 135.3 (C); 133.4 (C); 132.0 (CH); 129.9 (CH); 125.6 (CH); 119.3 (C); 79.1 (CH); 52.3 (CH 2 ); 52.3 (CH); 45.6 (CH 2 ); 45.6 (CH 2 ); 30.0 (CH 2 ); 29.8 (CH 2 ). a! D 25 =+25.8° (8.46 mg/2 mL MeOH).
Physical chemical data for the S-(-)-isomer: 13 C NMR (CDCl 3 ): 155.9 (C); 146.4 (CH); 140.5 (CH); 140.2 (C); 136.2 (C); 135.3 (C); 133.3(C); 132.0 (CH); 129.9 (CH); 125.5 (CH); 119.2(C); 79.1 (CH); 52.5 (CH 2 ); 52.5 (CH); 45.7 (CH 2 ); 45.7 (CH 2 ); 30.0 (CH 2 ); 29.8 (CH 2 ). a! D 25 =-27.9° (8.90 mg/2 mL MeOH).
PREPARATIVE EXAMPLE 9 ##STR64## Step A: ##STR65##
Dissolve 9.90 g (18.9 mmol) of the product of Preparative Example 4, Step B, in 150 mL CH 2 Cl 2 and 200 mL of CH 3 CN and heat to 60° C. Add 2.77 g (20.8 mmol) N-chlorosuccinimide and heat to reflux for 3 h., monitoring the reaction by TCL (30%EtOAc/H 2 O). Add an additional 2.35 g (10.4 mmol) of N-chlorosuccinimide and reflux an additional 45 min. Cool the reaction mixture to room temperature and extract with 1N NaOH and CH 2 Cl 2 . Dry the CH 2 Cl 2 layer over MgSO 4 , filter and purify by flash chromatography (1200 mL normal phase silica gel, eluting with 30% EtOAc/H 2 O) to obtain 6.24 g of the desired product. M.p. 193°-195.4° C.
Step B: ##STR66##
To 160 mL of conc. HCl at -10C add 2.07 g (30.1 mmol) NaNO 2 and stir for 10 min. Add 5.18 g (10.1 mmol) of the product of Step A and warm the reaction mixture from -10° C. to 0° C. for 2 h. Cool the reaction to -10° C., add 100 mL H 3 PO 2 and let stand overnight. To extract the reaction mixture, pour over crushed ice and basifiy with 50% NaOH/CH 2 Cl 2 . Dry the organic layer over MgSO 4 , filter and concentrate to dryness. Purify by flash chromatography (600 mL normal phase silica gel, eluting with 20% EtOAc/hexane) to obtain 3.98 g of product. Mass spec.: MH+=497.2.
Step C: ##STR67##
Dissolve 3.9 g of the product of Step B in 100 mL conc. HCl and reflux overnight. Cool the mixture, basify with 50% w/w NaOH and extract the resultant mixture with CH 2 Cl 2 . Dry the CH 2 Cl 2 layer over MgSO 4 , evaporate the solvent and dry under vacuum to obtain 3.09 g of the desired product. Mass spec.: MH+=424.9.
Step D: ##STR68##
Using a procedure similar to that described in Preparative Example 5, obtain 1.73 g of the desired product, m.p. 169.6°-170.1° C.; a! D 25 =+48.2° (c=1, MeOH).
PREPARATIVE EXAMPLE 10 ##STR69## Step A: ##STR70##
Combine 1.33 g of the (+)-enantiomer of the compound of Preparative Example 5, Step B, in anhydrous DMF with 1.37 g of 1-N-t-butoxy-carbonylpiperidinyl-4-acetic acid, and with DEC, HOBT and N-methylmorpholine. Stir the mixture at room temperature overnight. Concentrate in vacuo to remove the DMF and add 50 mL of saturated NaHCO 3 (aqueous). Extract with CH 2 Cl 2 (2×250 mL), wash the extracts with 50 mL of brine and dry over MgSO 4 . Concentrate in vacuo to a residue and chromatograph (silica gel, 2% CH 3 OH/CH 2 Cl 2 +10% NH 4 OH) to give 2.78 g of the product. Mass Spec.: MH+=694.0 (FAB); α! D 25 =+34.1° (5.45 mg/2 mL, MeOH).
Step B:
Combine 2.78 g of the product of Step A and CH 2 Cl 2 , then cool to 0° C. and add TFA. Stir the mixture for 3 h at 0° C., then add 1N NaOH (aqueous) followed by 50% NaOH (aqueous). Extract with CH 2 Cl 2 , dry over MgSO 4 and concentrate in vacuo to give 1.72 g of the product. M.p.=104.1° C.; Mass Spec.: MH+=594; α! D 25 =+53.4° (11.42 mg/2 mL, CH 3 OH).
PREPARATIVE EXAMPLE 11
(+)-1-(Aminoacetyl)-4-(3-dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)piperidine ##STR71## Step 1: (+)-1,1-Dimethylethyl 2- 4-(3,10-dibromo-8-chloro-6,11-dihydro-5 H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxoethyl!-carbamate ##STR72##
The product of Preparative Example 5, (+-isomer) (0.4 g, 0.85 mmol), was dissolved in DMF (10 mL) and then cooled to ˜4° C. BOC-Glycine (0.19 g, 1.1 mmol) was then added, followed by DEC (0.2 g, 1.1 mmol), HOBT (0.15 g, 1.1 mmol) and 4-methylmorpholine (0.11 g, 0.12 μL, 1.1 mmol). The reaction was stirred at room temperature overnight, then was concentrated in vacuo to a residue and partitioned between CH 2 Cl 2 and sat. NaHCO 3 (aqueous). The aqueous phase was extracted further with CH 2 Cl 2 , the combined CH 2 Cl 2 fractions were dried over MgSO 4 and concentrated in vacuo to give a residue that was chromatographed on silica gel column using 5% (NH 3 saturated CH 3 OH)/CH 2 Cl 2 as eluent to give the title compound as a white solid: 0.52 g, 99% yield, m.p.=95°-96° C., MH+=628.
Step 2:
The product of Step 1 (2.65 g, 4.2 mmol) was dissolved in CH 2 Cl 2 (20 mL) and cooled to 0° C. Trifluoroacetic acid (10 mL) was then added. The reaction mixture was stirred at room temperature for 4 h, then poured into ice and the pH was adjusted to 10 using 50%(w/v) aqueous NaOH. The reaction mixture was extracted with CH 2 Cl 2 , the combined CH 2 Cl 2 extracts were washed with H 2 O and brine, and dried over Na 2 SO 4 . The solvents were removed by rotary evaporation to give the title compound as a white solid: 2.18 g, 98% yield, m.p.=150-152° C., MH+=528.
PREPARATIVE EXAMPLE 12
(+)-1-(3-Amino-i-oxopropyl)-4-(3-dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)piperidine ##STR73## Step 1: (+)-1,1-Dimethylethyl 3- 4-(3,10-dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxopropyl!-carbamate ##STR74##
The title compound was prepared following essentially the same procedure as described in Preparative Example 11, Step 1, except that BOC-β-alanine was used instead of BOC-glycine to obtain a white solid. Yield=99%, MH+=642.
Step 2:
The title compound was prepared following essentially the same procedure as described in Preparative Example 11, Step 2, to obtain a white solid. Yield=100%, m.p.=136°-137° C., MH+=642.
PREPARATIVE EXAMPLE 13
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta- 1,2-b!pyridin-11-yl)-1- 4-amino!-1-oxobutyl!piperidine ##STR75## Step 1: (+)-1,1-dimethylethyl 4- 4-(3,10-dibromo-8-chloro-6,11-dihydro-5h-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxobutyl!-carboxamide ##STR76## Step 2:
The title compound was prepared following essentially the same procedure as described in Preparative Example 11, Step 1, except that BOC-α-amino butyric acid was used instead of BOC-glycine to obtain a white solid. Yield=79%, m.p.=102°-103° C., MH+=781.
Step 2:
The title compound was prepared following essentially the same procedure as described for Preparative Example 11, Step 2, to obtain a white solid. Yield=94%, m.p.=114°-115 0C., MH+=681.
PREPARATIVE EXAMPLE 14
(+)-1-(Aminoacetyl)-4- 2- 4-(3,10-dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta 1 ,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxoethyl!piperidine ##STR77## Step 1: (+)-1,1-Dimethylethyl 2- 4- 2- 4-(3,10-dibromo-8-chloro-6,11 -dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxoethyl!-1-piperidinyl!-2-oxoethyl!carbamate ##STR78##
The title compound was prepared following essentially the same procedure as described for Preparative Example 11, Step 1, except that the compound of Preparative Example 10-(+-isomer) was used instead of the compound from Preparative Example 5 to obtain a white solid. Yield=82%, m.p.=98°-99° C., MH+=753.
Step 2:
The title compound was prepared following essentially the same procedure as described in Preparative Example 11, Step 2 to obtain a white solid. Yield=89%, m.p.=130°-131° C., MH+=653.
PREPARATIVE EXAMPLE 15
(+)-1-(3-Amino-1-oxopropyl)-4- 2- 4-(3,10-dibromo-8-chloro-6,11 -dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxoethyl!piperidine ##STR79## Step 1: (+)-1,1-Dimethylethyl 3- 4- 2- 4-(3,10-dibromo-8-chloro-6,11 -dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2 -oxoethyl!-1-piperidinyl!-3-oxopropyl!carbamate ##STR80##
The title compound was prepared following essentially the same procedure as described for Preparative Example 12, Step 1, except that the compound from Preparative Example 10 was used instead of the compound of Preparative Example 5 to obtain a white solid. Yield=84%, m.p.=87°-88° C., MH+=767.
Step 2:
The title compound was prepared following essentially the same procedure as described for Preparative Example 11, Step 2, to obtain a white solid. Yield=84%, m.p.=120°-121° C., MH+=667.
PREPARATIVE EXAMPLE 16
(+)-1-(4-Amino-1-oxobutyl)-4- 2- 4-(3,10-dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2-oxoethyl!piperidine ##STR81## Step 1: (+)-1,1-Dimethylethyl 4- 4- 2- 4-(3,10-dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclo-hepta 1,2-b!pyridin-11-yl)-1-piperidinyl!-2 -oxoethyl!-1-piperidinyl!-4-oxobutyl!carbamate ##STR82##
The title compound was prepared following essentially the same procedure as described for Preparative Example 13, Step 1, except that the compound of Preparative Example 10 was used instead of the compound of Preparative Example 5 to obtain a white solid. Yield=79%, m.p.=102°-103° C., MH+=782.
Step 2:
The title compound was prepared following essentially the same procedure as described for Preparative Example 11, Step 2, to obtain a white solid. Yield=94%, m.p.=114°-115° C., MH+=681.
PREPARATIVE EXAMPLE 17 ##STR83##
Dissolve 2 g (12.7 mmol) of methyl 2-oxo-1-pyrrolidine acetate in 20 mL of EtOH and then add 20 mL of 1M LiOH. Stir the reaction mixture at room temperature for 16 h. Strip off the solvents, dissolve the resulting material in water and adjust the pH to ˜4. Concentrate the reaction mixture to give the product. Mass Spec.: MH+=144.
EXAMPLE 1
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- (2-oxo-1-pyrrolidinyl)acetyl!piperidine ##STR84##
The compound of Preparative Example 5 (0.15 g, 0.32 mmol) was dissolved in DMF (5mL) and then cooled to ˜4° C. The compound of Preparative Example 17 (0.06 g, 0.4 mmol) was then added, followed by DEC (0.08 g, 0.4 mmol), HOBT (0.6 g, 0.4 mmol), and 4-methylmorpholine (0.04 g, 50 μL, 0.4 mmol), and the reaction was then stirred at room temperature overnight. The reaction mixture was concentrated in vacuo to a residue that was partitioned between CH 2 Cl 2 and sat. NaHCO 3 (aqueous). The aqueous phase was extracted further with CH 2 Cl 2 , the combined CH 2 Cl 2 fractions were dried over MgSO 4 and concentrated in vacuo to give a residue that was chromatographed on silica gel column using 5% (NH 3 saturated CH 3 OH)/CH 2 Cl 2 as eluent to give the title compound as a white solid: 0.11 g, 61% yield, m.p.=118°-119° C., MH+=596.
EXAMPLE 2
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 1-oxo-3-(2-oxo-1-pyrrolidinyl)propyl!piperidine ##STR85##
The title compound of Preparative Example 12 (0.4 g, 0.74 mmol) was dissolved in CH 2 Cl 2 (10 mL), and 4-bromo butyryl chloride (0.2 g, 0.13 mL, 1.11 mmol) and Et 3 N (0.164 g, 0.23 ml, 1.62 mmol) were then added. The reaction mixture was stirred at room temperature for 16 h. The reaction mixture was partitioned between sat. NaHCO 3 and CH 2 Cl 2 . The aqueous phase was extracted with CH 2 Cl 2 , the combined CH 2 Cl 2 extracts were dried over MgSO 4 and the solvent was removed by rotary evaporation. The resulting product was dissolved in THF (10 mL), cooled to -10° C., NaH (0.09 g, 3.79 mmol) was added and the reaction mixture was stirred for 16 h, allowing the temperature to come to room temperature. The reaction mixture was then partioned between sat. NaHCO 3 and EtOAc. The organic phase was dried over MgSO 4 and purified by flash chromatography on silica gel, eluting with 3% CH 3 OH(sat. with NH 3 )/CH 2 Cl 2 to give the title compound as a white solid, MH+=610.
EXAMPLE 3
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 1-oxo-4-(2-oxo-1-pyrrolidinyl)butyl!piperidine ##STR86##
The title compound is prepared from the product of Preparative Example 13, following essentially the same procedure as described for Example 2 to obtain a white solid, m.p.=127°-128° C., MH=624.
EXAMPLE 4
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- (2-oxo-1-piperidinyl)acetyl!piperidine ##STR87##
The title compound is prepared from the product of Preparative Example 11, following essentially the same procedure as described for Example 2 except that 4-bromovaleryl chloride was used instead of 4bromo butyryl chloride to obtain a white solid. Yield=50%, m.p.=138°-139° C., MH=610.
EXAMPLE 5
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 1-oxo-3-(2-oxo-1-piperidinyl)propyl!piperidine ##STR88##
The title compound was prepared from the product of Preparative Example 12, following essentially the same procedure as described for Example 2 except that 4-bromovaleryl chloride was used instead of 4-bromo butyryl chloride to obtain a white solid.
Yield=50%, m.p.=138°-139° C., MH=610.
EXAMPLE 6
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 1-oxo-4-(2-oxo-1-piperidinyl)butyl!piperidine ##STR89##
The title compound is prepared from the product of Preparative Example 13, following essentially the same procedure as described for Example 2 except that 4-bromovaleryl chloride was used instead of 4-bromo butyryl chloride to obtain a white solid.
Yield=81%, m.p.=101°-102° C., MH=638.
EXAMPLE 7
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- (2-oxo-1-imidazolidinyl)acetyl!piperidine ##STR90##
The product of Preparative Example 11 (2.08 g, 3.9 mmol) was dissolved in CH 2 Cl 2 (20 mL) and 2-bromo ethyl isocyanate (0.8 g, 0.5 mL, 7.9 mmol) was added. The reaction mixture was stirred at room temperature for 16 h. The reaction mixture was partitioned between sat. NaHCO 3 and CH 2 Cl 2 . The aqueous phase was extracted with CH 2 Cl 2 , the combined CH 2 Cl 2 extracts were dried over MgSO 4 and the solvent was removed by rotary evaporation. The resulting product was dissolved in THF (20 mL), cooled to -10° C., NaH (0.46 g, 19.5 mml) was added and the reaction mixture was stirred for 16 h, allowing the temperature to come to room temperature. The reaction mixture was then partitioned between sat. NaHCO 3 and EtOAc. The organic phase was dried over MgSO 4 and purified by flash chromatography on silica gel, eluting with 5% CH 3 OH(saturated with NH 3 )/CH 2 Cl 2 to give the title compound as a white solid: 1.95 g, yield=80%, m.p.=167°-168° C., MH+=597.
EXAMPLE 8
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 3-(2-oxoimidazolidinyl)-1-oxopropyl!piperidine ##STR91##
The title compound is prepared from the product of Preparative Example 12, following essentially the same procedure as described in Example 7 to obtain a white solid.
Yield=45%, m.p.=202°-203° C., MH+=611.
EXAMPLE 9
((+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 1-oxo-4-(2-oxo-1-imidazolidinyl)butyl!piperidine ##STR92##
The title compound is prepared from the product of Preparative Example 13, following essentially the same procedure as described in Example 7 to obtain a white solid.
Yield=52%, m.p.=120°-123° C., MH+=625.
EXAMPLE 10
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- (hexahydro-2-oxo-1-pyrimidinyl)acetyl!piperidine ##STR93##
The title compound is prepared from the product of Preparative Example 11, following essentially the same procedure as described for Example 7, substituting 3-chloro propyl isocyanate for 2-bromo ethyl isocyanate to obtain a white solid.
Yield=56%, m.p.=155°-156° C., MH+=611.
EXAMPLE 11
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta- 1,2-b!pyridin-11-yl)-1- 1-oxo-3-(hexahydo-2-oxo-1-pyrimidinyl)-oxopropyl!piperidine ##STR94##
The title compound is prepared from the product of Preparative Example 12, following essentially the same procedure as described for Example 10 to obtain a white solid.
Yield=40%, m.p.=135°-136° C., MH+=625.
EXAMPLE 12
(+)-4-(3,10-Dibromo-8-chloro-6,11-dihydro-5H-benzo 5,6!cyclohepta 1,2-b!pyridin-11-yl)-1- 4-(hexahydo-2-oxo-1-pyrimidinyl)oxobutyl!piperidine ##STR95##
The title compound is prepared from the product of Preparative Example 13, following essentially the same procedure as described for Example 10 to obtain a white solid.
Yield=63%, m.p.=157°-158° C., MH+=639.
Using the staring materials described above and the appropriate procedure, compounds of the following structure are prepared:
__________________________________________________________________________ ##STR96##Ex. Starting Material Proceduce ##STR97## Analytical Data__________________________________________________________________________13 Prep. Ex. 10 and 17 Ex. 1 ##STR98## Mass spec: MH.sup.+ = 721; m.p. = 140-141° C.14 Prep. Ex. 15 Ex. 2 ##STR99## Mass spec: MH.sup.+ = 735; m.p. = 129-130° C.15 Prep. Ex. 16 Ex. 2 ##STR100## Mass spec: MH.sup.+ = 749; m.p. = 141-142° C.16 Prep. Ex. 14 Ex. 5 ##STR101## Mass spec: MH.sup.+ = 735; m.p. = 147-148° C.17 Prep. Ex. 15 Ex. 5 ##STR102## Mass spec: MH.sup.+ = 749; m.p. = 130-131° C.18 Prep. Ex. 16 Ex. 5 ##STR103## Mass spec: MH.sup.+ = 763; m.p. = 137-138° C.19 Prep. Ex. 15 Ex. 7 ##STR104## Mass spec: MH.sup.+ = 736; m.p. = 184-185° C.20 Prep. Ex. 16 Ex. 7 ##STR105## Mass spec: MH.sup.+ = 75021 Prep. Ex. 14 Ex. 10 ##STR106## Mass spec: MH.sup.+ = 736; m.p. = 168-169° C.22 Prep. Ex. 15 Ex. 10 ##STR107## Mass spec: MH.sup.+ = 750; m.p. = 146-147° C.23 Prep. Ex. 16 Ex. 10 ##STR108## Mass spec: MH.sup.+ = 764; m.p. = 148-149° C.__________________________________________________________________________
FPT IC 50 (inhibition of farnesyl protein transferase, in vitro enzyme assay), COS Cell IC 50 (Cell-Based Assay), GGPT IC 50 (inhibition of geranylgeranyl protein transferase, in vitro enzyme assay), Cell Mat Assay, and anti-tumor activity (in vivo anti-tumor studies) are determined by the assay procedures described in WO 95/10516.
The results are given in Tables 1 and 2.
TABLE 1______________________________________FPT INHIBITIONEXAMPLE FPT IC.sub.50 (μM) EXAMPLE FPT IC.sub.50 (μM)______________________________________1 0.0040 7 0.0233 0.085 9 0.0164 0.0028 10 0.00325 0.019 11 0.0206 0.08 12 0.056______________________________________
TABLE 2______________________________________ACTIVITY IN COS CELLS INHIBITION OF RAS PROCESSINGEXAMPLE IC.sub.50 (μM)______________________________________1 0.50010 0.016______________________________________
For preparing pharmaceutical compositions from the compounds described by this invention, inert, pharmaceutically acceptable carriers can be either solid or liquid. Solid form preparations include powders, tablets, dispersible granules, capsules, cachets and suppositories. The powders and tablets may be comprised of from about 5 to about 70 percent active ingredient. Suitable solid carriers are known in the art, e.g. magnesium carbonate, magnesium stearate, talc, sugar, lactose. Tablets, powders, cachets and capsules can be used as solid dosage forms suitable for oral administration.
For preparing suppositories, a low melting wax such as a mixture of fatty acid glycerides or cocoa butter is first melted, and the active ingredient is dispersed homogeneously therein as by stirring. The molten homogeneous mixture is then poured into convenient sized molds, allowed to cool and thereby solidify.
Liquid form preparations include solutions, suspensions and emulsions. As an example may be mentioned water or water-propylene glycol solutions for parenteral injection.
Liquid form preparations may also include solutions for intranasal administration.
Aerosol preparations suitable for inhalation may include solutions and solids in powder form, which may be in combination with a pharmaceutically acceptable carrier, such as an inert compressed gas.
Also included are solid form preparations which are intended to be converted, shortly before use, to liquid form preparations for either oral or parenteral administration. Such liquid forms include solutions, suspensions and emulsions.
The compounds of the invention may also be deliverable transdermally. The transdermal compositions can take the form of creams, lotions, aerosols and/or emulsions and can be included in a transdermal patch of the matrix or reservoir type as are conventional in the art for this purpose.
Preferably the compound is administered orally.
Preferably, the pharmaceutical preparation is in unit dosage form. In such form, the preparation is subdivided into unit doses containing appropriate quantities of the active component, e.g., an effective amount to achieve the desired purpose.
The quantity of active compound in a unit dose of preparation may be varied or adjusted from about 0.1 mg to 1000 mg, more preferably from about 1 mg. to 300 mg, according to the particular application.
The actual dosage employed may be varied depending upon the requirements of the patient and the severity of the condition being treated. Determination of the proper dosage for a particular situation is within the skill of the art. Generally, treatment is initiated with smaller dosages which are less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under the circumstances is reached. For convenience, the total daily dosage may be divided and administered in portions during the day if desired.
The amount and frequency of administration of the compounds of the invention and the pharmaceutically acceptable salts thereof will be regulated according to the judgment of the attending clinician considering such factors as age, condition and size of the patient as well as severity of the symptoms being treated. A typical recommended dosage regimen is oral administration of from 10 mg to 2000 mg/day preferably 10 to 1000 mg/day, in two to four divided doses to block tumor growth. The compounds are non-toxic when administered within this dosage range.
The following are examples of pharmaceutical dosage forms which contain a compound of the invention. The scope of the invention in its pharmaceutical composition aspect is not to be limited by the examples provided.
Pharmaceutical Dosage Form Examples
______________________________________EXAMPLE ATabletsNo. Ingredients mg/tablet mg/tablet______________________________________1. Active compound 100 5002. Lactose USP 122 1133. Corn Starch, Food Grade, 30 40 as a 10% paste in Purified Water4. Corn Starch, Food Grade 45 405. Magnesium Stearate 3 7 Total 300 700______________________________________
Method of Manufacture
Mix Item Nos. 1 and 2 in a suitable mixer for 10-15 minutes. Granulate the mixture with Item No. 3. Mill the damp granules through a coarse screen (e.g., 1/4", 0.63 cm) if necessary. Dry the damp granules. Screen the dried granules if necessary and mix with Item No. 4 and mix for 10-15 minutes. Add Item No. 5 and mix for 1-3 minutes. Compress the mixture to appropriate size and weigh on a suitable tablet machine.
______________________________________EXAMPLE BCapsulesNo. Ingredient mg/capsule mg/capsule______________________________________1. Active compound 100 5002. Lactose USP 106 1233. Corn Starch, Food Grade 40 704. Magnesium Stearate NF 7 7 Total 253 700______________________________________
Method of Manufacture
Mix Item Nos. 1, 2 and 3 in a suitable blender for 10-15 minutes. Add Item No. 4 and mix for 1-3 minutes. Fill the mixture into suitable two-piece hard gelatin capsules on a suitable encapsulating machine.
While the present invention has been described in conjunction with the specific embodiments set forth above, many alternatives, modifications and variations thereof will be apparent to those of ordinary skill in the art. All such alternatives, modifications and variations are intended to fall within the spirit and scope of the present invention.
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Compounds of the following formula useful for inhibiting Ras function and therefore inhibiting or treating the abnormal growth of cells are disclosed: ##STR1## or a pharmaceutically acceptable salt or solvate thereof, wherein: R and R 2 are halo;
R 1 and R 3 are H and halo, provided that at least one is H;
W is N, CH or C when the double bond is present at the C-11 position;
R 4 is --(CH 2 ) n --R 5 or ##STR2## R 5 is ##STR3## R 6 is R 5 or ##STR4## Z 1 and Z 2 are independently selected from the group consisting of ═O and ═S;
n is 1-6; and
n 1 is 0 or 1.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to an improved heart valve prosthesis, and more particularly to such a prosthesis device which may be implanted to replace a defective natural or artificial heart valve and which incorporates electronics for monitoring and telemetering operational conditions of the valve and other biodata to an external receiver, as well as for providing stimulation pulses for pacing. The improved prosthesis device of the present invention employs at least one, but preferably two or even three occluder means, each in the form of a flat or curved plate or leaflet, both functioning hemodynamically by a periodic opening and closing motion which is created through normal pumping action of the heart. The improved prosthesis device may alternatively employ multiple occluder means, such as two or three flat or curved plates, or alternatively, a ball and cage check occluder. A sensor is incorporated for detecting such things as the movement of the leaflets and a transmitter/receiver (transceiver) is incorporated for sending and receiving data and commands from an external apparatus.
2. Discussion of the Prior Art
As is well known in the art, prosthetic heart valves function essentially as check valves. Blood flow, which occurs as a result of the natural pumping action of the heart, causes periodic opening of the leaflets, with the system pressure closing the leaflets during periods of diastole when in the aortic position or during periods of systole when in the atrial-ventricular position.
A variety of prosthetic heart valves have been proposed and utilized in the past. Certain of these prosthetic devices have employed a caged ball arrangement which also function and control blood flow in response to normal pumping action of the heart. The caged-ball designs have been found objectionable from a psychologic standpoint because of the audible clicking sounds emitted as the ball is made to seat and unseat relative to the opening in the valve body. Other heart valve prostheses have employed occluders in the form of either a round disk or a pair of semi-circular and semi-elliptical plates. The latter are normally referred to as bi-leaflet valves. While various materials of construction have been employed in the past, the more recently utilized heart valve prostheses have been fabricated essentially from pyrolytic carbon.
Bi-leaflet valves normally employ a strategically designed pivot means to appropriately guide and otherwise control the motion of the leaflets as they are made to move between their open and closed dispositions. In addition, means have been provided to control or limit the extent of motion to which the leaflets are subjected during opening and closing, thereby providing an arrangement wherein the motion of the individual leaflets is carefully guided, controlled, limited and maintained.
It is further known that blood components, including those cells normally found in human blood, are extremely fragile and delicate. These cells can be damaged and/or destroyed if subjected to unusual mechanical forces. Thus, care must be taken to control the nature of the forces created during the occurrence of relative motion between the leaflets and their surrounding annular body. For example, reduction of the occurrences of rubbing contact between stationary and moving surfaces is of importance when such contact is likely to cause mechanical damage to the various cell types present in blood. The design and configuration of the heart valve prosthesis of the present invention is such that care has been taken to reduce the creation of zones or areas where blood passing through the device is exposed to substantial mechanical forces. As such, the operation of the valve of the present invention is practically noiseless and conventional acoustic techniques cannot be used to assess operational performance of such "silent" valves. Accordingly, it is desirable that some alternative method of monitoring valve performance and other physiologic parameters be incorporated in or with the valve.
SUMMARY OF THE INVENTION
The heart valve prosthesis of the present invention comprises an improvement which is particularly adapted for use as a modification of the valve described in co-pending application Ser. No. 08/122,802, filed Sep. 16, 1993 now U.S. Pat. No. 5,354,330, and entitled "HEART VALVE PROSTHESIS", the teachings of which are hereby incorporated fully by reference in this specification. It will be understood, of course, that the features of the present invention are readily adaptable for implementation in other types of valves, including other mechanical valves as well as tissue valves. In application Ser. No. 08/122,802 now U.S. Pat. No. 5,354,330, there is described a heart valve prosthesis having a generally annular body member with an interior surface defining a central passageway or lumen for blood flow therethrough. The annular body member is preferably formed from pyrolytic carbon and is provided with means for supporting a pair of pivotally moveable leaflets or occluders within the annular body in such a way that they alternately open and close under influence of the blood being pumped by the heart. The valves thereby allow only a unidirectional flow of blood through the lumen or passageway of the heart valve. The annular body is suspended within a stiffening ring and a locking wire of a predetermined diameter is contained within annular grooves formed in the outer surface of the annular body and the inner surface of the stiffening ring to prevent longitudinal movement of the annular body relative to the stiffening ring.
A fabric sewing cuff encompasses the outer surfaces of the stiffening ring. Disposed between a portion of the fabric sewing cuff and the stiffening ring is a moisture-proof, annular container for housing an electronic sensor, as well as a printed circuit board populated with appropriate electronic components for implementing a RF transceiver and an appropriate active or passive power supply for energizing same.
The sensor may comprise any one of a number of types capable of detecting the motion of the occluder and for providing an electrical signal indicative thereof to the transceiver circuitry. A blood flow sensor may also be used. The transceiver then functions to transmit analog or digital information to a suitable monitor located outside of the body of the patient in which the valve of the present invention is implanted. This sensor, in detecting the motion of the leaflets, may function to detect blood flow, cardiac output, as well as certain other information indicative of the function of the heart. The implanted transceiver can also receive commands from an external transmitter to accomplish some physiologic function, such as providing cardiac stimulating pulses in the event that post-surgical heart block occurs, or alternatively to control other cardiac arrhythmias.
DESCRIPTION OF THE DRAWINGS
The foregoing features, objects and advantages of the invention will become apparent to those skilled in the art from the following detailed description of the preferred embodiment, especially when considered in conjunction with the accompanying drawings in which like numerals in the several views refer to corresponding parts.
FIG. 1 illustrates a cross-section through the heart illustrating heart valve prostheses in accordance with the present invention used as replacements for the mitral valve and an aortic valve;
FIG. 2 is a greatly enlarged partial cross-sectional longitudinal view showing an electronics module contained within the sewing cuff of a typical heart valve prosthesis for transmitting and receiving information and commands transcutaneously to an external monitor system; and
FIG. 3 is a block diagram of the electronics associated with the heart valve prosthesis in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
For purposes of reference only, there is shown in FIG. 1 a vertically sectioned human heart 10 showing the right atrium 12, the left ventricle 14 and an artificial heart valve prosthesis 16 replacing the normal mitral valve and a further prosthetic heart valve 18 replacing the subject's aortic valve. The present invention may also be incorporated in a prosthesis replacing the tricuspid valve.
As will be explained in greater detail hereinbelow, either or both of the heart valve prostheses 16 and 18 may incorporate therein an appropriate sensor positioned and configured to detect the normal movement of the leaflets 20 and 22 as they open and close under influence of the blood flowing through the annular body of the artificial heart valve 16. The sensor module 24 is preferably contained within the valve structure, as will be further described, but in accordance with another feature of the present invention, the transceiver electronics may be in a separate moisture-proof container and coupled to the heart valve 16 in such a way that it can receive, amplify and transmit information transcutaneously through the chest wall 26 to an external transceiver/monitor 28.
Referring next to FIG. 2, the heart valve 16 is seen to include an annular body member 30 preferably formed from, but not limited to, pyrolytic carbon in which the occluder or leaflets 20 and 22 are pivotally suspended. The view of FIG. 2 does not show the leaflets themselves. As is fully explained in the aforereferenced co-pending application, the outer peripheral surface of the annular body 30 includes a groove 32 for receiving a lock wire 24 therein. Surrounding the valve body 30 is a metal or plastic stiffening ring 36 which also has an annular groove 38 formed therein for receiving a portion of the lock wire 34 therein. Stiffening ring 36 may be constructed of a non-conductive material. The tolerances are such that the lock wire 34 prevents relative longitudinal sliding motion between the annular body 30 and its surrounding stiffening ring 36.
Also formed inwardly of the annular surface of the stiffening ring 36 are upper and lower grooves designed to contain and trap a fabric sewing cuff 40 are first and second lock rings 42 and 44. Because of the manner in which the fabric sewing cuff 40 is wrapped about the stiffening ring 36 and the lock rings 42 and 44, the sewing cuff is prevented from coming free of the assembled heart valve 16.
In the embodiment of the heart valve disclosed in the aforereferenced '802 application, a plastic filler ring, identified therein by numeral 58, is fitted between the exterior of the stiffening ring 36 and the sewing cuff to create an annular flange. In the embodiment shown in FIG. 2 hereof, the filler ring is replaced by a moisture-proof ring-shaped container or housing 46, which is preferably a welded titanium can designed to house the circuitry identified by numeral 24 in FIG. 1. The cross-sectional view of FIG. 2 shows within can 46 a printed circuit substrate 48 which is populated with integrated and discrete electronic components comprising a transceiver circuit. A printed circuit coil antenna 50 is coupled to the electronic circuitry on the printed circuit board 48 for transmitting and receiving electrical signals.
Also housed within the container 46 is a suitable sensor element 52. The sensor 52 may be capacitive or inductive in nature and appropriately arranged to sense the movement of the leaflets 20 and 22 (FIG. 1). An inductive transducer may comprise a coil positioned in the stiffening ring to be cut by magnetic flux from a dipole mounted on or in the occluder. Those skilled in the art can appreciate that other forms of transducers for detecting movement and/or fluid flow through the annular body 30 can also be utilized in carrying out the principles of the present invention. For example, an ultrasonic Doppler flow sensor may be used to detect the behavior of the blood flow through the valve body as the leaflets open and close. Also, a quartz crystal transducer can be employed to sense vibration.
A suitable active power source, such as a lithium iodide battery of the type used in cardiac pacemakers may also be contained within the housing 46. Alternatively, a passive power source comprising the antenna 50 coupled through a suitable diode rectifying circuit to an energy storing capacitor may be provided so that the electronics within the housing 46 can be powered by a continuous wave RF signal transmitted percutaneous from the transceiver/monitor circuit 28 to the implanted valve electronics percutaneously.
When it is considered that the AV node, which controls the rate of the ventricles, is located in close proximity to both the mitral valve and the aortic valve and given the fact that during the post-operative period it is not uncommon for a patient to go into temporary or permanent heart block, it is also desirable that a means be provided for pacing the heart. In the past, it has been the practice to install temporary pacing leads percutaneously for connection to an external pacemaker. The heart pacing leads are relatively costly and require a channel through the skin which can become a site for infection, requiring ultimate removal of the leads.
Because the lock wire 32 is a conductor and is in blood contact, by connecting that wire to an electronic pulse generator within the housing 46 and controlling the pulse generator through an RF link between the antenna 56 of transceiver 28 and the antenna 50 of the implanted transceiver, pacing of the ventricles can be achieved.
In monitoring the operation of the implanted heart valve, information telemetered from the implanted electronics module to the external transceiver/monitor 28 allows assessment of such things as leaflet movement, pannus overgrowth on the ring, cardiac arrhythmias, cardiac output.
If it is desired to be able to assess a patient at a distance, the transceiver 28 located proximate the patient may be coupled, via modems 58 and 60, to a remotely located personal computer 62 located, for example, in the office of the cardiac surgeon, cardiologist, or paramedical personnel.
FIG. 3 is a system block diagram showing the implanted electronics within the broken line box 64. As earlier mentioned, the implanted electronic components may be contained as an integral part of the heart valve in the manner illustrated in FIG. 2 or, alternatively, the power source 66 and transceiver 68 may be separately packaged within a moisture-proof housing external to the heart but still within the patient's chest area. Only the sensor 70 and the electrode 72 would be disposed on or in the prosthetic heart valve itself. As before, messages may be transmitted percutaneously through the chest wall 26 to a local transceiver 28 and monitor 74 which may be a lap-top computer or similar device programmed to analyze the information provided by the sensor 70 to the implanted transceiver 68 and transmitted thereby to the transceiver 28. By using modems 58 and 60 joined to a telephone link 76, it is possible to monitor/control operation of the system from a remote location.
In the event an arrhythmia is detected, the system can be programmed to automatically initiate cardiac pacing. The monitor 74 will provide command pulses at a predetermined pacing rate to the transceiver 28 which will then send a command to the implanted transceiver 68 so that it can control the application of cardiac stimulating pulses from the pulse generator 69 to the electrode 72. As mentioned in connection with FIG. 2, the electrode 72 may comprise the lock wire 34 forming a part of the heart valve itself.
This invention has been described herein in considerable detail in order to comply with the Patent Statutes and to provide those skilled in the art with the information needed to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by specifically different equipment and devices, and that various modifications, both as to the equipment details and operating procedures, can be accomplished without departing from the scope of the invention itself.
For example, rather than disposing the electronics module in a moisture-proof container located between the sewing cuff 40 and the stiffening ring 36, some or all of the components comprising the electronics module may also be embedded in the stiffening ring 36. Hence the scope of the invention is to be determined from the following claims, when properly interpreted in light of the prior art.
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A heart valve prosthesis containing electronic circuitry for monitoring valve performance provides information to an implanted transceiver arranged to transmit digital or analog data transcutaneously to an external transceiver. The implanted electronics may be integrally contained within the heart valve prosthesis, or alternatively, may be separately housed in a moisture-proof container within the patient's body but external to the heart. By coupling the implanted transceiver to a pulse generator and electrode combination, electrical stimulating pulses can be applied to the heart upon command from an externally located monitor/transceiver combination.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Application No. PCT/JP2013/080517 filed Nov. 12, 2013, claiming priority based on Japanese Patent Application No. 2012-249792, filed Nov. 13, 2012, the contents of all of which are incorporated herein by reference in their entirety.
TECHNICAL FIELD
The present invention relates to novel 2-pyridone compounds having a glucokinase activating effect and to a medicine comprising the compound as an active ingredient. Further, the present invention relates to the crystals of the compounds and a method for producing the same.
BACKGROUND ART
The number of patients suffereing from type II diabetes is increasing worldwide, and progress of the patient's conditions and development of the complication cause a severe prognosis, under which the circumstances the development of a novel prophylactic agent or a therapeutic agent is eagerly desired. Type II diabetes, with the background of genetic predisposition and aging suggested to be associated with the development thereof, is considered to have a significantly increased risk of the development when the life style common in developed countries, namely, the condition involving an excessive energy intake to physical activities, is imposed. Also, the metabolic disorders, which are the underlying conditions, include poor glucose utilization in the skeletal muscle and fat tissues, insulin secretion disorder from pancreatic beta cells, and insufficient control of glucose release from the liver and an agent to improve these disorders is considered to be useful for preventing and treating type II diabetes.
For the glucose utilization in the skeletal muscle and fat tissues, a drug therapy using insulin sensitizers represented by a thiazolidine derivative (e.g., pioglitazone) is considered to be effective; however, aggravated obesity, body fluid retention, increased risk of cardiac insufficiency, increased incidence of bladder cancer, and the like, have been reported, where careful assessment is hence required when using these drugs. Further, for the insulin secretion disorder, sulfonylurea drugs (e.g., glimepiride, glibenclamide, glipizide) are considered to be effective; however, hypoglycemia and/or overweight is often caused, and also poor blood glycemic control (secondary failure) may occur due to reduced therapeutic effects when used for an extended period of time, thus leaving both safety and efficacy issues to be resolved. For the postprandial hyperglycemia, α-glucosidase inhibitors (e.g., acarbose, voglibose, and miglitol), or glinide drugs (e.g., nateglinide, repaglinide, and mitiglinide) are used but have limited therapeutic effects on diabetes. For controlling the glucose release from the liver, biguanide drugs (e.g., metformin) are effective, but glycemic control becomes difficult as conditions progress and additionally, in some cases, use of the drug may be limited due to the adverse effects on the digestive tract, lactic acidosis risk, or the like. As evident from the findings of the above major agents, the existing agents do not necessarily meet the medical requirements. In particular, metformin is substantially the only agent for directly improving the liver glucose metabolism, under which circumstance it is extremely essential to develop an agent capable of improving the liver glucose metabolism by a novel mechanism of action.
Glucokinase (hereinafter described as GK) belongs to the hexokinase family and catalyzes phosphorylation of glucose incorporated in cells such as pancreatic beta cells or hepatocytes. GK in the liver and pancreatic beta cells differ from each other in terms of the sequence of N-terminal 15 amino acids due to the difference in splicing but are enzymatically identical. GK has a high affinity to glucose S 0.5 of about 10 mM and is not inhibited by the product, glucose 6-phosphate. Therefore, its reaction rate sensitively responds to physiological changes of blood glucose levels. GK in pancreatic beta cells modulates glucose-dependent insulin secretion, while GK in the liver modulates the glycolytic pathway or glycogenesis, so that blood glucose levels are maintained and controlled. Therefore, GK is assumed to function as a glucose sensor to maintain homeostasis of blood glucose levels (see Non Patent Literature 1).
Genetically engineered mice and gene mutations discovered in humans support a hypothesis that GK functions as an in vivo glucose sensor. GK homozygous mice have been died of hyperglycemia immediately after birth, and heterozygous mice have been observed to have hyperglycemia and impaired glucose tolerance (see Non Patent Literature 2). In contrast, GK overexpressed mice have been confirmed to have hypoglycemia (see Non Patent Literature 3). Moreover, in human MODY2 (maturity onset diabetes of the young), in which GK gene mutation is observed, diabetes develops from his youth (see Non Patent Literature 4). These gene mutations have been confirmed to reduce GK activity. In contrast, families have been reported having gene mutations to enhance GK activity (see Non Patent Literature 5). These gene mutations have been observed to enhance affinity of GK to glucose and cause symptoms of fasting hypoglycemia associated with elevated blood insulin concentrations.
In this way, GK has been shown to function as a glucose sensor in mammals including humans.
Substances to increase GK activity (hereinafter described as GK activating substances) may improve hyperglycemia by increasing glucose metabolism and glycogenesis in the liver and glucose-responsive insulin secretion from pancreatic beta cells. In particular, the substances which increase GK activity predominantly in the liver may improve hyperglycemia by promoting the glucose metabolism in the liver in an insulin-independent manner. It can also expected that improvement of hyperglycemia leads to treatment and prevention of chronic diabetic complications such as retinopathy, nephropathy, neurosis, ischemic heart disease and arteriosclerosis and to treatment and prevention of diabetes-related diseases such as obesity, hyperlipidemia, hypertension and metabolic syndrome. Therefore, compounds to increase the function of GK are expected to be effective therapeutic agents for diabetes.
On the other hand, GK has been reported to be expressed not only in the pancreas and liver but also in the feeding center and to have an important function in the antifeeding effect by glucose (see Non Patent Literature 6). Accordingly, GK activating substances may act on the feeding center and have an antifeeding effect and can be expected not only as therapeutic agents for diabetes but also as therapeutic agents for obesity.
Incidentally, some compounds having 2-pyridone are reported as the GK activating substances but they are structurally far removed from those of the present invention (see Patent Literatures 1 and 2). Other 2-pyridone compounds having closely related structures are reported but the compounds of the present invention are not disclosed specifically (see Patent Literatures 3 and 4). The present invention differs from the report in that the report contains no description regarding the medical application and that it rather focuses on a synthetic method of 2-pyridone compounds (see Non Patent Literature 7). Further, certain acylurea compounds that may have a pseudocyclic structure have been reported as GK activating substances, but they are noncyclic compounds and differ from the compounds of the present invention (see Patent Literatures 5 and 6).
CITATION LIST
Non Patent Literature
Non Patent Literature 1: Matschinsky F. M. and Magnuson M. A., Frontiers in Diabetes, 16, 2004
Non Patent Literature 2: Grupe A. et al. Cell, 83, 1, 69-78, 1995
Non Patent Literature 3: Ferre T. et al. Proc. Natl, Acad. Sci., 93, 14, 7225-7230, 1996
Non Patent Literature 4: Vionnet N. et al. Nature, 356, 6371, 721-722, 1992
Non Patent Literature 5: Glaser B. et al. N. Engl. J. Med. 338, 4, 226-230, 1998
Non Patent Literature 6: Kang L. et al, Diabetes, 55, 2, 412-420, 2006
Non Patent Literature 7: Latif R. et al. J. Chem. Soc. C. Organic, 17, 2140-2144, 1968
Patent Literature
Patent Literature 1: WO 2008/079787
Patent Literature 2: WO 2010/013161
Patent Literature 3: US 4275069
Patent Literature 4: WO 2011/068211
Patent Literature 5: WO 2000/58293
Patent Literature 6: WO 2001/44216
SUMMARY OF INVENTION
Technical Problem
An object of the present invention is to provide compounds that have an excellent GK activating effect and are useful as pharmaceuticals.
Solution to Problem
In view of the circumstances mentioned above, the present inventors have carried out extensive studies to find compounds having a GK activating effect and, as a result, have found that the object can be achieved by a 2-pyridone compound represented by the following formula [1] (compound name: 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one), a tautomer of the compound, a pharmaceutically acceptable salt thereof (hereinafter the 2-pyridone compound, a tautomer of the compound, or a pharmaceutically acceptable salt thereof is represented by the term “the 2-pyridone compound or the relatives”), or a solvate of the 2-pyridone compound or the relatives, whereby the present invention has been accomplished.
(I) An embodiment of the present invention provides a 2-pyridone compound represented by formula [1]:
a tautomer of the compound, a pharmaceutically acceptable salt thereof, or a solvate of the 2-pyridone compound or the relatives.
(II) Another embodiment of the present invention provides a crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one according to (I), represented by the above formula [1] and having a physical property of the following (a):
(a) an X-ray powder diffraction pattern (Cu—Kα) showing peaks at diffraction angles 2θ of 8.5, 13.4, 19.1 and 24.5°.
(III) Another embodiment of the present invention provides a crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one according to (I), represented by the above formula [1] and having physical properties of the following (a) to (c):
(a) an X-ray powder diffraction pattern (Cu—Kα) showing peaks at diffraction angles 2θ of 8.5, 13.4, 19.1 and 24.5°;
(b) an infrared absorption spectrum showing characteristic absorption bands at 916, 1146, 1167, 1295, 1651, 1664, 2909, 2955, 3003 and 3146 cm −1 ; and
(c) a melting point of 199 to 201° C.
(IV) Another embodiment of the present invention provides a method for producing a crystal of 3 -cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one having the physical properties of the following (a) to (c):
(a) an X-ray powder diffraction pattern (Cu—Kα) showing peaks at diffraction angles 2θ of 8.5, 13.4, 19.1 and 24.5°;
(b) an infrared absorption spectrum showing characteristic absorption bands at 916, 1146, 1167, 1295, 1651, 1664, 2909, 2955, 3003 and 3146 cm −1 ; and
(c) a melting point of 199 to 201° C.,
the method comprising: dissolving 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one represented by the above formula [1] in an alcohol solvent while heating, to provide a solution; thereafter, adding a water solvent to the solution; cooling the resultant solution to 5° C. or lower to yield a crystal; and drying the obtained crystal at 60° C. or lower.
(V) Another embodiment of the present invention provides a medicine comprising, as an active ingredient, the 2-pyridone compound, a tautomer of the compound, a pharmaceutically acceptable salt thereof, or a solvate of the 2-pyridone compound or the relatives according to (I). (VI) Another embodiment of the present invention provides the medicine according to (V), wherein the medicine is used for preventing or treating a disease or condition that can be improved by a glucokinase activating effect. (VII) Another embodiment of the present invention provides the medicine according to (V), which is a hypoglycemic agent. (VIII) Another embodiment of the present invention provides the medicine according to (V), wherein the medicine is a prophylactic or therapeutic agent for diabetes.
Advantageous Effects of Invention
According to the present invention, there were provided 2-pyridone compounds having an excellent GK activating effect.
Moreover, according to the present invention, there was provided the crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one, which has a novel crystal useful as a pharmaceutical. The crystal is in the stable crystal form at around room temperature and has good storage stability.
Furthermore, according to the present invention, there was provided a novel production method for yielding the above crystal in a uniform quality in a safe and stable manner.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is an X-ray powder diffraction pattern of the crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one of the present invention.
FIG. 2 is an infrared absorption spectrum (ATR method, crystal: diamond) of the crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one of the present invention.
FIG. 3 shows differential thermal analysis/thermogravimetric curves of the crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one of the present invention.
DESCRIPTION OF EMBODIMENTS
The present invention will be described in detail below, but is not particularly limited to the exemplified embodiments.
In the present invention, “n” refers to normal, “i” refers to iso, “s” and “sec” refer to secondary, “tert” refers to tertiary, “c” refers to cyclo, “o” refers to ortho, “m” refers to meta and “p” refers to para.
First, the compounds of the present invention are described.
Examples of the pharmaceutically acceptable salts in the present invention include mineral acid salts such as hydrochlorides, hydrobromides, hydroiodides, phosphates, sulfates and nitrates; sulfonates such as methanesulfonates, ethanesulfonates, benzenesulfonates and p-toluenesulfonates; carboxylates such as oxalates, tartrates, citrates, maleates, succinates, acetates, benzoates, mandelates, ascorbates, lactates, gluconates and malates; amino acid salts such as glycine salts, lysine salts, arginine salts, ornithine salts, glutamates and aspartates; and mineral salts such as lithium salts, sodium salts, potassium salts, calcium salts and magnesium salts, and salts with organic bases such as ammonium salts, triethylamine salts, diisopropylamine salts and cyclohexylamine salts. Preferred examples include hydrochlorides, hydrobromides, phosphates, sulfates, methanesulfonates, p-toluenesulfonates, oxalates, tartrates, citrates, acetates, lactates, glutamates, aspartates, sodium salts, potassium salts, ammonium salts and triethylamine salts.
The solvates in the present invention are pharmaceutically acceptable solvates of the compounds or salts thereof of the present invention. The compounds and salts thereof of the present invention may absorb moisture, have adsorbed water, or form hydrates by exposure to the air, recrystallization or the like. The compounds of the present invention also include such hydrates.
The compounds of the present invention have two asymmetric centers and are optically active compounds, and the absolute configuration of both of the two asymmetric centers of the present compounds is (R). The compounds of the present invention can be obtained by the optical resolution of the corresponding racemic or diastereomer mixture. The optical resolution methods adoptable include those well known to a person skilled in the art such as fractional crystallization method or chiral column chromatography. Alternatively, the optically active compounds of the present invention can also be obtained by a well known technique in organic chemistry practiced for this purpose. Further, geometrical isomers such as (E) isomer and (Z) isomer may be present as the synthetic intermediates for obtaining the compounds of the present invention, and the ratio of these isomers can be in any proportion.
The compounds of the present invention encompass tautomers. The tautomer herein refers to a keto-enol tautomer of the compounds represented by the above formula [1].
The compounds represented by the above formula [1] and the tautomer [1′] thereof are shown below as an example.
The 2-pyridone compounds of the present invention may be pharmaceutically acceptable salts thereof or solvates of the 2-pyridone compound or the relatives. Hereinafter, the 2-pyridone compounds, tautomers of the compounds, pharmaceutically acceptable salts thereof, or solvates of the 2-pyridone compound or the relatives are collectively referred to as the “compounds of the present invention”.
The “compounds of the present invention” also include compounds commonly called prodrugs which have a chemically or metabolically decomposable group and form the pharmacologically active compounds of the present invention by solvolysis or in vivo under physiological conditions.
The compounds of the present invention have a GK activating effect. Therefore, the compounds of the present invention can improve hyperglycemia by increasing glucose metabolism mainly in the liver. Accordingly, the compounds can be used as novel drug therapies that differ in mechanism of action from the existing therapeutic agents for diabetes. Diabetes include type I diabetes, type II diabetes and other diabetes due to specific causes. The compounds of the present invention are also effective for the treatment and prevention of diabetic complications such as ketoacidosis, microangiopathy (retinopathy or nephropathy), arteriosclerosis (such as atherosclerosis, myocardial infarction, cerebral infarction or peripheral arterial occlusive disease), neuropathy (such as sensory neuropathy, motor neuropathy or autonomic neuropathy), foot gangrene and infections.
The compounds can also be used for the treatment and prevention of diabetes-related diseases such as obesity, hyperlipidemia, hypertension, metabolic syndrome, edema, hyperuricemia and gout.
The compounds of the present invention can also be used in combination with therapeutic agents having a mechanism of action other than a GK activating effect, such as those for diabetes, diabetic complications, hyperlipidemia, hypertension and the like. By combining the compounds of the present invention with those other agents, an additive effect can be expected for the above diseases as compared with the effect achieved by those respective agents each alone.
Examples of the therapeutic agents for diabetes and the therapeutic agents for diabetic complications usable in combination with the compounds of the present invention include insulin preparations, insulin sensitizers (such as PPARγ agonists, PPARα/γ agonists, PPARδ agonists and PPARα/γ/δ agonists) (e.g., pioglitazone, rosiglitazone, aleglitazar, peliglitazar, AVE-0897 and MBX-8025), α-glucosidase inhibitors (e.g., voglibose, acarbose and miglitol), biguanide drugs (e.g., metformin, buformin and phenformin), insulin secretion promoters (e.g., glibenclamide, glimepiride, repaglinide, nateglinide and mitiglinide), glucagon receptor antagonists, insulin receptor kinase promoters, dipeptidyl peptidase IV inhibitors (e.g., vildagliptin, alogliptin, sitagliptin, linagliptin, saxagliptin, teneligliptin, anagliptin), SGLT inhibitors (e.g., dapagliflozin, luseogliflozin, canagliflozin, empagliflozin, ipragliflozin, tofogliflozin), PTP1b inhibitors (e.g., sodium vanadate), glucose 6-phosphatase inhibitors, glycogen phosphorylase inhibitors (e.g., PSN-357 and FR-258900), FBPase inhibitors (e.g., MB-07803), PEPCK inhibitors, pyruvate dehydrogenase kinase inhibitors, D-chiro-inositol, GSK3 inhibitors, GLP-1 agonists (e.g., liraglutide and exenatide), amylin agonists (e.g., pramlintide), glucocorticoid receptor antagonists, 11βHSD1 inhibitors (e.g., INCB-13739, LY-2523199, Ro-5027838, Ro-5093151 and S-707106), protein kinase C inhibitors (e.g., ruboxistaurin), β3 adrenaline receptor agonists, phosphatidylinositol kinase inhibitors, phosphatidylinositol phosphatase inhibitors, ACC inhibitors, GPR40 receptor agonists (e.g., TAK-875), GPR119 receptor agonists (e.g., APD-597, PSN-821, MBX-2982 and DS-8500), GPR120 receptor agonists, TGR5 receptor agonists, AMPK activators, aldose reductase inhibitors (e.g., epalrestat, ranirestat, fidarestat) and AGE inhibitors.
Also, examples of the agents for diabetes-related diseases usable in combination with the compounds of the present invention include HMG-CoA reductase inhibitors, squalene synthase inhibitors, bile acid adsorbents, IBAT inhibitors, CETP inhibitors, CPT inhibitors, fibrates, ACAT inhibitors, MGAT inhibitors, DGAT inhibitors, cholesterol absorption inhibitors, pancreatic lipase inhibitors, MTP inhibitors, nicotinic acid derivatives, LXR agonists, LDL receptor promoters, angiotensin-converting enzyme inhibitors, angiotensin II antagonists, renin receptor antagonists, aldosterone antagonists, diuretics, calcium antagonists, alpha-blockers, beta-blockers,endothelin-converting enzyme inhibitors, endothelin receptor antagonists, appetite suppressants, uric acid production inhibitors and uricosuric agents.
The compounds of the present invention can be administered alone or with pharmaceutically or pharmacologically acceptable carriers or diluents. The compounds of the present invention used as GK activating substances may be orally or parenterally administered as such. The compounds of the present invention may also be orally or parenterally administered as agents containing the compounds as active ingredients. Examples of the parenteral administration include intravenous administration, nasal administration, transdermal administration, subcutaneous administration, intramuscular administration and sublingual administration.
The dosage of the compound of the present invention varies depending on the subject of administration, the route of administration, the disease of interest, the symptom and the like, and is usually about 0.01 to 1000 mg, and preferably 0.1 to 100 mg as a single dose when orally administered to an adult patient with diabetes, for example; it is desirable to administer this dose once, twice or three times per day.
Next, the method for producing the compounds of the present invention is described.
The compounds of the present invention can be synthesized by the processes shown below. The following production processes show general examples of production processes and do not limit the production processes.
The compounds of the present invention may also be synthesized using a method known in the field of chemistry per se or a method through one or more processes similar to that method. Examples of such methods include methods described in Organic Functional Group Preparations, 2nd ed., Academic Press, Inc., 1986, Comprehensive Organic Transformations, VCH Publishers Inc., 1989 and Fundamentals and Experiments of Peptide Synthesis, Maruzen Co., Ltd., 1985.
Suitable methods of protection and deprotection of functional groups contained in the starting materials, intermediates or the like in the synthesis of the compounds of the present invention can be performed according to the methods well known to a person skilled in the art such as the methods described in Greene's Protective Groups in Organic Synthesis, John Wily and Sons, 2006.
General processes for producing the compounds of the present invention are shown in Schemes 1 to 2. The following production processes do not limit the production processes. The compounds of the present invention can also be produced by using the methods well known to a person skilled in the art, for example, by changing the order of performing the steps; providing a protecting group for a hydroxy group or the like, carrying out a reaction and deprotecting in the subsequent step; or adding a new step in the course of respective steps.
Scheme 1: Process for synthesizing compound [1] of the present invention from compound (1-a).
(wherein in the scheme, G 1 represents a protecting group for the hydroxy group in the hydroxypyridyl group, R 1 represents a 2-benzothiazolyl group or 1-phenyl-1H-tetrazol-5-yl group.)
The compound (1-g) used in the step (1-4) may be obtained as a commercially available compound, a commonly known compound, or a compound easily obtainable using a variety of organic synthesis techniques known to a person skilled in the art.
Step (1-1):
Method for producing compound (1-b): the compound (1-b) can be produced by performing “fluorination” using a fluorinating reagent such as N,N-dimethoxyethylaminosulfur trifluoride (bis(2-methoxyethyl)aminosulfur trifluoride or Deoxo-Fluor (registered trademark)).
Examples of the fluorination include a method in which a fluorinating reagent such as Deoxo-Fluor (registered trademark) is reacted with the compound (1-a) in the absence of a solvent or in an inert solvent at a temperature of 0° C. to 100° C. to produce the compound (1-b).
Step (1-2):
Method for producing compound (1-d): the compound (1-d) can be produced by reacting the compound (1-c) with the compound (1-b) in an inert solvent in the presence of a base such as potassium acetate and a palladium catalyst.
Step (1-3):
Method for producing compound (14 the compound (1-0 can be produced by reacting a base such as n-butyllithium or n-butylmagnesium chloride with the compound (1-e) in an inert solvent and subsequently reacting N,N-dimethylformamide therewith.
The compound (1-e), a starting substance, can be obtained by the method described in WO 2011/068211 or a method in accordance therewith.
Steps (1-4, 1-5):
Method for producing compound (1-h): the compound (1-h) can be produced by reacting in an inert solvent bromine with (5R)-5[2-(5-cyclopropyl-6-methoxypyridin-2-yl)ethenyl]pyrrolidin-2-one (an E/Z mixture) obtained by a “coupling reaction” using the carbonyl compound (1-0 and the compound (1-g), and subsequently reacting a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) therewith.
Examples of the “coupling reaction” include a method for providing a compound (1-h) by generating an anion using the compound (1-g) as a matrix and an organometallic reagent such as n-butyllithium, sec-butyllithium or tert-butyllithium or a base such as lithium hexamethyldisilazide or potassium hexamethyldisilazide at a temperature of −78° C. to 100° C. in an inert solvent and then reacting the anion with a carbonyl compound (1-f). The olefin compound to be obtained is typically obtained in the form of E/Z mixtures, which however can be isolated respectively by resolution using silica gel column chromatography or HPLC.
The compound (1-g) used for the coupling reaction can be obtained by the method described in WO 2011/068211 or a method in accordance therewith.
Step (1-6):
Method for producing compound (1-i): the compound (1-i) can be produced by performing “coupling reaction” with the phenyl boron compound (1-d) using the compound (1-h) as a matrix in the presence of a palladium catalyst.
Examples of the coupling reaction include a method for reacting the compound (1-h) and the phenyl boron compound in an inert solvent at a temperature of 20° C. to 160° C. in the presence of a palladium catalyst and a base. The reaction can also be carried out by using microwaves.
Examples of the palladium catalyst used for the coupling reaction include palladium catalysts known to a person skilled in the art such as tetrakistriphenylphosphine palladium(0), bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), bis(triphenylphosphine)palladium(II) dichloride, bis(triphenylphosphine)palladium(H) acetate and a [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride-dichloromethane complex (1:1). Also, in the presence of a base, tris(dibenzylideneacetone)dipalladium(0) and tri(2-furyl)phosphine can be used for the reaction.
Step (1-7):
Method for producing compound (1-j): the compound (1-j) can be produced by reducing the compound (1-i) as a matrix by a catalytic hydrogenation reaction with a catalytic amount of palladium-activated carbon, rhodium-activated carbon or platinum-activated carbon in an inert solvent in the presence or absence of an acid at a temperature of 0° C. to 80° C.
Step (1-8):
Method for producing compound (1-k): the compound (1-k) can be produced by performing “deprotection reaction” of the protecting group G 1 possessed by a compound (1-j).
Examples of the deprotection reaction include (i) deprotection reactions where the protecting group G 1 is an alkyl group or an allyl group, such as a method of removing the protecting group by hydrolysis reaction in an inert solvent in the presence of an acid or a strong acid at a temperature of 0° C. to 200° C., a method using trimethylsilyl iodide, or the like, and a method using aluminum chloride and alkylthiol, and (ii) deprotection reactions where the protecting group G 1 is a benzyl group, a 4-methoxybenzyl group, a 2,4-dimethoxybenzyl group, a benzyloxycarbonyl group, a benzhydryl (diphenylmethyl) group or the like, such as a method of removing the protecting group by hydrogenolysis reaction using a catalytic amount of palladium-activated carbon, rhodium-activated carbon or the like in an inert solvent in the presence or absence of an acid at a temperature of 0° C. to 80° C., or a method using an oxidizing agent such as ammonium cerium(IV) nitrate or 2,3-dichloro-5,6-dicyano-p-benzoquinone.
Step (1-9):
Method for obtaining the compound [1] of the present invention: the compound [1] of the present invention can be obtained by diastereomeric resolution of compound (1-k) using, for example, HPLC.
The compound (1-a) and the compound (1-c) used as the raw material compounds in the above Scheme 1 can be obtained as commercial products or by a known method.
Scheme 2: Process for synthesizing the compound [1] of the present invention from compound (2-a)
(wherein in the scheme, G 1 and R 1 are as defined above. G 2 represents a protecting group for the nitrogen atom in the pyrrolidinyl group substituted with an oxo group.)
Step (2-1):
Method for producing compound (2-b): the compound (2-b) can be obtained by the method described in WO 2008/103185 or a method in accordance therewith.
Steps (2-2, 2-3):
Method for producing compound (2-c): the compound (2-c) can be produced by performing “addition reaction” using the compound (2-b) and an anion such as a lithium reagent such as heteroaryl lithium, a Grignard reagent such as heteroaryl magnesium bromide, and treating the obtained compound with an acid such as hydrochloric acid.
Examples of the “addition reaction” include a method for reacting the compound (2-b) with an anion generated by using the compound (1-e) as a matrix and an organometallic reagent such as n-butyllithium, sec-butyllithium, tert-butyllithium, or isopropyl magnesium bromide, a metal reagent such as magnesium or a base such as lithium hexamethyldisilazide or potassium hexamethyldisilazide in an inert solvent at a temperature of −78° C. to 100° C.
Step (2-4):
Method for producing compound (2-d): the compound (2-d) can be produced by performing “coupling reaction” using the carbonyl compound (2-c) and the compound (1-g).
Examples of the “coupling reaction” include the same coupling reactions as those previously described in Step (1-4).
The thus obtained compound (2-d) can be led to the compound [1] of the present invention by the method described in Steps (1-7) to (1-9) of the previously described Scheme 1.
Alternatively, the compound [1] of the present invention can also be produced by the following method.
Step (2-5):
Method for producing compound (2-e): the compound (2-e) possessing a protecting group G 2 can be produced by reacting di-tert-butyl dicarbonate or the like with the compound (2-d) containing a pyrrolidinyl group substituted with an oxo group.
Step (2-6):
Method for producing compound (2-f): the compound (2-f) can be produced by reducing the compound (2-e) as a matrix by a catalytic hydrogenation reaction with a catalytic amount of palladium-activated carbon, rhodium-activated carbon, platinum-activated carbon, or the like, in an inert solvent in the presence or absence of an acid at a temperature of 0° C. to 80° C.
Step (2-7):
Method for producing compound (2-g): the compound (2-g) can be produced by performing “deprotection reaction” of the protecting group G 2 possessed by the compound (2-f).
Examples of the deprotection reaction include a method using an acid such as hydrochloric acid or trifluoroacetic acid.
Step (2-8):
Method for producing compound [1] of the present invention: the compound [1] of the present invention can be produced by performing “deprotection reaction” of the protecting group G 1 possessed by the compound (2-g).
Examples of the “deprotection reaction” include the same deprotection reactions as those previously described in Step (1-8).
The compound (2-a) used as the raw material compound in the above Scheme 2 can be obtained as a commercial product or by a known method.
Finally, the crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one of the present invention and the method for producing the same are described.
The crystal of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one of the present invention (hereinafter sometimes referred to as “crystal of the present invention”) have the chemical structural formula represented by the above formula [1]. Further, the crystal of the present invention can be obtained in the form of single crystal having the consistent quality as described earlier with good reproducibility, can be supplied stably as the crystal of a drug substance used for producing pharmaceuticals, and has good storage stability.
The crystal of the present invention has physical properties of the following (a) to (c):
(a) an X-ray powder diffraction pattern (Cu—Kα, measurement method: transmission method) showing peaks at diffraction angles 2θ of 8.5, 10.8, 11.2, 11.6, 13.4, 16.8, 17.0, 17.9, 18.5, 18.8, 19.1, 19.4, 22.6, 23.1, 23.2 and 24.5°, particularly showing characteristic /peaks at diffraction angles 2θ of 8.5, 13.4, 19.1 and 24.5°;
(b) an infrared absorption spectrum (ATR method, crystal: diamond) showing characteristic absorption bands at 916, 1146, 1167, 1295, 1375, 1614, 1625, 1651, 1664, 2837, 2866, 2909, 2955, 2986, 3003, 3088 and 3146 cm −1 , particularly showing distinctive characteristic bands at 916, 1146, 1167, 1295, 1651, 1664, 2909, 2955, 3003 and 3146 cm −1 ; and
(c) a melting point of 199° C. to 201° C.
However, characteristic peaks by the X-ray powder diffraction may fluctuate depending on the measurement conditions. For this reason, peaks by the X-ray powder diffraction of the compounds of the present invention may sometimes have differences or may not be clear.
The crystal of the present invention has the X-ray powder diffraction pattern as shown in FIG. 1 , the infrared absorption spectrum (ATR method, crystal: diamond) as shown in FIG. 2 , and the differential thermal analysis/thermogravimetric curves as shown in FIG. 3 .
The crystal of the present invention can be produced by crystallizing 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one using an alcohol solvent.
The 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one as a raw material is an amorphous or a crystal before being dissolved in an alcohol solvent.
When the crystal of the present invention is obtained by the crystallization or recrystallization using an alcohol solvent, the dissolution of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one into an alcohol solvent and the crystallization of it from the alcohol solution can be carried out by the conventional manner. For example, a method in which an amorphous 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one is dissolved in an alcohol solvent while heating and subsequently cooled is employed.
Examples of the solvent compatible with an alcohol solvent include a water solvent and hydrocarbon solvents such as heptane.
The mixing ratio of an alcohol solvent to a solvent compatible with the alcohol solvent in the mixed solvent can be suitably changed.
The alcohol solvent used is preferably alcohol having 1 to 4 carbon atoms such as methanol, ethanol, 1-propanol, isopropyl alcohol, tert-butyl alcohol, 1-butanol, 2-butanol, 2-ethoxy ethanol, 2-methoxy ethanol, trifluoroethanol, ethylene glycol, and propylene glycol; more preferably methanol, ethanol, isopropyl alcohol or propylene glycol; and still more preferably methanol or ethanol.
The concentration of the dissolved 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one is 1 to 50% by mass, preferably 17 to 25% by mass. The % by mass used herein refers to the percent by mass of the 3 -cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one in the solution.
The crystallization of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one can be carried out at a temperature from −78° C. to the reflux temperature of a solvent, but a preferable example is a method comprising dissolving 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one in an alcohol solvent while heating the solution to 55° C. to 75° C.; subsequently, in some cases, adding a solvent compatible with the alcohol solvent such as water to the solution; and cooling down the solution to 5° C. or lower to allow the crystal to precipitate.
The cooling time is not particularly limited as long as it is 10 seconds or longer, but is typically 10 minutes to 24 hours, preferably 30 minutes to 5 hours. From the viewpoint of industrial production, it is preferably 2 hours to 4 hours.
The precipitated crystal is separated from the solution by filtering or centrifuging the suspension, which is subsequently dried at 60° C. or lower.
Further, a seed crystal can be used for the crystallization. The seed crystal can be prepared beforehand by a method well known to a person skilled in the art, such as scraping the wall of a container carrying a solution for crystal precipitation using a spatula.
The reaction temperature in the general processes for producing the compounds of the present invention is −78° C. to 250° C., and preferably −20° C. to 80° C. The reaction time is 5 minutes to 3 days, and preferably 30 minutes to 18 hours. The production processes may be performed under normal pressure, under pressure or under microwave irradiation, for example.
The base, the acid and the inert solvent in the description of the general processes for producing the compounds of the present invention will be more specifically described, but are not limited to the following illustrations. The usable isolation techniques will also be specifically described, but are similarly not limited to the following illustrations.
Examples of the “base” include inorganic bases such as alkali metal or alkaline earth metal hydrides (such as lithium hydride, sodium hydride, potassium hydride and calcium hydride), alkali metal or alkaline earth metal amides (such as lithium amide, sodium amide, lithium diisopropylamide, lithium dicyclohexylamide, lithium hexamethyldisilazide and potassium hexamethyldisilazide), alkali metal or alkaline earth metal C 1 -C 6 alkoxides (such as sodium methoxide, sodium ethoxide and potassium tert-butoxide), alkali metal or alkaline earth metal hydroxides (such as sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide), alkali metal or alkaline earth metal carbonates (such as sodium carbonate, potassium carbonate, calcium carbonate and cesium carbonate), alkali metal bicarbonates (such as sodium bicarbonate and potassium bicarbonate) and alkali metal or alkaline earth metal phosphates (such as tripotassium phosphate), amines (such as triethylamine, diisopropylethylamine and N-methylmorpholine) and basic heterocyclic compounds (such as pyridine, 4-dimethylaminopyridine, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DBN (1,5-diazabicyclo[4.3.0]nonane-5-ene), imidazole and 2,6-lutidine).
Examples of the “acid” include inorganic acids (such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid and phosphoric acid), organic acids (such as p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, formic acid, acetic acid and camphorsulfonic acid) and Lewis acids (such as boron trifluoride, boron tribromide, aluminum chloride, scandium triflate and ytterbium triflate).
The “inert solvent” is not limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, and the examples thereof include nitrile solvents, amide solvents, halocarbon solvents, ether solvents, aromatic solvents, hydrocarbon solvents, ester solvents, alcohol solvents, sulfoxide solvents and water. These solvents may be used as a mixture of two or more solvents in an appropriate proportion.
Examples of the nitrile solvents include acetonitrile and propionitrile. Examples of the amide solvents include N,N-dimethylformamide (hereinafter sometimes abbreviated as DMF), N,N-dimethylacetamide and N-methylpyrrolidone. Examples of the halocarbon solvents include dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride. Examples of the ether solvents include diethyl ether (hereinafter sometimes abbreviated as “ether”), tetrahydrofuran (hereinafter sometimes abbreviated as THF), 1,4-dioxane and 1,2-dimethoxyethane. Examples of the aromatic solvents include benzene, toluene, xylene and pyridine. Examples of the hydrocarbon solvents include hexane, pentane and cyclohexane. Examples of the ester solvents include ethyl acetate and ethyl formate. Examples of the alcohol solvents include methanol, ethanol, isopropyl alcohol, tert-butyl alcohol and ethylene glycol. Examples of the sulfoxide solvents include dimethyl sulfoxide (hereinafter sometimes abbreviated as DMSO).
Compounds obtained by the above production processes can be isolated and purified by known means such as solvent extraction, liquidity change, transfer, crystallization, recrystallization and various kinds of chromatography techniques.
Protecting groups that can be used by the compounds in the general processes for producing the compounds of the present invention will be described below, but are not limited to such illustrations; other protecting groups may also be suitably selected.
Examples of the protecting group G 2 include C 1 -C 6 acyl groups (such as formyl, acetyl and propionyl), C 2 -C 15 alkoxycarbonyl groups (such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, benzyloxycarbonyl and 9-fluorenylmethyleneoxycarbonyl), arylcarbonyl groups (such as benzoyl), a trityl group, a phthaloyl group, a N,N-dimethylaminomethylene group, substituted silyl groups (such as trimethylsilyl, triethylsilyl, dimethylphenylsilyl, tert-butyldimethylsilyl and tert-butyldiethylsilyl) and C 2 -C 6 alkenyl groups (such as 1-allyl), each of which is generally used in peptide synthesis. These groups may be substituted with one or more substituents selected from halogen atoms, C 1 -C 6 alkoxy groups (such as methoxy, ethoxy and propoxy) and a nitro group.
EXAMPLES
The present invention will be described in more detail by the following Examples and Test Examples. These examples do not limit the present invention and may be changed within the scope of the present invention.
In the following Examples, NH silica gel column chromatography refers to a column chromatography separation and purification using an NH2 type silica gel (Chromatorex (registered trademark) NH2 type, Biotage (registered trademark) SNAP KP-NH Catridge). The elution solvent ratio is expressed by the volume ratio unless indicated otherwise.
For silica gel column chromatography, Kanto Chemical Co. “Silica Gel 60”, Fuji Silysia “PSQ60B” or a packed column (YAMAZEN HiFlash™ Column, MORITEX Purif Pack or Biotage (registered trademark) SNAP KP-Sil Catridge) was used.
The abbreviations used in the present specification mean as follows.
s: singlet d: doublet t: triplet q: quartet dd: double doublet m: multiplet br: broad J: coupling constant Hz: Hertz CDCl 3 : Chloroform-d
1 H-NMR (proton nuclear magnetic resonance spectrum) was measured using the following Fourier transform NMRs.
300 MHz: JNM-ECP300 (JEOL), JNM-ECX300 (JEOL) 600 MHz: JNM-ECA600 (JEOL)
ACD/SpecManager ver.12.01 (tradename), or the like, was used for the analysis.
MS (mass spectrum) was measured using the following apparatuses. micromass ZQ (Waters)
LTQ XL (Thermo Fisher Scientific) LCMS-2010EV (Shimadzu) LCMS-IT-TOF (Shimadzu) Agilent 6150 (Agilent) LCQ Deca XP (Thermo Fisher Scientific)
For the ionization method, an ESI (Electrospray Ionization) method or a dual ionization method of ESI and APCI (Atmospheric Pressure Chemical Ionization) was used.
The optical rotation measurement was carried out using a JASCO Corporation polarimeter (Model No.: P-1020).
The X-ray powder diffraction measurement was carried out using a PANalytical X′Pert PRO MPD (source of radiation: Cu.Kα).
The infrared absorption spectrum measurement was carried out by the ATR method (attenuated total reflection) using a Thermo Fisher Scientific Nicolet iS5.
The melting point measurement was carried out using a Mettler Toledo MP90 automatic melting point determination system.
For the preparative HPLC column, Daicel Chemical Industries, LTD. CHIRALPAK IB 5 μm (I. D. 20 mm, Length 250 mm), or the like, was used.
For the analytical HPLC column, Daicel Chemical Industries, LTD. CHIRALPAK IB 5 μm (I. D. 4.6 mm, Length 250 mm), or the like, was used.
The nomenclature for chemical compounds was based on ACD/Name ver.12.01 (tradename), or the like.
Example 1
3 -Cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one
(1) 1-Bromo-4-(1,1-difluoroethyl)benzene
Deoxo-Fluor (registered trademark) (22.2 g) was added to 1-(4-bromophenyl)ethanone (20.0 g) and the mixture was stirred at 85° C. for 15 hours. Under ice-cooling, ice water and an aqueous solution of potassium carbonate were added to the reaction solution, followed by extraction with chloroform. The solvent was evaporated under reduced pressure and the obtained residue was purified by silica gel column chromatography (hexane) to give the title compound (13.0 g, yield 59%) as a yellow oil.
1 H NMR (600 MHz, CDCl 3 ) δ ppm 1.91 (t, J=18.2 Hz, 3H), 7.50 (d, J=8.3 Hz, 2H), 7.86 (d, J=8.3 Hz, 2H).
(2) 2-[4-(1,1-Difluoroethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
Bispinacol diborate (22.5 g), [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride-dichloromethane complex (904 mg) and potassium acetate (8.70 g) were added to a solution of 1-bromo-4-(1,1-difluoroethyl)benzene (9.80 g) synthesized in Example 1-(1) in 1,4-dioxane (60 mL), and stirred at 90° C. for 10 hours. The reaction solution was poured into water, followed by extraction with chloroform. The solvent was evaporated under reduced pressure and the obtained residue was purified by silica gel column chromatography (hexane) to give the title compound (7.87 g, yield 66%) as a colorless solid.
1 H NMR (600 MHz, CDCl 3 ) δ ppm 1.35 (s, 12H), 1.91 (t, J=18.2 Hz, 3H), 7.50 (d, J=7.8 Hz, 2H), 7.86 (d, J=7.8 Hz, 2H).
(3) 5-Cyclopropyl-6-methoxypyridin-2-carbaldehyde
A 2M solution of n-butylmagnesium chloride in tetrahydrofuran (74.5 mL) was added to a mixed solvent of toluene (433 mL)-tetrahydrofuran (116 mL) in an argon atmosphere. A 1.6M solution of n-butyllithium in tetrahydrofuran (186 mL) was added dropwise at −12° C., stirred for 40 minutes, and subsequently 6-bromo-3-cyclopropyl-2-methoxypyridine (34.0 g) was added thereto. After stirring further 1 hour, N, N-dimethylforamide (32.7 g) was added dropwise thereto. After further stirring for 1 and a half hours, the reaction solution was added to a 13% aqueous solution of citric acid and extracted, and subsequently the organic layer was washed with water. The solvent was evaporated under reduced pressure and the obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=95:5 90:10) to give the title compound (21.2 g, yield 80%) as a yellow oil.
1 H NMR (600 MHz, CDCl 3 ) δ ppm 0.73-0.78 (m, 2H), 1.03-1.08 (m, 2H), 2.14-2.21 (m, 1H), 4.07 (s, 3H), 7.19 (d, J=7.4 Hz, 1H), 7.49 (d, J=7.4 Hz, 1H), 9.92 (s, 1H).
MS (+): 178[M+H] + .
(4), (5) (5R)-5-[(Z)-2-Bromo-2-(5-cyclopropyl-6-methoxypyridin-2-yl)ethenyl]pyrrolidin-2-one
(4) A 1M solution of potassium hexamethyldisilazide in tetrahydrofuran (405 mL) was added dropwise at −78° C. to a solution of (5R)-5-[(1,3-benzothiazol-2-ylsulfonyl)methyl]pyrrolidin-2-one (30.0 g) and lithium chloride (8.58 g) in tetrahydrofuran (1.2 L), and subsequently stirred for 1 hour. A solution of 5-cyclopropyl-6-methoxypyridine-2-carbaldehyde (17.9 g) synthesized in Example 1-(3) in tetrahydrofuran (600 mL) was added dropwise thereto and further stirred for 0.5 hour. A saturated ammonium chloride solution (500 mL) was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, followed by separating the desiccant by filtration, and evaporating the solvent under reduced pressure. The obtained residue was purified twice by silica gel column chromatography (hexane:ethyl acetate=100:0→70:30) to obtain (5R)-5-[(Z)-2-(5-cyclopropyl-6-methoxypyridin-2-yl)ethenyl]pyrrolidin-2-one (8.40 g, yield 34%) as a yellow oil.
1 NMR (600 MHz, CDCl 3 ) δ ppm 0.62-0.68 (m, 2H), 0.93-0.99 (m, 2H), 1.89-1.97 (m, 1H), 2.03-2.09 (m, 1H), 2.33-2.56 (m, 3H), 3.98 (s, 3H), 5.53-5.55 (m, 1H), 5.70 (dd, J=11.56, 7.84 Hz, 1H), 5.94-6.03 (br.s., 1H), 6.34 (dd, J=11.56, 1.24 Hz, 1H), 6.70 (d, J=7.43 Hz, 1H), 7.07 (d, J=7.43 Hz, 1H).
MS (+): 259[M+H] + .
(5) Bromine (1.33 mL) was added dropwise to a solution of (5R)-5-[(Z)-2-(5-cyclopropyl-6-methoxypyridin-2-yl)ethenyl]pyrrolidin-2-one (8.40 g) synthesized in Example 1-(4) in chloroform (126 mL) at 0° C. After stirring for 1 hour, a solution of 1,8-diazabicyclo[5.4.0]undec-7-ene (9.7 mL) in chloroform (42 mL) was added dropwise over a period of 30 minutes and stirred for 15 minutes. One M hydrochloric acid (200 mL) was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, followed by separating the desiccant by filtration, and evaporating the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=50:50→0:100) to give the title compound (7.50 g, yield 68%) as a yellow solid.
1 H NMR (600 MHz, CDCl 3 ) δ ppm 0.65-0.68 (m, 2H), 0.95-1.00 (m, 2H), 1.96-2.10 (m, 2H),
2.40-2.59 (m, 3H), 4.00 (s, 3H), 4.80 (q, J=7.4 Hz, 1H), 5.68-5.70 (br.s., 1H), 7.10 (d, J=7.8 Hz, 1H), 7.15 (d, J=7.8 Hz, 1H), 7.24 (d, J=7.8 Hz, 1H).
MS (+): 337[M+H] + .
(6) (5R)-5-{(E)-2-(5-Cyclopropyl-6-methoxypyridin-2-yl)-2-[4-(1,1-difluoroethyl)phenyl]ethenyl}pyrrolidin-2-one
In a nitrogen atmosphere, 2-[4-(1,1-difluoroethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.59 g) synthesized in Example 1-(2), cesium carbonate (1.92 g), tris(dibenzylideneacetone)dipalladium (0) (271 mg), tri(2-furyl)phosphine (412 mg) and distilled water (10 mL) were added to a solution of (5R)-5-[(Z)-2-bromo-2-(5-cyclopropyl-6-methoxypyridin-2-yl)ethenyl]pyrrolidin-2-one (1.0 g) synthesized in Example 1-(5) in 1,4-dioxane (50 mL), and the mixture was stirred at 90° C. for 2 hours. The reaction solution was poured into water, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, followed by separating the desiccant by filtration, and evaporating the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→0:100), further by NH silica gel column chromatography (hexane:ethyl acetate=100:0→0:100) to give the title compound (1.13 g, yield 96%) as a colorless amorphous.
1 H NMR (600 MHz, CDCl 3 ) δ ppm 0.56-0.64 (m, 2H), 0.90-0.97 (m, 2H), 1.93-2.09 (m, 5H), 2.20-2.34 (m, 2H), 2.37-2.45 (m, 1H), 4.04 (s, 3H), 4.07-4.16 (m, 1H), 5.73-5.75 (br.s., 1H), 6.23 (d, J=7.4 Hz, 1H), 6.90 (d, J=9.9 Hz, 1H), 6.92 (d, J=7.8 Hz, 1H), 7.24 (d, J=8.3 Hz, 2H), 7.57 (d, J=7.8 Hz, 2H).
MS (+): 399[M+H] + .
(7) (5R)-5-{2-(5-Cyclopropyl-6-methoxypyridin-2-yl)-2-[4-(1,1-difluoroethyl)phenyl]ethyl}pyrrolidin-2-one
In a nitrogen atmosphere, 10% palladium-activated carbon (110 mg) was added to a solution of (5R)-5-{(E)-2-(5-cyclopropyl-6-methoxypyridin-2-yl)-2-[4-(1,1-difluoroethyl) phenyl]ethenyl}pyrrolidin-2-one (1.1 g) synthesized in Example 1-(6) in methanol (44 mL) and the mixture was stirred at room temperature for 1 hour in a hydrogen atmosphere. After filtering the reaction solution using Celite (registered trademark), the solvent was evaporated under reduced pressure to give the title compound (1.10 g, yield 99%) as a colorless amorphous.
MS(±): 401[M+H] + .
(8) 3-Cyclopropyl-6-{1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one
Chlorotrimethylsilane (707 μL) and potassium iodide (1.37 g) were added to a solution of (5R)-5-{2-(5-cyclopropyl-6-methoxypyridin-2-yl)-2-[4-(1,1-difluoroethyl)phenyl]ethyl}pyrrolidin-2-one (1.1 g) synthesized in Example 1-(7) in acetonitrile (30 mL) and the mixture was stirred at 60° C. for 1 hour. The reaction solution was poured into water, followed by extraction with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, followed by separating the desiccant by filtration and evaporating the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography (chloroform:methanol=100:0→80:20) to give the title compound (880 mg, yield 83%) as a colorless amorphous.
MS(+):387[M+H] + .
(9) 3-Cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one
ARS mixture (180 mg) of 3-cyclopropyl-6-{1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one synthesized in Example 1-(8) was fractionated using a chiral HPLC column (CHIRALPAK IB, hexane:ethanol=70:30 v/v, 40° C., 12 mL/min, 254 nm) to give the title compound (70 mg) as a colorless amorphous and the diastereomer (67 mg) of the title compound as a colorless amorphous.
1 H NMR (600 MHz, CDCl 3 ) δ ppm 0.54-0.67 (m, 2H), 0.90-0.98 (m, 2H), 1.68-1.75 (m, 1H), 1.88 (t, J=18.2 Hz, 3H), 2.07-2.14 (m, 1H), 2.14-2.40 (m, 5H), 3.43-3.52 (m, 1H), 4.07-4.12 (m, 1H), 6.00 (d, J=7.0 Hz, 1H), 6.92 (d, J=7.0 Hz, 1H), 7.41-7.47 (m, 4H), 7.60-7.68 (m, 1H), 12.28-12.49 (br.s., 1H).
MS (+): 387[M+H] + .
CHIRALPAK IB 4.6×250 mm 5 μm (DAICEL), hexane:ethanol=70:30 v/v, 40° C., 1.0 mL/min, 210 nm, Rt=7.5 min.
Diastereomer
1 H NMR (600 MHz, CDCl 3 ) δ ppm 0.54-0.66 (m, 2H), 0.95-1.05 (m, 2H), 1.75-1.84 (m, 1H), 1.90 (t, J=18.0 Hz, 3H), 2.15-2.41 (m, 6H), 3.54-3.64 (m, 1H), 4.16 (dd, J=10.1, 5.57 Hz, 1H), 6.01 (s, 1H), 6.96 (d, J=7.0 Hz, 1H), 7.39 (d, J=8.26 Hz, 2H), 7.47 (s, 2H), 7.83-7.92 (m, 1H), 13.14-13.34 (br.s., 1H).
MS (+): 387[M+H] + .
CHIRALPAK IB 4.6×250 mm 5 μm (DAICEL), hexane:ethanol=70:30 v/v, 40° C., 1.0 mL/min, 210 nm, Rt=18.9 min.
Example 2
(5R)-5-{2-(5-Cyclopropyl-6-methoxypyridin-2-yl)-2-[4-(1,1-difluoroethyl)phenyl]ethenyl}pyrrolidin-2-one
(1) (5-Cyclopropyl-6-methoxypyridin-2-yl)[4-(1,1-difluoroethyl)phenyl]methanone
In a nitrogen atmosphere, a 1.6 M solution of n-butyllithium in tetrahydrofuran (127 mL) was added dropwise to a solution of 6-bromo-3-cyclopropyl-2-methoxypyridine (41.5 g) in tetrahydrofuran (273 mL) at −78° C. over a period of 50 minutes, followed by stirring at −78° C. for 1 hour. Subsequently, a solution of 4-(1,1-difluoroethyl)benzonitrile (24.3 g) in tetrahydrofuran (137 mL) was added dropwise to the reaction solution while maintaining the temperature at −78° C. over a period of 75 minutes, further followed by stirring for 1 hour. After the temperature of the reaction solution was raised to 0° C., 1M hydrochloric acid (437 mL), tetrahydrofuran (365 mL) and 1M hydrochloric acid (146 mL) were sequentially added dropwise thereto.
The reaction solution was separated into the organic layer and the aqueous layer, followed by extracting the aqueous layer with ethyl acetate (1000 mL). The combined organic layers were dried over anhydrous magnesium sulfate, the desiccant was separated by filtration, and subsequently the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→95:5) to give the title compound (34.0 g, yield 74%) as a colorless oil.
1 H NMR (300 MHz, CDCl 3 ) δ ppm 0.72-0.81 (m, 2H), 1.00-1.10 (m, 2H), 1.96 (t, J=18.2 Hz, 3H), 2.10-2.25 (m, 1H), 3.95 (s, 3H), 7.24 (d, J=6.9 Hz, 1H), 7.59 (d, J=9.0 Hz, 2H), 7.67 (d, J=7.8 Hz, 1H), 8.21 (d, J=8.6 Hz, 2H).
MS (+): 318[M+H] + .
(2) (5R)-5-{2-(5-Cyclopropyl-6-methoxypyridin-2-yl)-2-[4-(1,1-difluoroethyl)phenyl]ethenyl}pyrrolidin-2-one
In a nitrogen atmosphere, a 1.0 M solution of lithium hexamethyldisilazide in tetrahydrofuran (317 mL) was added dropwise to a solution of (5-cyclopropyl-6-methoxypyridin-2-yl)[4-(1,1-difluoroethyl)phenyl]methanone (33.5 g) obtained in Example 2-(1) and (5R)-5-[(1,3-benzothiazol-2-ylsulfonyl)methyl]pyrrolidin-2-one (37.5 g) in dichloromethane (1007 mL) over a period of 50 minutes at −78° C. and the mixture was stirred at −78° C. for 4 hours and 40 minutes.
After the temperature of the reaction solution was raised to 0° C., a saturated aqueous ammonium chloride solution (335 g) was added dropwise to complete the reaction. The reaction solution was separated into an organic layer and an aqueous layer, followed by extracting the aqueous layer with chloroform (339 mL) and washing the combined organic layers with water (502 g). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was separated by filtration, and subsequently the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=50:50→0:100) to give the title compound which was a E/Z mixture as a light yellow amorphous (42.7 g, E:Z=50:50).
The mixing ratio was determined by the area percentage of liquid chromatography.
The conditions for liquid chromatography were as follows.
L-Column ODS, CH 3 CN:0.01 M acetate buffer (0.01 M aqueous acetic acid solution: 0.01 M aqueous sodium acetate solution=8:1)=80:20 v/v, 1.0 mL/min, 40° C., 254 nm, E: Rt=5.40 min, Z:Rt=5.08 min.
MS(+) :399[M+H] + .
Hereinafter, the title compound can be proceeded to the compound [1] by the methods described in Examples 1 (7) to (9) or a method in accordance therewith.
Example 3
Crystal of compound [1]
Method for Crystallizing Compound [1]
Water (29 g) was added dropwise to a solution of 3-cyclopropyl-6-{(1R)-1-[4-(1,1-difluoroethyl)phenyl]-2-[(2R)-5-oxopyrrolidin-2-yl]ethyl}pyridin-2(1H)-one (14.4 g) in ethanol (72 g) at 75° C. While gradually cooling down from 75° C., a piece of seed crystal was added at the time of reaching an inner temperature of 40° C. and the temperature was cooled to room temperature. The temperature was further cooled to 0° C., and the solution was stirred overnight to prepare a suspension.
The temperature was returned to room temperature, the obtained solid was collected by filtration, washed with water and dried (50° C., 6 hours) to give 8.7 g (yield 60%) of a colorless crystal.
(a) An X-ray powder diffraction pattern (Cu—Kα, measurement method: transmission method) shows peaks at diffraction angles 2θ of 8.5, 10.8, 11.2, 11.6, 13.4, 16.8, 17.0, 17.9, 18.5, 18.8, 19.1, 19.4, 22.6, 23.1, 23.2 and 24.5°. (b) An infrared absorption spectrum (ATR method, crystal: diamond) shows characteristic absorption bands at 916, 1146, 1167, 1295, 1375, 1614, 1625, 1651, 1664, 2837, 2866, 2909, 2955, 2986, 3003, 3088 and 3146 cm −1 . (c) A melting point is 199° C. to 201° C. (d) A specific optical rotation is [α] D 23 =+36 (c0.1, MeOH).
The GK activating effect of the compounds of the present invention can be evaluated in accordance with a known technique such as the method described in Test Examples.
The GK activating effects of the compound [1] of the present invention, the compound A (Example 4-302), the compound B (Example 4-248) and the compound C (Example 4-340) disclosed in WO 2011/068211 were measured using the method described in the following Test Examples.
The structures of the compound A, the compound B and the compound C disclosed in WO 2011/068211 are shown below.
(Test Example 1.)
GK Activation Test
The GK activation test for the test compounds was carried out by the method of Van Schaftingen et al. (Eur. J. Biochem. 179:179-184, 1989) with partial modifications. The GK activity was measured by the change in the absorbance based on an amount of thio-NADH, which is a reduced form product converted from thio-NAD+ (thionicothinamide-adeninedinucleotide) when dehydrogenating glucose 6-phosphate, produced by GK using glucose as a matrix, with G6PDH (glucose-6-phosphate dehydrogenase).
The enzyme source used in this assay, human liver GK, was expressed in E. coli as a fusion protein with GST (glutathione S-transferase) added to the amino terminus and was purified using Glutathione Sepharose 4B (Amersham Biosciences).
The test was carried out using flat-bottom 96-well half area microplates (Corning). A solution of the test compound in dimethyl sulfoxide (DMSO) at a final concentration of 1% in DMSO and DMSO as a control were added to each well of the plates. Further, 25 mM Hepes-KOH (pH=7.1), 25 mM KCl, 2 mM MgCl 2 , 2 mM thio-NAD+, 4 mM glucose, 1 mM DTT (dithiothreitol), 0.01 units/μL G6PDH and 2 μg/mL human liver GK were added as the final concentrations, respectively, to each of the wells. Subsequently, ATP was added to each of the wells to give the final concentration of 2 mM, and the reaction was started. The microplates were allowed to stand at room temperature. After 15 minutes from the start of reaction, the absorbance at 405 nm was measured using an absorption spectrometer for microplate.
The GK activity maximally activated by the test compound was taken as the maximum activation ability, and the test compound concentration (nM) needed to activate 50% of that maximum activation ability was expressed as EC 50 .
The results are shown below.
TABLE 1
Compound
EC 50 [nM]
Compound [1]
295
Compound A
520
Compound B
1326
Compound C
597
(Test Example 2.)
Hypoglycemia Test using C57BL6/J Mice
The test to verify the hypoglycemic effect of the test compounds was carried out in accordance with a method commonly used and represented by the method of Grimsby et. al (Science 301: 370-373, 2003).
The body weight of C57BL6/J mice (N=6), who were ad libitum fed before the test, was measured. The test compound was suspended or dissolved in the base to be administered (0.5% methyl cellulose) at a concentration of 0.06 to 20 mg/mL. The mice were orally administered with 5 mL/kg of a drug solution (equivalent to 0.3 to 100 mg/kg of the test compound) or control (only the base to be administered). About 60 μL of blood was collected from the tail vein using a capillary tube immediately before administration of the test compound and 0.5, 1, 2, 4 and 6 hours after administration of the test compound. The collected blood was centrifuged and subsequently measured for the plasma glucose concentration. The area under the curve (AUC) was calculated from changes over time in the plasma glucose concentration after administration of the test compound, and a reduction rate (%) to AUC of the control group was calculated. The dose at which an AUC decreasing percentage was 20% (ED 20 value; mg/kg) was calculated from the dose response curve having the AUC reduction rate plotted on the vertical axis and the dose plotted on the horizontal axis.
The results are shown below.
TABLE 2
Compound
ED 20 [mg/kg]
Compound [1]
4.2
Compound A
11.5
Compound B
15.6
Compound C
32.0
The above test results ascertained that the compounds of the present invention show good hypoglycemic effects from a low dose range. In conclusion, the compounds of the present invention are useful as a prophylactic/therapeutic agent for diabetes, and the like, and the therapeutic range thereof is evidently wider than other compounds.
Further, the compounds of the present invention, when compared with three compounds disclosed in WO 2011/068211, were revealed to have a much stronger hypoglycemic effect.
Additionally, the compounds of the present invention have properties desirable to be pharmaceuticals. Examples of such a property include good hypoglycemic effects by exhibiting good physical properties and pharmacokinetics (e.g., hepatic metabolism stability).
INDUSTRIAL APPLICABILITY
The compounds of the present invention have an excellent GK activating effect and can provide therapeutic and prophylactic agents not only for diabetes but also for diabetes-related diseases such as obesity and hyperlipidemia or chronic diabetic complications such as retinopathy, nephropathy and arteriosclerosis.
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This 2-pyridone compound represented by formula [1] or a tautomer of said compound, or a pharmaceutically acceptable salt of said compound or said tautomer, or a solvate of said compound or the like has a superior GK-activating effect and is useful as a pharmaceutical.
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SUMMARY OF INVENTION
This invention relates to new and useful improvements in missile launching toys and more particularly, seeks to provide a hollow cylinder adapted to fit in and be twirled by one hand which causes rotation of a head through rotation of an integral handle extending out of the cylinder and being angularly disposed to thus move the head upwardly to compress a spring, air or other energy storage element that is subsequently used to launch a missile such as a projectile, balloon, etc.
OBJECTS OF THE INVENTION
It is an object of this invention to provide a simple hand toy that young children can use to launch missiles by merely placing the missile in the launcher and twirling the body of the toy.
It is a further object to provide a toy, the use of which can be easily repeated while the hollow cylinder is held in the child's hands.
With these and other objects, the nature of which will be apparent, the invention will be more fully understood by reference to the drawings, the accompanying detailed description, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a vertical section through a toy with the spring compressed and the missile ready to be released, constructed in accordance with this invention;
FIG. 2 is a vertical section just after release of said missile;
FIG. 3 is a verticle section after reloading of said missile but before spring compression;
FIG. 4 is an enlarged perspective view of a modified locking member for the threaded rotating head;
FIG. 5 is a vertical section through a second toy embodiment showing a balloon missile during inflation;
FIG. 6 is a vertical section taken along line 6--6 of FIG. 5; and,
FIG. 7 is a horizontal section taken along line 7--7 of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings in detail, the invention, as illustrated, is embodied in a missile launcher toy, which includes a hollow tubular body 11 of a size which can be conveniently gripped and twirled in one hand, provided with a bottom end closure cap 13 having a port 15 and a top opening 17 surrounded by a shoulder flange 19. The body 11 is provided with a semi-circular interior female threaded portion 21 at one side of its lowermost end, adjacent bottom end closure cap 13, with lateral ports 23, 25 to accommodate protruding operating buttons, and with resilient elements such as, springs 27, 29 mounted interiorly of the body, one adjacent each end thereof.
A hollow tubular form or barrel 31 is arranged epicentrically interiorly of the body 11 and is formed or provided with a semicircular interior female threaded portion 33, having threads of gauge and pitch to match the threaded portion 21, a launch button 35, and a reset button 37, disposed to protrude respectively through lateral ports 23 and 25 of body 11. As shown in the drawings, the generally overall tubular form of barrel 31 is cut or formed to approximate semi-circular cross sections at each end, the lower half-tubular section extending below the location of the reset button 37 comprising the threaded portion 33 and the upper half-tubular section extending above the location of the launch button 35 and mounting a missile launch lock protrusion 39, extending interiorly to engage a matching recess 55 on the missile shaft.
The energy imparting element of the embodiment shown comprises a shaft 41 provided with a male threaded head end 43, having threads of a gauge and pitch to engage the female threads of body and barrel portions 21 and 33, respectively, an arm 45 fixedly attached to and extending angularly from the lower extremity of shaft 41, and a counterweight 47 integral to arm 45. A locking mechanism for FIGS. 1 to 3 is shown as well 57 in barrel 31 enclosing a locking pawl 59 and pawl spring 61. When barrel 31 is vertical, head 43 is locked above pawl 59 after clearing same. However, once 31 moves to the right as shown in FIG. 2, the head can be threaded downwardly past pawl 59. As shown in FIG. 4, a modified head 43 has a groove 65 which engages barrel locking protrusion 63, when the head has moved upwardly to the proper point but only as long as barrel 31 is vertical.
Mounted above the male head 43 is a compressible spring 49 with an associated retainer 67 affixed to barrel 31. The free end of missile shaft 53 rides on the upper end plate of spring 49. The shaft has an intermediate recess 55 and four vanes 51 at the head end.
The body 11 is rapidly twirled by moving the hand holding same about a short radius through a circle of 6 to 12 inches diameter, which causes counterweight 47 to rotate the head 43 until it is at the bottom of body 11 as seen in FIG. 3. The missile shaft is then placed through the top opening 69 against spring 49 and the reset button 37 is pushed to the right so that barrel 31 is vertical, and launch lock protrusion 39 engages recess 55 to hold the missile in locked but uncharged position as shown in FIG. 3. Counterweight 47 is caused to rotate in the opposite direction by twirling body 11 until the head 43 passes pawl 59 to compress spring 49 and store energy therein, at which time the pawl is spring-driven toward the shaft 41 to lock the head 43 at the uppermost position shown in FIG. 1. At this point, the launch button 35 is pressed to the right, releasing the missile 53, which is forced upwardly by the compressed spring 49 as shown in FIG. 2 immediately after release.
Thereafter, the procedure for reloading and refiring is repeated sequentially through FIGS. 3, 1 and 2.
The embodiment shown in FIGS. 5-7 launches a balloon-type missile with escaping compressed air from the balloon serving to drive the missile after release from the hand held launcher. The balloon launcher has a counterweight 47, arm 45 and shaft 41, identical with similar elements of the missile launcher. Shaft 41 however rotates in small chamber 101, which opens into larger chamber 103, which is provided with guides 105, 105 on either side, the two chambers forming the interior of body 107 having a lower opening 109 and upper opening 111, terminated by circular plate 113 that extends radially outward from the body. A rotating head 115 extends upward from shaft 41 within enlarged chamber 103 and has a cam disposed upper surface 117. A reciprocating piston 119 with a lower mating cam surface 121 and guide ways corresponding to guides 105, 105, sits atop the rotating head and mates therewith at certain times. The remainder of enlarged chamber 103 encloses a compression spring 125 between the reciprocating piston 119 and the closure flange 127. A conical end 129 is provided at the top of body 107 with a one-way exit valve 131 and a one-way inlet valve 133.
Two opposed L-shaped brackets 135, 135 are fixed to the exterior walls of body 107 toward the upper end. Riding therein and surrounding said body is an oval-shaped release plunger 137 having an upper cam surface 139, and being spring biased to the left in FIG. 5 by spring 141. Riding above said release plunger is a reciprocating release ring 143 with extensions 144 that pass upwardly through plate 113.
Adapted to friction fit to cone 129 is a balloon missile 145, having a balloon 147, a female conical base 149, and a plurality of fins 151, secured to the conical base for flight stability. The conical base 149 has a lower circular flange 153 that fits immediately above reciprocating release ring extensions 144 and an upper smaller circular flange 155 about which the balloon is attached to the conical base 149. A balloon missile 145 is snugly fitted to the launcher 107 by bringing the friction mating conical surfaces 129 and 149 together.
Thereafter, body 107 is twirled which rotates handle 47 which in turn rotates head 115 and cam surface 117 against mating surface 121. Since piston 119 cannot rotate but can only reciprocate vertically, the action between the cam surfaces 117 and 121 against spring 125 causes a reciprocation movement of the piston which on the down stroke draws air through valve 133 and on the up stroke forces air through valve 131 into balloon 147. This action is continued until the balloon has been adequately inflated. Thereafter, release plunger 137 is pushed against spring 141 whereby the cam surface 139 forces release ring 143 upwardly to unseat the conical surface 149 from 129. Once this happens, the compressed air within the balloon escapes causing the missile to move rapidly upward until the compressed air is exhausted. Once the fingers are removed from release plunger 137, it is returned to the left, the release ring may be depressed and the launcher is ready to reload and repeat the sequence.
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A missile launching toy wherein twirling the body in one hand causes rotation of a head within a cylinder by an angularly disposed counterweight fixed to the head but extending outside the cylinder to provide stored energy by compressing a spring or air to launch on release the missile which is shown as an elongated projectile or a stabilized balloon.
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Genus and species: Gardenia jasminoides.
Varietal denomination: ‘Genie-2’.
FIELD OF INVENTION
The present invention relates to a new and distinct variety of the genus Gardenia and a member of the Rubiaceae family. This new Gardenia variety, hereinafter referred to as ‘Genie-2’, was discovered by Allyn Austin Cook in June. 2007. ‘Genie-2’ is characterized by its dense, low-profile growth habit, dark green foliage color and abundant fragrant, triple-whorl white flowers.
BACKGROUND OF THE INVENTION
‘Genie-2’ is derived and selected from gifted, unnamed, without traceable lineage and unpatented seed planted in Alachua County, Fla. Seed was received en masse in 2005. Ten (10) of the seeds were planted. After two (2) years, only one (1) grew with distinction. The exceptional plant subsequently named ‘Genie-2’ grew with a low and mounded profile and was a prolific bloomer.
The value of this new cultivar lies in its low-profile growth habit, compact dark green foliage color and abundant fragrant triple-whorl white flowers. The remarkable attributes of ‘Genie-2’ are its small size, low-profile growth habit, heat tolerance and disease resistance. ‘Genie-2’ is well suited for use in either formal or informal groupings and is quite attractive in mass plantings. ‘Genie-2’ is appropriate, adaptable and quite attractive as a container plant. ‘Genie-2’ is responsive to pruning and training and may be maintained without an excessive amount of care. Its natural propensity to remain small to maturity makes it valuable for landscape uses in any garden size.
Asexual propagation of the new plant by cuttings has been under Dr. Cook's direction and control in Alachua and Hillsborough counties of Florida. The new plant retains its distinctive characteristics and reproduces true to type in successive generations of asexual reproduction.
SUMMARY OF THE INVENTION
The following are the most outstanding and distinguishing characteristics of this new cultivar when grown under normal horticultural practices in Alachua County, Fla. The combination of these characteristics distinguishes ‘Genie-2’ from all other varieties in commerce known to the inventor. 1. Dense and low-profile in nature. 2. Attractive dark green foliage. 3. The flowers are triple whorl, white, fragrant and profuse. 4. Reaches mature size under normal fertilization and moisture conditions. 5. Hardy to Zone 7. 6. Tolerates part sun to part shade. 7. Heat tolerant. 8. Adaptable to a wide range of soil types. 9. Easily propagated with semi-hardwood cuttings in late spring through summer or through the process known in the industry as “tissue culture.” 10. Requires little pruning but is tolerant if pruning is desired. 11. Relatively pest resistant. 12. Very desirable in containers.
DESCRIPTION OF THE DRAWINGS
This new Gardenia jasminoides cultivar is illustrated by the accompanying photographic prints. The colors shown are as true as is reasonably possible to obtain by conventional photographic procedures. Colors in the photographs may appear different than actual colors due to light reflectance. The colors of the various plant parts are defined with reference to The Royal Horticultural Society Colour Chart. Descriptions of colors in ordinary terms are presented where appropriate for clarity in meaning.
FIG. 1 shows the overall appearance of a plant of ‘Genie-2’ planted in the ground.
FIG. 2 shows a close-up view of a flower of ‘Genie-2’.
FIG. 3 shows the overall appearance of a plant of ‘Genie-2’ in a container.
BOTANICAL DESCRIPTION OF THE PLANT
The following is a detailed description of the new variety of Gardenia based on observations made of two-year-old plants grown in one to three gallon containers and in established landscape plantings in Alachua and Hillsborough Counties, Fla., utilizing common gardening techniques. The description includes a comparison with Gardenia jasminoides ‘Leeone’ (U.S. Plant Pat. No. 21,983) and Gardenia jasminoides ‘Daisy’ (unpatented).
TABLE 1
COMPARATIVE CHARACTERISTICS
Genus species
Gardenia
Gardenia
Gardenia
jasminoides
jasminoides
jasminoides
Varietal
‘Genie-2’
‘Leeone’
‘Daisy’
denomination
Height
1-1½′
3-4′
3-3½′
(Mature)
(0.3-0.5 m)
(0.9-1.2 m)
(0.9-1.05 m)
Width
2-3′
2½-3′
3-3½′
(Mature)
(0.6-0.9 m)
(0.75-0.9 m)
(0.9-1.05 m)
Leaf Length
1⅝-2⅜″
1½-2¾″
1¼-2¼″
(4.1-6.0 cm)
(3.8-7 cm)
(3.1-5.7 cm)
Leaf Width
¼-¾″
⅝-1⅛″
⅝-1 3/16″
(0.7-2.0 cm)
(1.6-2.9 cm)
(1.6-3.02 cm)
Leaf Shape
Elliptic-Lanceolate
Elliptic-lanceolate
Ovate-rounded
Growth Habit
Dense, Low-profile
Dense upright
Dense globose
Flower Form
Triple
Double
Single
Bloom Period
May-August
May-November
May-October
Gardenia jasminoides ‘Leeone’ and Gardenia jasminoides ‘Daisy’ are well known in the industry and are comparable to ‘Genie-2’ in that all have green foliage color and white fragrant blooms. However, there are many differences. The growth habit of ‘Genie-2’ is compact, dense and low in profile to a mature height of 1½′ (0.5 m) tall compared to ‘Leeone’ which is upright, globose and much taller—4′ (1.2 m) tall. The flower form of ‘Genie-2 is a triple whorl where ‘Leeone’ is double and ‘Daisy’ is single.
DETAILED DESCRIPTION
In the following description, color references are made to The Royal Horticultural Society Colour Chart, 2001 Edition, except where general terms of ordinary dictionary significance are used. Plants used for the description were approximately 2 years old and were grown in 1-3 gallon containers in part shade outdoor conditions in Alachua County, Fla.
Botanical classification: ‘Genie-2’ is a cultivar of ‘ Gardenia jasminoides’. Parentage: “Genie-2’ is derived and selected from seed received as a gift, unnamed and without traceable lineage planted in Alachua County, Fla. Seed was received en masse in 2005. Plant description: The claimed variety is a compact, low-profile evergreen shrub. The plant is hardy in USDA Zones 7 to 9.
Propagation .—Stem cuttings. Time to initiate roots in summer: approximately 4 weeks. Tissue culture. Root description .—Numerous, fibrous and well-branched. Plant size .—About 30 cm high from the soil level to the top of the foliage and about 60 cm wide after 2 years. First year stems .—Diameter of 3-5 mm. Shape: round. Color: 137A. Stem strength .—Flexible when young, more easily broken once mature. Internode length .—Partially dependent upon sun exposure; 1.5-2 cm. Second year and older stems .—Diameter of 5-8 mm or more. Shape: round. Color: N199B.
Foliage description:
Arrangement .—Opposite. Mature foliage color: 147A upper Surface, 146B undersurface. Shape .—Elliptical. Apex: acuminate. Base: cuneate. Margin: entire to revolute. Texture .—Glabrous, lustrous. Venation .—Pinnate. Petiole length: 1-2 mm.
Flower description:
Flower type and habit .—Flowers are borne singly from mid branch to the distal end. Individual flowers are showy for about 4 days and remain on the plant for 1 to 2 weeks after they have senesced. Bloom period: Spring, Flowers are produced abundantly from May to June and then sporadically through August in Alachua County, Fla. Fragrance: Exceedingly sweet fragrance. Flower diameter .—About 5 cm. Height or depth: About 3.5 cm. Flower bud diameter .—About 1 cm. Flower bud length: about 2.5 cm. Flower bud shape: oblong. Color: 144A.
Petals:
Quantity.— 6 to 8 true petals and 16 to 18 petaloids per flower. True petal length .—About 1 cm. Width: About 0.9 cm. Shape: obovate with entire, undulating margins and overlapping in arrangement to form a whorl. Texture: Thick, glabrous. Petaloid petal length.— 0.3 to 0.5 cm, becoming smaller toward the center of the flower. Shape: Obovate. Texture: Thick, glabrous. Color: At peak bloom the upper and lower surfaces 155C.
Stamens; pistils: There is no physical evidence of reproductive structures despite the common appearance of the colored imprints. Fruit: None observed. Disease/pest resistance: No specific pest or disease resistance or susceptibility has been observed, however the variety performs well under normal disease pressures in Alachua County, Fla.
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A new and distinct variety of Gardenia jasminoides plant named ‘Genie-2’, characterized by its dense, low-profile growth habit, dark green foliage color and abundant fragrant, triple-whorl white flowers is disclosed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of the filing date of German Patent Application No. 10 2011 105 005.5 filed Jun. 20, 2011 and of U.S. Provisional Patent Application No. 61/498,700 filed Jun. 20, 2011, the disclosures of which applications are hereby incorporated herein by reference.
FIELD OF THE INVENTION
The invention relates to a movable storage compartment for a passenger cabin of, for example, an aircraft. The invention relates in particular to an upwardly movable storage compartment. The invention also relates to the use of a storage compartment of this type in an aircraft.
BACKGROUND OF THE INVENTION
There are currently two different luggage storage systems for aircraft cabins. There are stationary luggage bins (fixed bins) in the form of a storage compartment provided with a cover flap on the passenger side. Alternatively, there are pivotable luggage bins (movable bins) in the form of a storage compartment which is pivotable on the passenger side and does not have a cover flap. All luggage bins of which the loading edge can be moved in any manner are referred to as movable bins. A fundamental aspect of a movable storage compartment is that the open loading position differs from the closed position.
Common to the two variants is the fact that, particularly for the central region (middle hatrack), it is difficult to reach a compromise between advantageous loading height and comfortable headroom.
An example of a movable bin which is preinstalled in a housing box as a storage compartment module can be found in DE 10 2007 030331 A1 and WO 2009/003945 A1.
BRIEF SUMMARY OF THE INVENTION
An aspect of the invention provides a storage compartment which achieves a good compromise between loading height and headroom. Another aspect of the invention provides a storage compartment, the fixing structure of which has low-complexity kinematics.
By means of the combination of two fixing elements at the chute, one being a rotational element and one being a translational element, a very simple construction can be achieved using standard industry components.
This combination allows the following effects and optional functionalities:
a good loading possibility by means of translation towards the passenger a good integration of the storage compartment into a cabin design by means of rotation into a closed end position (continuous lining) a reduced manual force required to move the storage compartment, owing to a moving centre of rotation a fully-automated closure can take place by means of a linear drive having an electrically driven spindle a linear drive having an electrically driven spindle allows power feedback and power storage in the aircraft power system during opening (electric drive is used as a generator) a damper can be integrated into the linear drive (additional dampers dispensed with) in powerless states of an aircraft, the linear drive can easily be moved/overridden by manual force.
In general, a movable storage compartment for a passenger cabin according to the invention comprises a housing and fixing structures on the side walls of the housing, the housing being open on one side and being able to be moved back and forth between an open and a closed position, that is to say being able to be opened and closed. The fixing structures are formed in such a way that, when moving from the open position to the closed position, the housing can be moved first rotationally and then translationally upwards.
It is noted that the rotatory movement also includes a predominantly rotatory movement. That is to say that the actual movement can comprise a plurality of movement components, in such a way that the housing does not pivot exclusively about a pivot axis from the open position, but rather also simultaneously carries out a further movement such as a translatory movement. As the movement progresses, that is to say towards the closed position, the translatory movement component predominates, although there may still be a simultaneous minor rotatory movement.
According to an embodiment of the invention, the fixing structures comprise a pivot arm and a linear guide means. It is noted that one pivot arm and one linear guide means can conventionally be provided on each of the two side walls of the storage compartment housing.
Owing to the fixing structures according to the invention, the following processes can take place during the closure. The closure is initiated by a rotation about a centre of rotation close to the centre of gravity on the pivot arm, the system being statically fixed by a second pivot point on the linear guide means. During the further closure along the linear guide means, the rotational movement transitions into a translational movement, this translational movement being able to extend obliquely upwards at approximately 45°, that is to say obliquely upwards in a range between 35° and 55°. In the closed end position, a continuous lining can be achieved, that is to say the storage compartment disappears inconspicuously in the ceiling lining and produces no hard contour, in contrast to a fixed bin solution.
According to another embodiment of the invention, the fixing structures also comprise an electric drive for driving the linear guide means. For example, the linear guide means can comprise a spindle drive which has a spindle and a spindle nut, the electric drive being connected to the spindle, in order to drive it. The spindle nut can serve as a pivot point for the housing of the storage compartment, in such a way that the housing can be moved along the linear guide means when the spindle is arranged on a rigid structure such as a receiving space for the storage compartment. The electric drive which acts via the spindle is used for power assistance during closure.
It is noted that the linear guide means can also be arranged in such a way that the spindle is arranged on the storage compartment housing and the pivot point is, for example, arranged on a wall of the receiving space for the storage compartment.
According to a further embodiment of the invention, the electric drive can be used as a generator, in such a way that when the storage compartment housing is opened, that is to say when the storage compartment housing moves downwards, electricity is produced, which can either be supplied to a general electricity supply, or stored, in order to be used again subsequently for driving the storage compartment housing during a closure movement.
According to another embodiment, the fixing structures comprise a damper to damp movements of the housing. The damper can be integrated into the linear guide means or the damper can be provided by a corresponding control system of the electric drive. Alternatively, the linear guide means can comprise a rotation damper which acts via an integrated spindle to provide a defined movement speed during opening. The damper can also be a separate element which is fixed at a suitable place on the housing of the storage compartment.
In this context, it is noted that the damper can also be formed as a spring damper, in such a way that during a downward movement (opening), energy can be absorbed by a spring, which energy can then be released again during an upward movement (closure), whereby damping of the downward movement and power assistance for the upward movement can be provided.
According to a further embodiment of the invention, the fixing structures comprise an element for locking the housing in the closed position. The primary function of an element of this type is to prevent unintentional opening of the storage compartment body. The element can either be formed as a locking latch which engages in a corresponding recess in a side wall of a receiving space for the storage compartment, if the locking latch is arranged laterally on the storage compartment body, or the element can engage directly in a recess in the frame of the aircraft structure, if the element is arranged on a rear side or a lateral edge of the rear side of the storage compartment body.
The housing can be produced from a glass-fibre-reinforced or carbon-fibre-reinforced material.
A handle can also be integrated into the housing wall which is visible in the closed position. Preferably, the visible wall of the housing can be integrated into a lining of an interior of, for example, an aircraft.
According to an embodiment of the invention, the storage compartment can be used in a passenger cabin of an aircraft or a vehicle.
According to a further embodiment of the invention, an aircraft comprises a storage compartment having the above-described features. The aircraft can also comprise a lining panel which is arranged above the storage compartment in the passenger cabin of the aircraft. At its lower edge, the lining panel can comprise a portion which extends in the direction of the aircraft structure. This portion of the lining panel cannot be seen from the passenger cabin and can be configured in such a way that the storage compartment body, in the closed state, forms a closed box together with this portion. This prevents, for example, objects which are located in the storage compartment body from engaging the lining panel from behind.
The above-described aspects and further aspects, features and advantages of the invention can also be derived from the examples of the embodiments, which are described below with reference to the appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view of a storage compartment according to the invention in an open position.
FIG. 2 is a schematic side view of the storage compartment according to the invention in an intermediate position.
FIG. 3 is a schematic side view of the storage compartment according to the invention in a closed position.
DETAILED DESCRIPTION
FIG. 1 to 3 are side views of a storage compartment according to an embodiment of the invention, a movement sequence from an open position ( FIG. 1 ) to a closed position ( FIG. 3 ), via a middle intermediate position ( FIG. 2 ), being illustrated.
FIG. 1 shows a storage compartment having a housing 100 and fixing structures, together with a receiving space 200 for the storage compartment. The housing 100 comprises a wall 102 , into which a handle structure 104 is integrated. The housing 100 also comprises a first side wall 106 , and a second side wall (not shown), to which the fixing structures are attached. The housing 100 is open on one side, the housing 100 in the figures being open on the left side.
The fixing structures comprise a pivot arm 110 , a linear guide means 120 and a damper 130 . A first end 112 of the pivot arm 110 is fixed to the side wall 106 of the housing and the second end 114 of the pivot arm can be fixed to a bearing structure of the receiving space 200 for the storage compartment. In this manner, the housing can be rotated about a pivot axis near the centre of gravity. The linear guide means 120 can be formed as a spindle drive having a guide rail 124 , a spindle and a spindle nut, which drive is mounted on the housing of the storage compartment and, for example, on a wall of the receiving space for the storage compartment. As can be seen in the figures, a fixing point 122 is arranged on the spindle nut, near a back wall of the housing 100 . The guide rail 124 extends at an angle of approximately 45° obliquely upwards into the receiving space for the storage compartment.
In FIG. 1 , an electric drive 140 is shown schematically at the upper end of the linear guide means 120 . The electric drive can be connected to the spindle in the linear guide means, and the spindle nut, and thus the housing, can be actively pulled upwards along the linear guide means via the driven spindle.
FIG. 1 also shows a damper 130 , which is connected to the housing 100 via a coupling joint. The coupling joint comprises a first coupling member 131 and a second coupling member 133 , which are connected to each other via a joint. The first coupling member 131 is connected to the bearing structure of the receiving space 200 for the storage compartment via a first pivot point 134 , and the second coupling member 133 is connected to the housing 100 of the storage compartment via a second pivot point 136 . One end 132 of the damper 130 is connected to the first coupling member 131 , approximately in the centre thereof, and the other end 138 is in turn connected to the bearing structure of the receiving space for the storage compartment.
Finally, FIG. 1 shows an arrow R, which denotes a starting movement of the housing 100 about a pivot axis, for the case in which the housing is to be closed from an open position. That is to say, the arrow R illustrates a rotatory movement at the beginning of a closing movement.
The elements of the storage compartment according to the invention are also shown in FIG. 2 , but in a position between the open position and a closed position. It can be seen in FIG. 2 that the fixing point at the second end 114 of the pivot arm 110 , the pivot point 134 of the first coupling member 131 , the fixing point at the second end 138 of the damper 130 and the guide rail 124 of the linear guide means 120 are fixed points which do not change position. In contrast thereto, the pivot arm 110 , the coupling members 131 and 133 and the fixing point 122 on the spindle nut do change position.
The arrow T in FIG. 2 denotes a translatory movement which extends in the direction of the linear guide means 120 and which prevails in the second half of the closure movement.
FIG. 3 shows the storage compartment in a closed position, that is to say in a position in which the housing 100 of the storage compartment is received completely in the receiving space 200 for the storage compartment. It can be seen in FIG. 3 that the wall 102 of the housing 100 is configured in such a way that a closed lining is produced together with the lining parts 202 and 204 when the storage compartment is in the closed position. FIG. 3 also shows that a catch 150 can be provided, which can prevent unintentional opening of the storage compartment. The catch is shown schematically at an upper edge of the wall 102 , and can engage in a corresponding structure on the lining part 202 , in order to lock the storage compartment in the closed position.
While the invention has been illustrated and described in detail in the drawings and the preceding description, illustrations and descriptions of this type are intended to be merely illustrative or exemplary and not restrictive, and the invention is therefore not limited by the disclosed embodiments. Other variations of the disclosed embodiments can be understood by a person skilled in the art when implementing the claimed invention, and can be produced by studying the drawings, the disclosure and the appended claims.
In the claims, the word “comprising” does not exclude other elements or steps and the indefinite article “a” does not exclude a plurality.
Merely the fact that certain features are referred to in different dependent claims does not limit the subject-matter of the invention. Any combinations of these features can also advantageously be used. The reference numerals in the claims should not restrict the scope of the claims.
List of Reference Numerals
100 storage compartment 102 wall 104 handle structure 106 side wall 110 pivot arm 112 first end of the pivot arm 114 second end of the pivot arm 120 linear guide means 122 fixing point 124 guide rail 130 damper 131 first coupling member 132 first end of the damper 133 second coupling member 134 first pivot point 136 second pivot point 138 second end of the damper 140 electric drive 150 catch 200 receiving space for the storage compartment 202 , 204 lining parts
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A movable storage compartment for a passenger cabin comprises a housing and fixing structures on the side walls of the housing, the housing being open on one side and being able to be moved back and forth between an open and a closed position, that is to say being able to be opened and closed. The fixing structures are formed in such a way that during a movement from the open position to the closed position the housing can be moved first predominantly rotationally and then predominantly translationally upwards.
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BACKGROUND OF THE INVENTION
The present invention generally relates to fabrication processes that include a joining operation. More particularly, this invention is directed to a technique for fabricating rotating hardware, as an example, rotating components of a turbomachine, joining techniques used in their fabrication, and the hardware formed thereby.
Components within the combustor and turbine sections of a gas turbine engine are often formed of superalloy materials in order to achieve acceptable mechanical properties while at elevated temperatures resulting from the hot combustion gases produced in the combustor. Higher compressor exit temperatures in modern high pressure ratio gas turbine engines can also necessitate the use of high performance superalloys for compressor components, including blades, spools, disks (wheels) and other components. Suitable alloy compositions and microstructures for a given component are dependent on the particular temperatures, stresses, and other conditions to which the component is subjected. For example, the rotating hardware such as compressor spools, compressor disks, and turbine disks are typically formed of superalloys that must undergo carefully controlled forging, heat treatments, and surface treatments to produce a controlled grain structure and desirable mechanical properties. Notable superalloys for these applications include gamma prime (γ′) precipitation-strengthened nickel-base superalloys containing chromium, tungsten, molybdenum, rhenium and/or cobalt as principal elements that combine with nickel to form the gamma (γ) matrix, and contain aluminum, titanium, tantalum, niobium, and/or vanadium as principal elements that combine with nickel to form the desirable gamma prime precipitate strengthening phase, principally Ni 3 (Al,Ti). Examples of gamma prime nickel-base superalloys include René 88DT (R88DT; U.S. Pat. No. 4,957,567) and René 104 (R104; U.S. Pat. No. 6,521,175), as well as certain nickel-base superalloys commercially available under the trademarks Inconel®, Nimonic®, and Udimet®. Disks and other critical gas turbine engine components are often forged from billets produced by powder metallurgy (P/M), conventional cast and wrought processing, and spraycast or nucleated casting forming techniques. Forging is typically performed on fine-grained billets to promote formability, after which a supersolvus heat treatment is often performed to cause uniform grain growth (coarsening) to optimize properties.
A turbine disk 10 of a type known in the art is represented in FIG. 1 . The disk 10 generally includes an outer rim 12 , a central hub 14 , and a web 16 between the rim and hub 12 and 14 . The rim 12 is configured for the attachment of turbine blades (not shown) in accordance with known practice. A hub bore 18 in the form of a through-hole is centrally located in the hub 14 for mounting the disk 10 on a shaft, and therefore the axis of the hub bore 18 coincides with the axis of rotation of the disk 10 . The disk 10 is presented as a unitary forging of a single alloy, and is representative of turbine disks used in aircraft engines, including but not limited to high-bypass gas turbine engines such as the GE90® and GEnx® commercial engines manufactured by the General Electric Company. The weight and cost of single-alloy forgings have driven the desire to develop materials, fabrication processes, and hardware designs capable of reducing forging weight and costs for rotating hardware of gas turbines. One approach is prompted by the fact that the hubs and webs of compressor spools and disks and turbine disks have lower operating temperatures than their rims, and therefore can be formed of alloys with properties different from those required at the rims. Depending on the particular alloy or alloys used, optimal microstructures for the hub, web and rim can also differ. For example, a relatively fine grain size may be optimal for the hub and web to improve tensile strength and resistance to low cycle fatigue, while a coarser grain size may be optimal in the rim for improving creep, stress-rupture, and crack growth resistance.
Implementing a multi-alloy design generally entails separately fabricating the hub and rim of a disk from different materials and then joining the hub and rim by welding or another metallurgical joining process, as disclosed in U.S. Published Patent Application Nos. 2008/0120842 and 2008/0124210. Though a variety of joining techniques are available for producing multi-alloy disks, each has certain shortcomings. For example, electron beam (EB) welding creates a resolidified weld zone that is always weaker than the materials welded together, and joints formed by diffusion bonding (DB) and brazing are also weaker than the materials they join as a result of providing no mechanical work to the joint region. Solid-state welding processes such as inertia welding are disclosed in U.S. Pat. No. 6,969,238. While well suited for certain applications, weld joints formed by inertia welding are fine grained and therefore limit the high temperature operation of a disk. Furthermore, if the disk is heat treated to produce coarser grain size, the inertia weld joint is prone to cracking and critical grain growth during supersolvus heat treatment.
Further examples of metallurgical joining techniques for fabricating multi-alloy disks and spools are disclosed in U.S. Pat. Nos. 5,106,012 and 5,161,950. These patents describe a technique termed forge enhanced bonding, by which separately formed regions of a disk can be bonded together during a forging operation. In a particular example, preforms of the rim region and the hub and web region of a disk are placed in a forging die and bonded together during forging as a result of material at the interface of the preforms being displaced into vents in the die halves. Potential defects originally present at the interface surfaces are displaced with the material that flows into the vents, forming sacrificial ribs that can be removed from the resulting bonded disk after forging, so that the portion of the bond line remaining in the finish part is of high integrity and substantially free from defects. While effective for bonding hub and rim preforms, the process requires producing the preforms so that their mating surfaces are very clean and closely shape-conforming, carefully assembling the preforms in a can while avoiding contamination, and hot isostatic pressing (HIP) the preforms prior to forging.
BRIEF DESCRIPTION OF THE INVENTION
The present invention provides a process of fabricating rotating hardware, as an example, rotating components of turbomachines, joining techniques used in their fabrication, and rotating hardware formed thereby.
According to a first aspect of the invention, a process for fabricating a rotating component includes fabricating at least two preforms corresponding to at least two portions of the component. Each of the preforms comprises an interface surface at which the preforms can be joined to locate a first of the portions in a radially outward direction from a second of the portions. The preforms are then inertia welded together to form a profile, and such that the interface surfaces of the preforms form a solid-state weld joint located between portions of the profile corresponding to the portions of the component. The solid-state weld joint contains a finer-grained material relative to material in the portions of the profile and define joint surfaces located on opposite axial surfaces of the profile. The profile is then forged with dies to produce a forging containing forging portions corresponding to the portions of the component. The dies define first and second die cavities, of which at least one has a recess into which the finer-grained material from the solid-state weld joint is expelled during forging to purge a joint region of the forging between the forging portions of the finer-grained material. The joint region contains grains distorted in an axial direction of the forging.
Another aspect of the invention is a rotating component having a rotational axis and at least two portions that are welded together. A first of the portions is disposed in a radially outward direction from a second of the portions. A joint region is located between the portions of the component that is free of weld material and free of finer-grained material relative to material in the portions of the component. The joint region also contains grains distorted in an axial direction of the component.
A technical effect of the invention is the ability to produce a rotating component using a welding operation, but with finer-grained materials associated with a weld joint being expulsed from the component. This aspect is advantageous when producing, for example, a multi-alloy rotating component (such as a disk or spool) having rim and hub portions formed of different materials that can be tailored or otherwise particularly selected for the different operating conditions of the rim and hub. In addition, the joint interface between the rim and hub portions of a rotating component is capable of having improved properties without disadvantages associated with the prior art, including cracking and critical grain growth during supersolvus heat treatment. The process of this invention can potentially be applied to a wide variety of alloys, heat treatments, and forging conditions to achieve different grain sizes and structures within the rim and hub regions of the component.
Other aspects and advantages of this invention will be better appreciated from the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a turbine disk of a type used in gas turbine engines.
FIGS. 2 through 5 represent steps performed in fabricating a rotating component, such as the disk of FIG. 1 , by inertia welding a rim preform to a hub preform and then forging the welded assembly in accordance with an embodiment of the present invention.
FIG. 6 graphically represents the material flow that occurs in and around the weld joint of a disk during the forging operation of FIG. 5 , in which the weld joint material is displaced into offset vents in accordance with an embodiment of the present invention.
FIG. 7 graphically represents the material flow that occurs in and around a weld joint of a disk produced by an alternative forging operation, in which the weld joint material is displaced into opposed vents during forging in accordance with an embodiment of the present invention.
FIG. 8 represents a fragmentary cross-sectional view of a multi-alloy disk that can be produced by a welding-forging process of this invention, and shows the appearance of the disk following removal of an annular flange produced by the forging process of either FIG. 6 or 7 .
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described with reference to rotating hardware of the type used in turbomachines, and particularly turbine and compressor disks and compressor spools of high-bypass gas turbine engines. For convenience, the invention will be described in particular reference to the turbine disk 10 represented FIG. 1 , though it should be understood that the teachings and benefits of the invention are not limited to this particular disk 10 and can be adapted and applied to a wide range of rotating hardware.
FIGS. 2 through 5 and 8 represent steps involved in fabricating the disk 10 using an inertia welding technique. A first step represented in FIG. 2 is to prepare rim and hub preforms 22 and 24 , which are then inertia welded together in FIG. 3 and then machined in FIG. 4 to yield a disk profile 40 in preparation for forging. The disk profile 40 is then placed in dies 42 and 44 of a forge press that substantially fit the profile 40 everywhere except at the weld joint 28 shown in FIG. 3 . FIG. 5 represents the result of the forging operation, during which material flows from the weld joint 28 into cavities or vents 52 and 54 of the dies 42 and 44 . Finally, FIG. 8 depicts the result of removing annular flanges 69 from each axial face of the forging 60 produced in FIG. 5 , after which finish processing of the disk (for example, heat treatment, sonic inspection, machining to final shape, etc.) can be performed. These steps are discussed in greater detail below.
In FIG. 2 , portions of the rim preform 22 and hub preform 24 are represented in cross-section. It should be appreciated that, because of the axisymmetric configuration of the disk 10 , there is a diametrically opposite portion of the disk 10 that is not shown in FIG. 2 . The preforms 22 and 24 can be produced by a variety of known processes, including billets produced by powder metallurgy (P/M), conventional cast and wrought processing, and spraycast or nucleated casting forming techniques. The preforms 22 and 24 preferably are fine-grained to promote their forgeability. The outlines of rim and hub profiles 32 and 34 are shown in FIGS. 2 and 3 , and illustrate that the hub and rim preforms 22 and 24 could be forged or otherwise fabricated prior to inertia welding to produce a disk profile 40 ( FIG. 4 ) that more closely corresponds to the desired geometries of the rim 12 , hub 14 and web 16 in the final disk 10 .
The preforms 22 and 24 can be produced from a wide variety of materials chosen on the basis of the operating conditions to which the rim 12 , hub 14 and web 16 will be subjected when the disk 10 is installed in a turbomachine, such as a gas turbine engine. Nonlimiting examples of suitable materials include the aforementioned gamma prime nickel-base superalloys R88DT and R104, as well as certain nickel-base superalloys commercially available under the trademarks Inconel®, Nimonic®, and Udimet®. Importantly, the rim and hub preforms 22 and 24 can be produced from different alloys, so that the disk 10 is a multi-alloy component whose rim 12 , hub 14 and web 16 can be formed of materials better tailored for different operating conditions to which the rim 12 , hub 14 and web 16 will be subjected. Also, as will be noted below, the rim and hub preforms 22 and 24 can be produced from different alloys that enable the final article to respond to a mono-temperature heat treatment with different grain growth responses, or to enable the use of a dual heat treatment method to achieve a range of desired structures between the bore 14 and rim 12 .
The preforms 22 and 24 are shown in FIG. 2 as having two machined interface surfaces 26 , at which joining occurs by inertia welding in FIG. 3 . The interface surfaces 26 are represented as being oriented at an angle other than parallel to the axis 20 of the eventual disk 10 , providing a contact (draft) angle that facilitates assembling and mating of the annular-shaped rim preform 22 within the hub preform 24 , as indicated by the arrows in FIG. 2 . Consequently, the resulting weld joint 28 shown in FIG. 3 is also inclined at the same angle. However, it is foreseeable that the interface surfaces 26 of the rim and hub preforms 22 and 24 could be parallel to the disk axis 20 . To further facilitate assembly and contact between the preforms 22 and 24 , the surfaces 26 are preferably conformably shaped so that they readily slide into contact with each other.
The inertia welding process represented by the steps of FIGS. 2 and 3 is a solid-state welding technique accomplished by rotating the rim preform 22 and/or hub preform 24 about the disk axis 20 . As a matter of convenience, the rim preform 22 may be held stationary and the hub preform 24 rotated. While relative rotation is occurring, the rim and hub preforms 22 and 24 are moved together parallel to the axis 20 until the interface surfaces 26 of the preforms 22 and 24 come in contact. As relative rotation continues, the contacting surfaces 26 generate frictional heating, and increasing the application of force in the axial direction increases the temperatures of the regions underlying the surfaces 26 of the rim and hub preforms 22 and 24 to a temperature approaching the incipient melting temperatures of the materials from which the preforms 22 and 24 are made. The axial force, relative rotational speeds and input rotational energy at initiation of welding, and required relative displacements necessary to inertia weld the preforms 22 and 24 will vary, depending on the size, mass and materials of the preforms 22 and 24 and the surface area of their interface surfaces 26 . The preforms 22 and 24 are held in contact under these conditions for a period of time sufficient to cause them to bond together along their contacting surfaces 26 as the rotational speed decays to zero, forming a solid-state weld joint 28 that contains fine-grained material as a result of the temperatures sustained during inertia welding.
The disk preform 30 produced by the welded preforms 22 and 24 can be forged or machined after welding to acquire a disk profile 40 represented in FIG. 4 , whose geometry is preferably suitable for a forging operation represented in FIG. 5 . Alternatively, and as noted above, the preforms 22 and 24 could have been forged or machined prior to welding as indicated by the outlines of the rim and hub profiles 32 and 34 in FIGS. 2 and 3 , such that the welding operation approximately yields the disk profile 40 of FIG. 4 . FIG. 5 represents a forging 60 produced by subjecting the disk profile 40 of FIG. 4 to a forging operation within two die halves 42 and 44 . Die cavities 46 and 48 are defined in the mating surfaces 50 of the die halves 42 and 44 that closely correspond to the final geometry desired for the disk 10 , yielding the forging 60 with rim, hub and web portions 62 , 64 and 66 corresponding to the rim 12 , hub 14 and web 16 of the final disk 10 . However, the die cavities 46 and 48 diverge from the desired profile of the disk forging 60 as a result of the presence of two annular-shaped cavities or vents 52 and 54 defined in their surfaces. The vents 52 and 54 are represented as coaxial but having different diameters, so that the vents 52 and 54 are not axially aligned in the axial direction of the disk axis 20 but instead are radially offset from each other. The offset is selected so that the exposed surfaces 58 ( FIG. 4 ) of the solid-state weld joint 28 at each axial surface of the disk profile 40 will face one of the die cavity vents 52 and 54 when forging is initiated, and during forging the exposed surfaces 58 will be displaced or expelled into the vents 52 and 54 .
The effect of this offset is graphically represented in a model prediction shown in FIG. 6 , which indicates a very large degree of metal flow and grain distortion within a joint region 68 of the disk forging 60 where the weld joint 28 of the disk profile 40 was originally present. As evident from FIG. 6 , grain distortion within the joint region 68 of the forging 60 is largely in the axial direction of the forging 60 , roughly coinciding with the contact angle of the interface surfaces 26 of the preforms 22 and 24 and the angle of the weld joint 28 in the disk profile 40 from which the forging 60 was produced. The effect of this distortion is to purge the forging 60 of the weld joint 28 and the fine-grained material that was present there. As evident from FIG. 5 , the vents 52 and 54 are filled with material that was within and immediately adjacent the weld joint 28 , resulting in the creation of an annular flange 69 at each of the axial faces of the forging 60 . The forging operation is ideally performed so that the flanges 69 contain the fine-grained material originally present within the weld joint 28 . This result may be achieved with a single or multiple strokes during the forging operation. Furthermore, it is foreseeable that the disk profile 40 could undergo forging in two steps, such that one of the flanges 69 is first formed with a first set of dies in which a single vent 52 or 54 is present, and then the other flange 69 is formed with a second set of dies in which the other vent 52 or 54 is present. The flanges 69 are then removed during final machining of the forging 60 to produce the desired profile of the disk 10 , as shown in FIG. 8 .
FIG. 7 is a graph plot similar to FIG. 6 , but showing a model prediction of a forging 70 produced from preforms (not shown) whose preform surfaces and resulting weld joint were parallel to the disk axis 20 , and then forged with a die (not shown) in which the vents were axially aligned with each other instead of being radially offset as shown in FIG. 5 . As evident from FIG. 7 , the model predicts that the flanges 79 formed within the vents contain material that was previously within and immediately adjacent the weld joint, though a significant amount of the weld joint material is still within the joint region 78 between the rim and hub forgings 72 and 74 . According to this prediction, the offset vents 52 and 54 of FIG. 5 are expected to be more effective in purging a forging of the fine-grained material originally present within the weld joint 28 . In view of the above, the contact angle of the preform surfaces 26 ( FIG. 2 ) and the offset of the vents 52 and 54 are considered together to optimize the forging process. A particularly suitable range for the contact angle is believed to be about zero to about forty-five degrees to the disk axis 20 , and a preferred range is believed to be about seven to about thirty degrees. However, it is expected that an optimal contact angle will be determined by various factors, including the material(s) of the preforms 22 and 24 and the sizes of the rim and hub preforms 22 and 24 (or the rim and hub profiles 32 and 34 ). As such, contact angles of as much as sixty degrees and even up to about ninety degrees could possibly be used with the invention.
Suitable forging and heat treatments conditions will depend on the particular materials and sizes of the preforms 22 and 24 or profiles 32 and 34 and are generally within the knowledge and capability of those skilled in the art, particularly in view of the following discussion as well as the teachings of U.S. patent publications cited below, and therefore will not be discussed in any detail here. In most cases, the desire will be to obtain a smoothly varying grain size across the joint region 68 / 78 , while avoiding the fine-grained inertia weld zone associated with conventional inertia welding.
The forging operation performed on the disk profile 40 can be carried out using controlled strain and strain rates to achieve a desired final grain size throughout the forging 60 / 70 , including the joint region 68 / 78 between the rim and hub portions 62 / 72 and 64 / 74 corresponding to the original location of the weld joint 28 within the disk profile 40 . The forging parameters are preferably controlled so that the material flow into the vents 52 and 56 within the die cavity is accomplished at controlled strain rates, generally within the regime of superplastic deformation (but for certain alloys possibly outside the region of superplasticity), so that subsequent supersolvus heat treatment of the entire joint region 68 / 78 in and around the joint 28 of the disk forging 60 / 70 can be performed without critical grain growth. For example, see the teachings of U.S. Pat. Nos. 4,957,567 to Krueger et al., 5,529,643 to Yoon et al., 5,584,947 to Raymond et al., and 5,759,305 to Benz et al., and U.S. Published Patent Application No. 2009/0000706 to Huron et al. Typically the desire will be to supersolvus heat treat the entire forging 60 / 70 to produce a metallurgically clean, fully supersolvus disk 10 having a substantially uniform grain size, including the joint region 68 / 78 encompassing the original location of the weld joint 28 .
Grain sizes within the rim 12 , hub 14 , and web 16 can be further controlled and, if desired, modified by the manner in which the disk profile 40 was produced. For example, the rim and hub profiles 32 and 34 can be separately forged prior to welding, and the rim profile 32 can undergo relatively slower forging at higher temperatures than the hub profile 34 to yield a coarser grain size in the rim profile 32 and, subsequently, a coarser grain size in the rim 12 . In addition or alternatively, a dual heat treatment can be performed on the forging 60 / 70 , in which the rim 12 and hub 14 are subjected to different supersolvus and/or different stabilization/aging temperatures to optimize grain size and properties within the rim 12 and hub 14 . Examples of dual heat treatment techniques are disclosed in U.S. Pat. Nos. 4,820,358, 5,527,020, 5,527,402 and 6,478,896.
It should also be noted that the alloys chosen for the rim 12 and bore 14 can be optimized via their major element chemistry composition (for example, to influence gamma-prime solvus composition and content) and their minor element chemistry composition (for example, to influence degree of grain refinement). In addition or alternatively, the rim and hub preforms 22 and 24 can be produced from different alloys that enable or cause the final article to respond to controlled and even mono-temperature heat treatments to achieve different grain growth responses in the rim 12 and bore 14 .
While the invention has been described in terms of a specific embodiment, it is apparent that other forms could be adopted by one skilled in the art. Therefore, the scope of the invention is to be limited only by the following claims.
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A process of fabricating a rotating component and components formed thereby. The process includes fabricating preforms corresponding to portions of the component. Each preform has an interface surface at which the preforms can be joined to locate a first of the portions in a radially outward direction from a second of the portions. The preforms are then inertia welded together to form a profile having a solid-state weld joint containing a finer-grained material than other portions of the profile. The profile is then forged with dies to produce a forging. At least one of the dies has a recess into which the finer-grained material from the weld joint is expelled during forging to purge a joint region of the forging between the forging portions of the finer-grained material. The joint region contains grains distorted in an axial direction of the forging.
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FIELD OF THE INVENTION
The present invention relates to coated magnet wire of the type used to wind electrical transformers and more particularly to such wire that is coated with an insulating polymeric layer on only one facet thereof.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 5,151,147 issued Sep. 29, 1992 describes a method and apparatus for the production of, among other continuous elongated articles, a coated magnet wire of the type used in the winding of electrical transformers. The product produced by the apparatus and method described in that patent comprises a conductive core, preferably of a metal such as copper or aluminum, surrounded by an adherent layer of an insulating polymer. In the production of transformers, multiple layers of this coated magnet wire are concentrically wound with paper or other insulating material interleaves between the sequential layers to form the core of an electrical transformer.
While the magnet wire produced by this system has proven entirely adequate and to a certain extent revolutionized the production of magnet wire based transformer systems, it can be relatively expensive to produce. The cost of such a product is in large extent affected by the cost of the polymer applied about the metallic core. This is particularly so in the case of high temperature transformers (operating temperature on the order of 200° C. or more) where the applied polymer is a so-called engineering polymer. Such materials while exhibiting excellent insulating and heat resistance properties are quite costly vis-à-vis lower temperature capability insulating polymers or other competitive insulating products.
Accordingly means to reduce the amount of polymer used in the insulating layer have been sought after for many years. The most obvious and generally simplest approach to achieving such polymer material volume reduction is, of course applying a thinner layer (on the order of 2–3 mils) of the insulating polymer. While these approaches have been successful in reducing the amount/volume of insulating polymer applied to the magnet wire to a minimum, attempts to further reduce the thickness of such coatings have, for all practical purposes, stressed the limits of the manufacturing process to further reduce the thickness of the polymeric insulating layer. Additionally, the currently applied insulating polymers have substantially reached the limits of their dielectric strength at current levels/thicknesses of application. Thus, practically, there is no currently known way to further reduce the thickness of such layers within the currently known manufacturing processes and with the currently available materials.
There thus exists a need for a method of further reducing the amount of applied insulating polymer in such products to further reduce the costs inherent in the production thereof.
OBJECTS OF THE INVENTION
It is therefore an object of the present invention to provide a method and apparatus for the production of a polymer coated insulated magnet wire that performs in a manner equivalent to prior art such magnet wire products with a significantly reduced requirement for insulating polymer coating volume.
It is another object of the present invention to provide an insulated magnet wire that, while performing equivalently to prior art products in transformer winding processes, utilizes a significantly reduced amount of the insulating polymer.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a novel continuously coated magnet wire that includes an insulating polymeric coating on only one facet thereof. Such a magnet wire can be conventionally wound using current transformer manufacturing processes but can be produced at significantly lower cost due to the almost 75% reduction in the volume of insulating polymeric material applied to the magnet wire core. A method for the manufacture of such a product provides for the application of the insulating polymeric coating to only a single minor axis facet of the magnet wire core through the use of custom dies and a modified manufacturing process that allows for conventional handling and packaging of the modified product.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a greatly enlarged cross-sectional view of the polymer coated magnet wire of the prior art.
FIG. 2 is a greatly enlarged cross-sectional view of the polymer coated magnet wire of the present invention.
FIG. 3 is a cross-sectional view showing the conductive core of the magnet wire of the present invention as it passes through a die for the application of the polymeric insulating material to a minor axis facet or extremity thereof in accordance with the present invention.
FIG. 4 is a schematic depiction of the magnet wire product orientation in one of the steps in the manufacture of magnet wire in accordance with the present invention.
FIG. 5 is a side view showing the manner in which the magnet wire of the present invention is wound in the manufacture of electrical transformers.
DETAILED DESCRIPTION
Referring now to the accompanying drawings, FIG. 1 shows a greatly enlarged cross-sectional view of the magnet wire 10 of the prior art. The magnet wire products described herein generally have cross-sectional dimensions below about one inch by one inch, but have been enlarged in the accompanying Figures so that details thereof can be more easily seen. As can be seen in FIG. 1 , prior art magnet wire 10 comprises a metallic/conductive core 12 with a continuous layer 14 of polymeric insulating material completely about its periphery. Such is the product that was manufactured in accordance with the practice of the invention described in U.S. Pat. No. 5,151,147 previously described (hereinafter the '147 patent) and which is incorporated herein by reference in its entirety particularly as it describes details of the continuous metal extrusion and polymer coating process. While such a product possesses entirely adequate properties for its intended use, its production cost shortcomings, as described above, make it less than ideal for continued use, particularly in lower temperature capability/lower cost transformer applications.
Referring now to FIG. 2 that depicts an enlarged cross-sectional view of the improved coated magnet wire 10 A of the present invention, it is apparent that the insulating polymer coating 14 A over the metallic/conductive core 12 A is present on only one facet, one of the minor axis facets, 16 of metallic core 12 A, and at about the same thickness as used in the prior art embodiment depicted in FIG. 1 . As used herein, the terms “minor axis”, “minor axis facet”, “minor axis surface” and “minor axis extremty(ies)” are all clearly meant and intended to mean the short dimensions and/or side(s) of the generally rectangular magnet wire product 10 A described herein. In the case of a square wire, the minor axes and major axes extremities will be equal in size. In such a case, the term “minor axis extremity”, or the like, is intended to mean one of such equal sides. A comparison of this structure 10 A (having a polymer coating on only one minor axis extremity thereof) with that depicted in FIG. 1 , namely structure 10 , immediately reveals that the amount of insulating polymer used in the case of wire 10 A is on the order of less than about 25% by volume of that used on wire 10 as depicted in the embodiment of FIG. 1 . It is this saving of polymeric coating that forms the basis for the advantages of the present invention.
As described in the '147 patent, the continuous extrusion and coating process comprises extruding a product shape by the action of a rotary extrusion press forcing input metal through a metal forming die, in our current case the shape is a metallic/conductive generally rectangular magnet wire 10 A, cooling the wire and then passing the cooled wire through a die for extruding polymer. In the case described in the '147 patent, the polymer extrusion die is of an annular shape and extends around the entire periphery of the elongated shape or wire 12 so that the central axis of the polymer extrusion die coincides with the central axis of the path of the wire 12 as it is drawn from the metal extrusion die to a take up reel.
In accordance with the present invention, the metal extrusion die instead of forming a purely rectangular wire (as shown at 12 in FIG. 1 ) forms the shape depicted for the core 12 A depicted in FIG. 2 . This shape includes at one minor axis extremity 16 of the cross section of the extruded wire 12 A, a pair of shoulders 18 and 20 . According to a preferred embodiment of the wire of the present invention, shoulders 18 and 20 extend, stand off, on the order of from 2 to about 4 thousandths from surfaces 17 and 19 of core 12 A respectively. The purpose of these shoulders will be described in greater detail hereinafter.
Referring now to FIG. 3 that depicts a cross-sectional view of extruded core 12 A as it passes through polymer extrusion die 24 , it can be seen that polymer extrusion die 24 in lower region 26 thereof abuts closely to core 12 A eliminating the application of any polymer in this region while in the area of polymer extrusion die 24 that abuts minor axis extremity 16 , i.e. area 27 , polymer is extruded in the general shape depicted for minor axis extremity 16 depicted in FIG. 2 , resulting in the selective application of an appropriate thickness of polymer to minor axis extremity 16 and shoulders 18 and 20 . According to a preferred embodiment of the present invention, polymer is also applied along a short distance (on the order of about 10-30 thousandths of an inch) of major axis surfaces 17 and 19 in the regions abutting shoulders 18 and 20 to provide better adhesion of polymer layer 14 A about the shoulders 18 and 20 . Serrations 22 further assist with the adhesion of polymer layer 14 A to minor axis extremity 16 . While it is possible to perhaps apply a very thin layer of polymer in lower region 26 , any application of polymer in this region detracts from the cost savings achieved by the instant invention and accordingly is recommended against.
As can be envisioned, in order for the product 10 A described herein to survive the manufacturing processes involved in producing a transformer (winding, shipping, unwinding and wrapping), polymer layer 14 A must be fairly adherent to core 12 A. Additionally, the adhesion requirements of transformer manufacturers can vary. Such adhesion is controlled largely by the temperature of core 12 A as it enters the polymer extrusion die. Thus, depending upon the requirements of a particular transformer manufacturer, the adhesion level can be tailored to their particular need.
As will be apparent to those skilled in the art to which the '147 patent and the instant application apply, while it is preferable to apply polymer layer 14 A to core 12 A with core 12 A in the vertical position (that shown in the accompanying Figures wherein the minor axis extremity is at the top of the polymer extrusion die) 20 it is very difficult to coil the product on a continuous coiler of the type shown in the '147 patent in this configuration. Accordingly, in a preferred practice of the fabrication practice described herein, wire 10 A is rotated 90 degrees as shown in FIG. 4 prior to coiling. This rotation results in a much more manageable coiling operation wherein the individual wraps of wire 10 A appear as shown in FIG. 5 that depicts the wire configuration obtained when wire 10 A is used to wind a transformer. As is seen from FIG. 5 , when wire 10 A is coiled in a transformer, polymer layer 14 A forms the insulation between abutting wires 10 A. The insertion of paper or other material interleaving 30 between adjacent overlapping layers in the conventional fashion allows for the conventional fabrication of a transformer from wire 10 A all while reducing the cost of wire 10 A by eliminating a substantial amount of the volume of insulating polymer 14 A applied to wire 10 A and used in the transformer wound using wire 10 A.
Although a wide variety of polymeric materials can be applied to the wire, according to the preferred practice of the present invention for the manufacture of magnet wire useful particularly in the fabrication of high temperature transformers (180° C.+) the following polymers are preferred: RADELI® R; ACUDEL®; and HYFALON® the first two of which are polyphenylsulfones (of 180° C. and 220° C. capability respectively) and the third is a tetrafluoroethylene copolymer. All of these materials are commercially available from Solvay Advanced Polymers, LLC, 3702 Clanton Rd., Augusta, GA 30906.
Thus, what have been described are a novel single extremity coated magnet wire and a method for its production that result in the significant reduction of the amount of high cost insulating polymer that is applied to the wire and further result in a significant reduction in the cost of a transformer manufactured from the wire.
As the invention has been described, it will be apparent to those skilled in the art that the same may be varied in many ways without departing from the intended spirit and scope of the invention, and any and all such modifications are intended to be included within the scope of the appended claims.
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A novel polymer coated magnet wire that includes an insulating polymeric coating on only one facet thereof. Such a magnet wire can be conventionally wound using current transformer manufacturing processes but can be produced at significantly lower cost due to the almost 75% reduction in the volume of insulating polymeric material applied to the magnet wire core as compared to similar prior art such products. The method provides for the application of the insulating polymeric coating to only a single minor axis facet of the magnet wire core through the use of custom dies and a modified manufacturing process.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a United States National Phase application of International Application PCT/DE2007/001975 and claims the benefit of priority under 35 U.S.C. §119 of German Patent DE 10 2006 053 857.9 filed Nov. 14, 2006, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention pertains to a breathing tube connecting device for connecting a breathing tube to at least two respirators.
BACKGROUND OF THE INVENTION
Breathing tube connecting devices are used in a known manner for connecting a breathing tube or a breathing tube system, designated as breathing tube below for the sake of simplicity, to a respirator. A respirator may comprise an anesthesia apparatus. The breathing tube connecting devices differ with respect to the diameter of a breathing gas through duct. Thus, breathing tube connecting devices for neonatal use have smaller diameters compared to breathing tube connecting devices for connecting a breathing tube to a respirator for adults. Breathing tube connecting devices have either a male or female connection. A connection complementary thereto can be found in each case on the respirator. Breathing tube connecting devices for a connection to a neonatal respirator are usually designed with a female connection, whereas breathing tube connecting devices for a connection to a respirator for adults can be designed with a male or female connection. On the other hand, the connections to the neonatal respirator are usually designed as a male connection and the connections to the adult respirator are designed as a combination of male and female connections.
For the breathing tube connecting devices there is a current standard of 11, 15 and 22 mm diameters of the breathing gas through duct. Here, breathing tube connecting devices for neonatal use have a diameter of the breathing gas through duct of 11 mm, whereas breathing tube connecting devices for respirators for adults may have a breathing gas through duct diameter of 15 mm or 22 mm.
Respirators for adults generally have a breathing mode for newborns. If a neonatal patient shall now be respirated with a respirator for adults, it is desirable that the breathing tube connecting device of the neonatal breathing tube, which is designed for a connection to a neonatal respirator, can be connected both to the neonatal respirator and to the respirator for adults. Moreover, it should be possible to produce the breathing tube connecting device in a simple and cost-effective manner.
SUMMARY OF THE INVENTION
Accordingly, the object of the present invention is to provide a breathing tube connecting device that is simple to produce, which eliminates the problem described above.
According to the present invention, this object is accomplished by a breathing tube connecting device for connecting a breathing tube to at least two respirators consisting of a base body with a breathing gas through duct embodied in the base body, a jacket body, which can be meshed with the base body in a positive-locking manner and thereby encloses at least a part of the base body in a coaxial manner, and a transponder, which is provided between the base body and the jacket body. The breathing gas through duct and jacket body are designed at least partly as a coupling section for a selective connection of the breathing tube to one of the at least two respirators. In this context, the transponder is defined as an element for wireless sending and for receipt of data.
The idea of the present invention is to provide a base body with a breathing gas through duct corresponding to the diameter of the neonatal breathing tube and a jacket body designed in terms of dimensions corresponding to the connection to the respective respirator for adults, whereby the base body can be combined with the jacket body provided for the corresponding respirator for adults and in the combination the base body and the jacket body are meshed in a positive-locking manner, such that a neonatal breathing tube can be connected by means of the breathing tube connecting device according to the present invention both to a neonatal respirator and to a respirator for adults.
The advantages gained with the present invention are especially that the breathing tube connecting device according to the present invention can be produced in a very cost-effective manner. In this case, a base body can be produced, which can be combined and can be meshed (engaged) in a positive-locking manner with a corresponding jacket body according to the respective respirator for adults in such a way that the breathing tube connecting device can be connected both to the neonatal respirator and to the respirator for adults. A respectively identical base body may thus be combined with a jacket body, which has a diameter required for connection to the corresponding respirator for adults. The breathing tube connecting device according to the present invention thus makes possible a connection of a breathing tube both to a first and a second respirator, whereby the first and second respirators have a different connecting structure. The first respirator is a neonatal respirator and the second respirator a respirator for adults. In addition, the respirator for adults has a breathing mode for the respiration of neonates.
The structure of the breathing tube connecting device according to the present invention is designed in such a way that both the outer surface of the base body and the inner wall of the jacket body have a preferably cylindrical design. This design makes possible a stable connection of the base body and jacket body. The base body and jacket body are connected in a positive-locking manner preferably by means of a meshing of a circumferential beading provided on the outer surface of the base body with a complementary circumferential groove provided on the inner wall of the jacket body. To prevent a rotation of the jacket body in relation to the base body after the meshing of the base body and jacket body in a positive-locking manner, particularly when connecting or disconnecting the breathing tube connecting device to or from the respirator, means that prevent rotation are provided in another embodiment of the device according to the present invention. For this, preferably the base body has a lug directed at right angles to the outer surface of the base body and the jacket body has a complementary cutout directed at right angles to its inner wall. The lug of the outer surface of the base body meshes with the cutout of the inner wall of the jacket body when they are connected in a positive-locking manner. A material of the base body and the jacket body preferably consists of polypropylene. As is well known, polypropylene is an elastic material that promotes the positive-locking connection of the base body and jacket body. In addition, the part of the breathing gas through duct of the base body directed toward a respirator and the outer surface of the jacket body run in a cone-shaped manner for an optimal connection of the breathing tube connecting device to a respirator.
The transponder is advantageously provided between the base body and jacket body. Transponders have a high heat sensitivity. Insertion into the base body or jacket body during a production of the base body or jacket body in the injection molding process is almost impossible without destroying its functions. A positioning of the transponder on the outer surface of the breathing tube connecting device, for example, by bonding, may, on the one hand, cause damage to the transponder during the connection of the breathing tube connecting device to the respirator, and, on the other hand, lead to an untightness of the respirator/patient connection.
The structure of the breathing tube connecting device according to the present invention does make it possible to position the transponder between the outer surface of the base body and the inner wall of the jacket body, such that the transponder is protected against damage by the jacket body of the breathing tube connecting device surrounding it.
Auxiliary means for positioning the transponder on the base body are preferably provided on the outer surface of the base body. For example, the circumferential beading provided on the outer surface of the base body can be provided as a positioning aid when mounting the transponder on the base body. The transponder is preferably mounted on a side of the base body pointing toward the respirator. Thus, passive transponders with a highly limited range may also be used. This may be, for example, an RFID transponder that has a range of ca. 18 mm.
The transponder is preferably mounted on the outer surface of the base body by means of a suitable bonding process. Bonding processes for mounting transponders on the surface of a certain part are known from the state of the art; hence, this will not be discussed in detail at this point. However, in a preferred process step shortly before completion or after the production of the base body by means of an injection molding process, provisions may also be made for mounting the transponder on the base body, while the base body preferably initially remains in an injection molding die after its production and the transponder is mounted onto the outer surface of the base body by means of a suitable injection molding technique, without the transponder being entirely surrounded by injection molding material.
In an especially preferred embodiment of the breathing tube connecting device, the transponder is equipped with a function for storing data. By means of the storage function of data, the transponder advantageously makes possible a filing of breathing parameters. For example, a respiration rate, a breath, a breathing pressure and/or an identification of the breathing tube can be filed as breathing parameters. When the respirator is changed, e.g., because of a change within the clinical area of the patient, the breathing tube remains at the patient. The data filed in the transponder are thus available with the breathing tube and make possible an automatic or semi-automatic setting of the breathing parameters required at this respirator when the breathing tube is connected to a different respirator. Thus, the setting parameters of a first respirator can be transmitted in a simple manner to a second respirator. Furthermore, data about forbidden parameters of other apparatuses can be filed in the transponder of the breathing tube connecting device. For example, a breathing mode for adults can be blocked when the neonatal breathing tube is connected to a respirator for adults after recognition of the neonatal breathing tube.
Furthermore, the transponder of the device according to the present invention makes it possible to detect and file such personal data as, for example, a identification number. By means of a patient identification number, a respirator connected to a clinical network can be set to the breathing parameters required for the corresponding patient.
In another embodiment of the breathing tube connecting device according to the present invention, parameters are transmitted for a guarantee of a perfect function of the breathing tube. For example, a shelf life of the breathing tube can be stored on the transponder and corresponding information can be sent to the user after the end of a time, e.g., a time determined and fixed for a guarantee of a perfect function of the breathing tube.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which preferred embodiments of the invention are illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a simplified sectional view of the breathing tube connecting device according to the present invention in a first embodiment;
FIG. 2 is a simplified sectional view of the breathing tube connecting device according to the present invention for explaining a connection of a neonatal breathing tube to a neonatal respirator;
FIG. 3 is a simplified sectional view of the breathing tube connecting device according to the present invention for explaining a connection of a neonatal breathing tube to a respirator for adults, and
FIG. 4 is a simplified sectional view of the breathing tube connecting device according to the present invention in a second embodiment with a transponder.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings in particular, the breathing tube 1 shown in FIG. 1 is provided in its end area with a breathing tube connecting device 2 , which has a base body 3 and a jacket body 4 enclosing a part of the base body 3 directed toward a respirator 12 . A breathing tube fastening section 6 , in which the breathing tube 1 is fixed, is formed in the area of the base body 3 on the breathing tube side. The base body 3 has a breathing gas through duct 5 , whose through cross section essentially corresponds to the through cross section of the breathing tube 1 connected to the breathing tube fastening section 6 . Both the outer surface of the base body 3 and the inner wall of the jacket body 4 of the breathing tube connecting device 2 shown in FIG. 1 have a cylindrical design.
In a middle area of the base body 3 , a circumferential beading 8 is provided on the outside thereof, via which a positive-locking connection with a complementary circumferential groove 9 located on the inner wall of the jacket body 4 , which is favorable from mechanical points of view, is achieved. To prevent a rotation of the jacket body 4 against the base body 3 when connecting or disconnecting the breathing tube connecting device 2 to or from a respirator 12 , a lug 10 directed at right angles to an outer surface of the base body 3 is provided, which meshes with a complementary cutout directed at right angles to the outside of the jacket body 4 . A snapping of the lug 10 of the base body 3 into the cutout of the jacket body 4 signals an accurate connection of the base body 3 and jacket body 4 . The base body 3 and jacket body 4 are preferably made of polypropylene (PP) because of good elastic properties. However, it is also possible to make the base body 3 and the jacket body 4 out of other suitable materials.
For the purpose of explaining the connection of the breathing tube connecting device according to the present invention to a respirator 12 , FIGS. 2 and 3 show a respirator-side connecting structure 16 , which has a design essentially complementary to the coupling section 7 embodied by the base body 3 and jacket body 4 . FIG. 2 shows a breathing tube connecting device 2 for connecting to a neonatal respirator 12 . A neonatal respirator 12 is generally designed with a male connecting structure 16 , which has a diameter of 11 mm. A respirator 12 for adults, as it is shown in FIG. 3 , usually has, by contrast, a male and a female connecting structure 16 , whereby the male connecting structure 16 has a diameter of 15 mm and the female connecting structure 16 has a diameter of 11 mm. The breathing tube connecting device 2 according to the present invention may advantageously connect a neonatal breathing tube 1 to a neonatal respirator 12 and to a respirator 12 for adults. In the connection of a breathing tube connecting device 2 of a neonatal breathing tube 1 to a connecting structure 16 of a neonatal respirator 12 schematically shown in FIG. 2 , the coupling section of the breathing tube connecting device 2 identified by reference number 7 meshes with a pin section 15 of the connecting structure of the neonatal respirator 12 . The coupling section 7 is formed by the inner wall of the base body 3 , [i.e.] the breathing gas through duct 5 . A part of the breathing gas through duct 5 of the base body 3 directed toward the respirator 12 advantageously has a cone-shaped design. The pin section 15 of the connecting structure 16 of the neonatal respirator 12 shown in FIG. 2 has a shape complementary to the coupling section 7 .
During the connection of the breathing tube connecting device 2 of a neonatal breathing tube 1 to a connecting structure 16 , as is schematically shown in FIG. 3 , of the respirator 12 for adults, the coupling section 7 of the breathing tube connection device 2 meshes with a recess 14 and with the pin section 15 of the connecting structure 16 of the respirator 12 for adults. The coupling section 7 is formed by the inner wall of the base body 3 and the outer surface of the jacket body 4 . With the breathing tube connecting device 2 according to the present invention, a neonatal breathing tube 1 can thus be connected both to the connecting structure 16 of the neonatal respirator 12 (shown in FIG. 2 ) and to the connecting structure 16 of a respirator 12 for adults (shown in FIG. 3 ). The outer surface of the jacket body 4 advantageously has, as shown in FIG. 3 , a cone-shaped design and cooperates with the cone-shaped recess 14 of the connecting structure 16 of the respirator 12 for adults.
FIG. 4 shows a very particularly preferred embodiment of the breathing tube connecting device 2 . A transponder is provided between the outer surface of the base body 3 and the inner wall of the jacket body 4 . The transponder 11 is used for the wireless sending and the wireless receipt of data and is additionally equipped with a function for storing data. The circumferential beading 8 provided on the outer surface of the base body 3 is used as a positioning aid during the mounting of the transponder 11 on the base body 3 . It is thereby guaranteed that the transponder 11 has a reproducible position and is provided very close at one end of a side of the base body 3 pointing toward the respirator 12 . This makes it possible to use passive transponders 11 , for example, an RFID transponder 11 with a range of ca. 18 mm. The receipt and sending of data are thus optimally guaranteed. The transponder 11 of the breathing tube connecting device 2 according to the present invention of FIG. 4 makes it possible, by means of a data storage function, to advantageously file such breathing parameters as, for example, a respiration rate, a breath, a breathing pressure and/or a form of respiration. If only the breathing tube 1 is uncoupled from the neonatal respirator 12 and is coupled to a respirator 12 for adults, the breathing parameters of the neonatal respirator 12 stored on the transponder 11 can be transmitted to the respirator 12 for adults, or these breathing parameters are released to the respirator 12 for adults. A setting of too-high breathing pressures for newborns, as they are necessary for a respiration of adults, is thus ruled out. Furthermore, personal data, for example, a patient identification number can be stored with the transponder 11 of the breathing tube connecting device 2 according to the present invention. In case of a change of the clinical area and thus of the respirator, the breathing tube 1 remains at the patient. The data stored in the transponder 11 are thus available with the breathing tube 1 and make possible a transmission of the data to the respirator 12 when the breathing tube 1 is connected to the respirator 12 for adults. By means of a patient identification number, for example, a respirator 12 connected to a clinical network can be set to the breathing parameters required for the corresponding patient.
In another embodiment of the breathing tube connecting device 2 shown in FIG. 4 , parameters for a guarantee of a perfect function of the breathing tube 1 are transmitted to the transponder 11 . For example, the time of using the breathing tube 1 at the respective respirator 12 is measured and then sent to the transponder 11 . Thus, the overall shelf life of the breathing tube 1 can be stored on the transponder 11 and after reaching a time duration that defines an end for the guarantee of the perfect function of the breathing tube 1 , corresponding information can be sent to the user.
A preferred process for the manufacture of the breathing tube connecting device 2 according to the present invention is explained below based on the exemplary embodiment shown in FIG. 4 . In a first process step, the base body 3 is produced by means of an injection molding process. The base body 3 has thereby a circumferential beading 8 protruding from the outer surface, which is used for the positioning of a transponder 11 to be mounted on the outer surface of the base body 3 in another process step. The transponder 11 is thereby mounted on a part of the outer surface of the base body 3 pointing toward the respirator 12 . After that or in parallel thereto, the jacket body 4 is produced by means of an injection molding process. In another process step, the base body 3 is connected to the jacket body 4 in a positive-locking manner.
While specific embodiments of the invention have been described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.
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A breathing tube connecting device is provided for connecting a breathing tube to at least two respirators. The breathing tube connecting device includes a base body with a breathing gas through duct embodied in the base body, a jacket body, which can be meshed with the base body in a positive-locking manner and thus encloses at least a part of the base body in a coaxial manner, and a transponder. The transponder is provided between the base body and the jacket body. The breathing gas through duct and the jacket body are embodied at least partly as a coupling section for a selective connection of the breathing tube to one of the at least two respirators.
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This application is based on Japanese Patent Application No. Hei 9-216765 filed on Aug. 11, 1997, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
a) Field of the Invention
The present invention relates to a method of manufacturing a semiconductor device, and more particularly to a method of manufacturing a semiconductor device including a process of patterning a lamination of a silicon film and a metal film formed thereon.
b) Description of the Related Art
Low resistance of gate electrodes is becoming the requisite for the recent high performance of MOS transistors. Low resistance techniques, especially using a lamination of a silicon film and a metal film as a gate electrode, have drawn much attention.
Technique of patterning a laminated structure of tungsten (W) and TiN is disclosed in JP-A-4-219929. With this technique, the upper W layer is first etched with F containing gas by using as an etching mask a resist pattern formed on the W layer. Thereafter, the lower TiN layer is etched with Cl 2 or Br containing gas. After the TiN layer is etched, the resist pattern is removed to form a patterned lamination structure of W and TiN films. With this technique, a gate electrode structure of a lamination of W/TiN/Si can be formed.
When a lamination structure of gate electrode layers is etched to leave the gate electrode structure, the gate insulating layer is exposed on both sides of the gate electrode structure. In order not to damage a silicon layer under the gate insulating layer, it is desired to automatically stop etching when the gate insulating layer is exposed. To this end, it is necessary to set a high etching selection ratio of the lamination structure of gate electrode layers to the gate insulating layer. The etching conditions disclosed in JP-A-4-219929, however, use an insufficient etching selection ratio, and the silicon layer under the gate insulating layer is likely to be damaged.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method of manufacturing a semiconductor device capable of reducing damages of an underlying surface layer when a lamination pattern of a silicon film and a metal film is patterned.
According to one aspect of the present invention, there is provided a method of manufacturing a semiconductor device comprising the steps of: depositing a first film essentially consisting of silicon on the surface of a semiconductor substrate; depositing on the first film a second film essentially consisting of material having a proper etching selection ratio relative to tungsten; depositing on the second film a third film essentially consisting of tungsten; forming a resist pattern on the third film; etching and patterning the third film to the surface of the second film, by using the resist pattern as a mask; patterning the second film to have the same shape as the third film; and patterning the first film to have the same shape as the third film, and the method further comprising the steps of: after said step of patterning the third film and before said step of patterning the first film, heating the resist pattern to a temperature of 80° C. or higher; exposing the semiconductor substrate in atmospheric air; and removing the resist pattern.
Since the resist pattern is heated to a temperature of 80° C. or higher before the semiconductor substrate is exposed in atmospheric air, residues left after the resist pattern is removed can be easily removed. The resist pattern is already removed when the first film is etched. It is therefore possible to avoid adverse effects of carbon to be emitted from the resist pattern. For example, if there is an SiO 2 film formed under the first silicon film and an etching atmosphere contains carbon, the etching selection ratio of the silicon film to the SiO 2 film is lowered.
According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device comprising the steps of: depositing a first film essentially consisting of silicon on the surface of a semiconductor substrate; depositing on the first film a second film essentially consisting of material having a proper etching selection ratio relative to tungsten; depositing on the second film a third film essentially consisting of tungsten; forming a resist pattern on the third film; etching and patterning the third film to the surface of the second film, by using the resist pattern as a mask; patterning the second film to have the same shape as the third film; and patterning the first film to have the same shape as the third film, and the method further comprising the step of: after said step of patterning the third film and before said step of patterning the first film, removing the resist pattern without exposing the semiconductor substrate into atmospheric air.
Since the semiconductor substrate is not exposed in atmospheric air before the resist pattern is removed, the resist pattern can be removed cleanly without leaving residues.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A to 1D are cross sectional views illustrating the main processes of a semiconductor device manufacture method according to a first embodiment of the invention.
FIGS. 2A to 2C are cross sectional views illustrating the main processes of a semiconductor device manufacture method according to a second embodiment of the invention.
FIGS. 3A to 3D are cross sectional views illustrating the main processes of a semiconductor device manufacture method according to a third embodiment of the invention.
FIG. 4 is a diagram showing the outline of an etching system used by the embodiments.
FIG. 5 is a diagram showing the outline of a resist ashing system used by the embodiments.
FIGS. 6A and 6B are cross sectional views illustrating the states of a substrate after some processes of preliminary experiments.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the method described in the above-cited JP-A-4-219929, a W film and a TiN film are etched by using a resist pattern as a mask. With this method, however, an etching selection ratio of the gate electrode to the gate insulating film of SiO 2 is lowered by carbon atoms contained in the resist pattern. In order to maintain the etching selection ratio high, it is desired to remove the resist pattern at least before the gate insulating film is exposed.
Preliminary experiments performed basing upon the above concept will be first described prior to the description of preferred embodiments of the invention.
As shown in FIG. 6A, a substrate structure was prepared which had a lamination of an SiO 2 film 101, a polysilicon film 102, a TiN film 103, a W film 104 and an SiON film 105 stacked in this order from the bottom on a silicon substrate 100. A resist pattern 106 was formed on the SiO 2 film 105 which was used as a reflection preventing film during photolithography.
By using the resist pattern 106 as a mask, the SiON film 105 and W film 104 were etched with NF 3 gas. In this case, the TiN film functions as an etching stopper. Thereafter, the substrate was exposed in atmospheric air and loaded into a process chamber of a down-flow type resist ashing system using microwave plasma. The resist pattern 106 was removed by using plasma of O 2 and H 2 O.
FIG. 6B is a cross sectional view of the substrate after the resist pattern 106 was removed. As shown, residues 106 and 107 were left. The residue 106 had a wall shape protruding upward along the side walls of the lamination structure of patterned SiON film 105 and W film 104, and the residue 107 was formed at the lower portion of the side walls of the patterned lamination structure. Although the residue 106 was removed by amine containing solution (ACT935 manufactured by Advanced Chemical for Advanced Technology), the residue 107 was unable to be removed.
Since the residue 107 is left, the TiN film 103 and polysilicon film 102 cannot be patterned with good controllability by using the W film 104 and SiON film 105 as a mask. The embodiments of the invention can prevent the formation of these residues or can remove these residues so that the TiN film 103 and polysilicon film 102 can be etched with good controllability.
The first embodiment of the invention will be described with reference to FIGS. 1A to 1D.
As shown in FIG. 1A, the surface layer of a silicon substrate 1 is thermally oxidized at a temperature of about 900° C. to form a silicon oxide gate insulating film 2 of about 10 nm thick. On the gate insulating film 2, a polysilicon film 3 of about 50 nm thick is deposited by chemical vapor deposition (CVD) using SiH 4 as source gas. On the polysilicon film 3, a TiN film 4 of about 25 nm thick is deposited through reactive sputtering using a Ti target and N 2 gas and Ar gas. On the TiN film 4, a W film 5 of about 150 nm thick is deposited by CVD using WF 6 as source gas. On the W film 5, an SiON film 6 of about 90 nm thick is deposited by CVD using SiH 4 , O 2 and N 2 as source gas. In place of the polysilicon film 3, an amorphous silicon film may be deposited.
On the SiON film 6, a resist pattern 7 is formed. By using this resist pattern 7 as a mask, the SiON film 6 and W film 5 are etched.
The outline of an etching system is shown in FIG. 4. A process vessel 60 with upper and lower openings has an electrode 61 hermetically mounted over the upper opening. The electrode 61 is applied with a radio frequency (RF) voltage from an RF power source 72 operating at a frequency of 13.56 MHz. An electrostatic chuck is provided in the electrode 61 to hold a substrate 66 at the bottom surface of the electrode 61.
A coolant flow passage 64 is also formed in the electrode 61. A low temperature chiller 63 introduces coolant into the coolant flow passage 64 to cool the substrate 66 held by the electrostatic chuck. A gas supply pipe 65a and a gas exhaust pipe 65b are open at the chuck surface holding the substrate 66. He gas is supplied from the gas supply pipe 65a. The He gas is filled in a space between the substrate holding surface and the substrate 66 and discharged via the gas exhaust pipe 65b. The He gas filled in the space between the substrate holding surface and the substrate 66 operates as a heat conducting medium to efficiently cool the substrate 66.
At the center of the lower opening of the process chamber 60, an etching gas supply port 70 is mounted. Etching gas is supplied from the etching gas supply port 70 into the process chamber 60. The etching gas supplied into the process chamber 60 is discharged via a gap formed between the inner circumference of the lower opening and the etching gas supply port 70.
Returning back to FIG. 1A, the etching conditions of the SiON film 6 and W film 5 will be described. First, NF 3 gas at a flow rate of 140 sccm and Ar gas at a flow rate of 70 sccm are used as the etching gas to perform an etching process for 15 seconds at an inner pressure of the process chamber of 0.1 Torr, an applied power of 500 W and a chiller temperature of -50° C. The W film 5 is etched preferably at a substrate temperature of -20° C. or lower. Next, SF 6 gas at a flow rate of 75 sccm and N 2 gas at a flow rate of 3 sccm are used as the etching gas to perform an etching process at an inner pressure of the process chamber of 0.08 Torr, an applied power of 230 W and a chiller temperature of -50° C. As the etching gas of the W film 5, gas which contains fluorine such as NF 3 gas, mixed gas of NF 3 and Ar, SF 6 gas, or mixed gas of SF 6 and N 2 may be used.
The etching completion timing of the W film 5 is detected by monitoring emission spectra of the plasma in the process chamber. The etching completion timing of the W film 5 is presumably when the intensity of the emission peak caused by F atoms increases sharply. After the intensity of the emission peak caused by F atoms increases sharply, over-etch is further performed. The time of this over-etch is about 10% of the time duration from the introduction of SF 6 gas to the detection of the etching completion of the W film 5. Since the TiN film 4 serves as an etching stopper, the W film 5 can be removed with good reproductivity.
FIG. 1B is a cross sectional view of the substrate after the W film 5 is etched. This substrate is maintained in the etching system and the process chamber 60 is evacuated to perform a heat treatment for one minute at a temperature of 80° C. After this heat treatment, the substrate is picked up from the process chamber into atmospheric air and then placed in a down-flow type resist ashing system using microwave plasma and operating at a frequency of 2.45 GHz to remove the resist pattern 7.
FIG. 5 shows the outline of the resist ashing system used by the embodiment. The inner space of a process chamber 80 made of Al is divided into an upper plasma generating chamber 82 and a lower process chamber 83 by a meshed shower head 81. Microwaves transmitted via a waveguide 84 pass through a microwave transmitting window 85 and are introduced into the plasma generating chamber 82. Process gas is also introduced via a gas guide tube 86 into the plasma generating chamber 82. A stage 88 for placing a substrate 87 thereon is mounted in the lower process chamber 83.
The process gas supplied into the plasma generating chamber 82 is changed into a plasma state by the microwaves. This plasma flows downward via the shower head 81 and reaches the surface of the substrate 87 placed on the stage 88. This plasma ashes and removes the resist pattern formed on the surface of the substrate 87. The plasma and its byproducts in the lower process chamber 83 are discharged from a lower gas outlet 89.
Returning back to FIG. 1B, the ashing conditions of the resist pattern 7 will be described. O 2 gas at a flow rate of 1350 sccm and H 2 O gas at a flow rate of 150 sccm were used as the ashing gas. The inner pressure of the process chamber was 1.0 Torr, the microwave power was 1.4 kW, and the substrate temperature was 200° C. Under these conditions, the resist pattern 7 was ashed. The residue 107 at the lower side wall portion such as shown in FIG. 6B was not found. The wall residue 106 protruding upward along the side wall portion was able to be removed by processing it with amine containing solution (ACT935 manufactured by Advanced Chemical for Advanced Technology) for 15 minutes at a temperature of 75° C.
As ashing gas, gas which contains F atoms, such as CF 4 , SF 6 or NF 3 may also be used.
After the resist pattern 7 is removed, the TiN film 4 and polysilicon film 3 are etched in the etching system shown in FIG. 4, by using the patterned SiON film 6 as a mask.
The TiN film 4 is etched by using Cl 2 as etching gas under the conditions of a gas flow rate of 50 sccm, a pressure of 0.05 Torr, an applied power of 500 W, the electrode 61 temperature of 80° C. and an etching time of about 10 seconds. The polysilicon film 3 is etched by using HBr as etching gas under the conditions of a gas flow rate of 100 sccm, a pressure of 0.1 Torr, an applied power of 300 W and the electrode 61 temperature of 80° C.
FIG. 1C is a cross sectional view showing the substrate after the TiN film 4 and polysilicon film 3 are etched. As shown in FIG. 1C, a gate lamination structure inclusive of layers from the polysilicon film 3 to the SiON film 6 with generally vertical side walls can be formed while the surrounding gate insulating film 2 is left unetched. In the above manner, a gate electrode of three layers, the polysilicon film 3, TiN film 4 and W film 5, can be formed.
As etching gas of the polysilicon film 3, Cl 2 gas, mixed gas of Cl 2 and O 2 , or mixed gas of HBr and O 2 may be used.
FIG. 1D is a schematic cross sectional view showing a MOS transistor with its source/drain regions being formed after the gate electrode is formed. The processes after the process of FIG. 1C will be briefly described.
Impurity ions are implanted into the surface layer of the silicon substrate by using the gate lamination structure as a mask, to thereby form a low impurity concentration structure in the surface layer. The gate insulating film 2 exposed on both sides of the gate lamination structure is etched and removed. Thereafter, side wall insulating films 9 are formed on the side walls of the gate lamination structure. Impurity ions for the formation of source/drain regions are then implanted by using the sidewall insulating films 9 and gate lamination structure as a mask. The substrate is annealed to activate the implanted impurity ions to form a source region 8S and a drain region 8D in the substrate surface layer on both sides of the gate lamination structure.
In this first embodiment, after the process shown in FIG. 1B, the substrate is subjected to a heat treatment at 80° C. before it is exposed into atmospheric air. This heat treatment can prevent residue which is hard to be removed from being left after the resist pattern 7 is ashed. The residue after the ashing can be removed with amine containing solution.
A heat treatment at a temperature of 50° C. left residue which is hard to be removed. It is therefore preferable to set the heat treatment temperature to 80° C. or higher before the substrate is exposed in atmospheric air. In order to avoid decomposition of resist, it is preferable to set the heat treatment temperature to 200° C. or less. In order to have sufficient heat treatment effects, it is preferable to perform the heat treatment for 30 seconds or longer.
When the polysilicon film 3 is etched at the process shown in FIG. 1C, the lamination of the SiON film 6 and W film 5 is used as an etching mask. In this case, since the resist pattern is not left, adverse effects by carbon atoms can be avoided. Therefore, the polysilicon film 3 can be etched at a high etching selection ratio relative to the gate insulating film 2 made of SiO 2 .
Next, the second embodiment will be described with reference to FIGS. 2A to 2C.
The processes of forming the structure shown in FIG. 2A are the same as those of forming the structure shown in FIG. 1A of the first embodiment. In the first embodiment, the SiON film 6 and W film 5 are etched by using the resist pattern 7 as a mask. In the second embodiment, by using this resist pattern 7 as a mask, the underlying TiN 4 is also etched. The etching conditions of the SiON film 6 and W film 5 are the same as the first embodiment.
After the W film 5 is etched, the substrate is transported into another process chamber while the vacuum state is maintained. The TiN film 4 is etched for about 10 seconds by using Cl 2 as etching gas under the condition of a flow rate of 50 sccm, a pressure of 0.05 Torr, an applied power of 500 W and the electrode 61 temperature of 80° C.
In this case, the resist pattern 7 is heated to the temperature of 80° C. Therefore, similar to the first embodiment, the resist pattern 7 undergoes a thermal history prior to the exposure in atmospheric air.
FIG. 2B is a cross sectional view of the substrate after the TiN film 4 is etched. This substrate is once exposed in atmospheric air and placed in the resist ashing system shown in FIG. 5 to remove the resist pattern 7. The ashing conditions are the same as the ashing conditions used for removing the resist pattern shown in FIG. 1B of the first embodiment. Residue after the resist pattern 7 was removed was able to be removed cleanly with amine containing solution.
The polysilicon film 3 is etched by using the SiON film 6 as a mask. The etching conditions of the polysilicon film 3 are the same as the etching conditions used for etching the polysilicon film 3 shown in FIG. 1B of the first embodiment.
FIG. 2C is a cross sectional view of the substrate after the polysilicon film 3 is removed. Also in this embodiment, since the residue after the resist pattern 7 is removed can be removed easily, the gate lamination structure with upright side walls from the polysilicon film 3 to SiON film 6 can be formed with good reproductivity, similar to the first embodiment. Furthermore, since the resist pattern 7 is not left when the polysilicon film 3 is etched, the polysilicon film 3 can be etched at a high etching selection ratio relative to the gate insulating film 2.
As shown in FIGS. 1A and 2A of the first and second embodiments, the SiON film 6 is formed on the W film 5, and at the later processes shown in FIGS. 1B and 2B the polysilicon film 3 is etched by using the SiON film 6 as a mask. Instead, without depositing the SiON film 6 on the W film 5, the polysilicon film 3 may be etched by using W film 5 as a mask.
The third embodiment of the invention will be described with reference to FIGS. 3A to 3D. In the first and second embodiments, the substrate is once exposed in atmospheric air before the resist pattern is removed. In the third embodiment, the resist pattern is removed without exposing the substrate in atmospheric air.
The processes of forming the structure shown in FIG. 3A are generally the same as those of forming the structure shown in FIG. 1A. Only a different point is that the SiON film 6 shown in FIGS. 1A and 2A is not formed. The W film 5 is etched by using a resist pattern 7. The W film 5 is etched by using NF 3 and Ar as etching gas under the conditions of an NF 3 gas flow rate of 150 sccm, an Ar gas flow rate of 150 sccm, a pressure of 0.1 Torr, an applied power of 200 W and a chiller temperature of -50° C.
FIG. 3B is a cross sectional view of the substrate after the W film 5 is etched. Without being exposed in athospheric air, the substrate is loaded in the process chamber of the resist ashing system shown in FIG. 5. The resist pattern 7 is removed under the same ashing conditions used for removing the resist pattern 7 shown in FIG. 1B of the first embodiment. It was possible to cleanly remove the resist pattern without leaving residue. The TiN film 4 and polysilicon film 3 are etched by using the W film 5 as a mask.
FIG. 3C is a cross sectional view of the substrate after the polysilicon film 3 is etched. Also in this case, the polysilicon film 3 can be etched at a high etching selection ratio relative to the gate insulating film, similar to the first embodiment.
FIG. 3D shows a MOS transistor with the gate lamination structure shown in FIG. 3C. The processes of forming a source region 8S, a drain region 8D and side wall insulating films 9 are similar to those of forming the structure shown in FIG. 1D of the first embodiment.
In the third embodiment, although the TiN film 4 and polysilicon film 3 are etched by using the W film 5 as a mask at the process shown in FIG. 3B, an SiON film 6 such as shown in FIG. 1A of the first embodiment may be deposited on the W film 5 to use this SiON film as an etching mask.
In the first to third embodiments, the TiN film 4 is formed under the W film 5 such as shown in FIG. 1A. Instead of the TiN film 4, other films made of material having a sufficient etching selection ratio relative to W may be used, for example, a two-layer structure film of TiN and Tin may be used.
In the first and second embodiments, the SiON film 6 is deposited on the W film 5 such as shown in FIG. 1A. Instead of the SiON film, other films made of inorganic material which does not contain carbon may be used, for example, an SiN film, an SiO 2 film or a lamination film thereof may be used.
In the first to third embodiments, the TiN film 4 and polysilicon film 3 are etched, for example, after the process shown in FIG. 1B in a reactive ion etching (RIE) system. Instead of an RIE system, an electron cyclotron resonance (ECR) plasma etching system may be used. In this case, the etching conditions may be a Cl 2 gas flow rate of 30 sccm, an O 2 gas flow rate of 5 sccm, a pressure of 5 mTorr, a microwave power of 1200 W, a bias RF power of 30 W and a chiller temperature of 20° C.
The present invention has been described in connection with the preferred embodiments. The invention is not limited only to the above embodiments. It is apparent that various modifications, improvements, combinations, and the like can be made by those skilled in the art.
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In a method of manufacturing a semiconductor device, a first film essentially consisting of silicon is deposited on the surface of a semiconductor substrate. A second film essentially consisting of material having a proper etching selection ratio relative to tungsten is deposited on the first film. A third film essentially consisting of tungsten is deposited on the second film. A resist pattern is formed on the third film. The third film is etched and patterned to the surface of the second film, by using the resist pattern as a mask. The second film is etched to have the same shape as the third film. The first film is etched to have the same shape as the third film. After the step of patterning the third film and before the step of patterning the first film, the resist pattern is heated to a temperature of 80° C. or higher, the semiconductor substrate is exposed in atmospheric air, and the resist pattern is removed.
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This application is a divisional of U.S. application Ser. No. 11/855,198 filed on Sep. 14, 2007 which claims the priority of U.S. Provisional Application Ser. No. 60/845,387 filed on Sep. 18, 2006.
FIELD OF THE INVENTION
The present invention generally pertains to vitreoretinal surgery and more particularly to improved systems for helping to perform fluid exchanges typically used in such surgeries.
DESCRIPTION OF THE RELATED ART
In a healthy human eye, the retina is physically attached to the choroid in a generally circumferential manner behind the pars plana. The vitreous humor, a transparent jelly-like material that fills the posterior segment of the eye, helps to cause the remainder of the retina to lie against, but not physically attach, to the choroid.
Sometimes a portion of the retina becomes detached from the choroid. Other times a portion of the retina may tear, allowing vitreous humor, and sometimes aqueous humor, to flow between the retina and the choroid, creating a build up of subretinal fluid. Both of these conditions result in a loss of vision.
To surgically repair these conditions, a surgeon typically inserts a vitrectomy probe into the posterior segment of the eye via a scleratomy, an incision through the sclera at the pars plana. The surgeon typically also inserts a fiber optic light source and an infusion cannula into the eye via similar incisions, and may sometimes substitute an aspiration probe for the vitrectomy probe. While viewing the posterior segment under a microscope and with the aid of the fiber optic light source, the surgeon cuts and aspirates away vitreous using the vitrectomy probe to gain access to the retinal detachment or tear. The surgeon may also use the vitrectomy probe, scissors, a pick, and/or forceps to remove any membrane that has contributed to the retinal detachment or tear. During this portion of the surgery, a saline solution is typically infused into the eye via the infusion cannula to maintain the appropriate intraocular pressure.
Next, the surgeon must manipulate the detached or torn portion of the retina to flatten against the choroid in the proper location. A soft tip cannula, forceps, or pick is typically utilized for such manipulation. Many surgeons also inject perfluorocarbon liquid as a retinal tamponading fluid into the posterior segment of the eye while aspirating the saline solution in the posterior segment to help cause the detached or torn portion of the retina to flatten against the choroid in the proper location. This procedure is typically referred to as a “fluid/perfluorocarbon” exchange. Other surgeons inject air as a retinal tamponading fluid into the posterior segment of the eye while aspirating the saline solution. This procedure is typically referred to as a “fluid/air” exchange. Finally, other surgeons inject a mixture of air and a gas such as SF 6 , C 3 F 8 , or C 2 F 6 as a retinal tamponading fluid into the posterior segment of the eye while aspirating the saline solution. This procedure is typically referred to as a “fluid/gas” exchange. As used herein, a “fluid” may include any liquid or gas that is suitable for use in the eye, including, but not limited to, saline solution with or without additives, silicone oil, a perfluorocarbon liquid, air, or a perfluorocarbon gas. The fluid exchange process is most typically performed by using a syringe filled with gas.
The process of filling the syringe with gas is currently time consuming. The process of filling the syringe with gas is a two person activity, requiring one person to be sterile, and one person not to be sterile. Often times, the coordination of activity between the two individuals results in the loss of gas and a waste of time, and, possibly, the violation of the sterile field.
As a result, a need still exists in vitreoretinal surgery for an improved system for helping to fill syringes with gas to be used in a fluid/gas exchange. The system should allow a scrub nurse to fill the gas syringe single handed, allow the nurse to maintain the integrity of the sterile field, eliminate the waste of expensive gas, provide early warning when gas bottles are depleted, and eliminate time lost as a result of mistakes.
SUMMARY OF THE INVENTION
In one aspect, the present invention is an ophthalmic surgical system for filling a syringe with a retinal tamponading gas. The system includes a surgical console having a user interface, a computer, first and second bottles containing pressurized retinal tamponading gases, and a port for fluidly coupling to an automatic gas filling consumable including a syringe. A user selects a particular retinal tamponading gas via the user interface, and the system fills the syringe.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention, and for further objects and advantages thereof, reference is made to the following description taken in conjunction with the accompanying drawing in which FIG. 1 is a schematic view of a surgical system including an automatic gas filling module and an automatic gas filling consumable.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiments of the present invention and their advantages are best understood by referring to FIG. 1 of the drawings. Surgical system 10 generally includes a surgical console 11 and an automatic gas filling consumable 26 . Surgical system 10 is preferably an ophthalmic surgical system.
Surgical console 11 preferably includes a pressurized gas bottle 12 having an integral valve 16 and regulator 20 , a pressurized gas bottle 14 having an integral valve 18 and regulator 22 , an automatic gas filling module 24 having an automatic gas filling port 34 , a microprocessor 98 electrically coupled to automatic gas filling module 24 via an interface 99 , a graphical user interface 100 electrically coupled to microprocessor 98 via interface 101 , and a pressurized air line 102 capable of providing pressurized air in a proportional manner. Pressurized gas bottle 12 preferably holds a first retinal tamponading gas such as, by way of example, C 3 F 8 . Pressurized gas bottle 14 preferably holds a second retinal tamponading gas such as, by way of example, SF 6 . Gas bottles 12 and 14 , valves 16 and 18 , and regulators 20 and 22 are fluidly coupled with automatic gas filling module 24 via connection points 30 and 32 . Likewise, automatic gas filling module 24 is fluidly coupled with automatic gas filling consumable 26 via automatic gas filling port 34 .
Automatic gas filling module 24 preferably includes shutoff valves 50 and 52 , each of which is fluidly coupled with a regulator 54 . Regulator 54 is fluidly coupled to timing valve 56 . A pair of pressure transducers 60 and 62 are positioned on either side of regulator 54 to monitor gas pressure and flow. Alternatively, pressure transducer 60 may be positioned between regulator 54 and transducer 62 . Pressurized air line 102 is fluidly coupled to automatic gas filling module 24 via connection point 66 , and is also fluidly coupled with timing valve 56 via a gas line 64 . A gas line 68 fluidly couples timing valve 56 and automatic gas filling port 34 . A gas line 65 fluidly couples gas line 64 and automatic gas filling port 34 via timing valve 56 . Alternatively, timing valve 56 may be eliminated, and a shutoff valve (not shown) may be included on pressurized air line 102 instead.
Automatic gas filling consumable 26 preferably includes a check valve 80 fluidly coupled to automatic gas filling port 34 via gas line 68 . A relief valve 82 is fluidly coupled with gas line 68 via a gas line 90 . Gas line 68 also fluidly couples filter 84 , stop cock 86 , filter 88 , and a distal end 89 of a syringe 104 . Pressurized air line 102 is fluidly coupled to an end cap 108 of syringe 104 via gas lines 64 and 65 .
Gas bottles 12 and 14 are installed in console 11 with valves 16 and 18 open, and with regulators 20 and 22 pre-set. During operation, a scrub nurse will insert a sterile automatic gas filling consumable 26 into automatic gas filling port 34 on automatic gas filling module 24 . Preferably, an RFID tag 200 on consumable 26 will be read by an RFID receiver 202 within surgical console 11 . RFID receiver 202 is electrically coupled to microprocessor 98 via an interface 204 . Surgical console 11 will thus detect that consumable 26 is an automatic gas filling consumable, and will populate the graphical user interface 100 appropriately. Alternatively, population of graphical user interface 100 may be performed manually in the event that RFID is not available.
Using graphical user interface 100 , the scrub nurse will then select the retinal tamponading gas to be used and initiate the automatic gas filling process. At this point, depending on the retinal tamponading gas selected, microprocessor 98 opens one of gas shutoff valves 50 or 52 . Regulator 54 will regulate the gas to a preset pressure that will flow to timing valve 56 . Pressure transducers 60 and 62 will be monitored to verify that sufficient gas pressure and flow are available (i.e. that the readings in pressure transducers 60 and/or 62 are at or near the set point of regulator 54 ). In the event that sufficient gas pressure and flow are not available, microprocessor 98 will signal the scrub nurse via graphical user interface 100 that the active gas bottle 12 or 14 needs to be replaced.
Next, timing valve 56 will be energized, and retinal tamponading gas will flow through automatic gas filling port 34 into automatic gas filling consumable 26 , and into distal end 89 of syringe 104 . Gas pressure will overcome the friction of a stopper 106 within syringe 104 , and stopper 106 will travel toward end cap 108 , filling syringe 104 with retinal tamponading gas. Pressurized air within pressurized air line 102 will be vented to atmosphere during this process.
Timing valve 56 will then be closed and pressurized air from pressurized air line 102 will be supplied to end cap 108 of syringe 104 , overcoming the friction of stopper 106 and allowing retinal tamponading gas to flow through syringe 104 , filter 88 , stop cock 86 , and filter 84 . Relief valve 82 is overcome so that retinal tamponading gas is vented to atmosphere. Microprocessor 98 repeats this cycle of introducing gas to syringe 104 , and purging gas from syringe 104 , a sufficient number of times until the concentration of retinal tamponading gas within syringe 104 is at or near 100%. In the embodiment where timing valve 56 is not utilized, microprocessor 98 controls the opening, closing, and cycling of (a) either shutoff valve 50 or 52 and (b) the shutoff valve on pressurized air line 102 in a manner similar to that described above.
The scrub nurse will then remove end cap 108 from syringe 104 and will install a plunger (not shown) into syringe 104 . The scrub nurse then closes stop cock 86 and disconnects consumable 26 from surgical console 11 at section A. Gas filled syringe 104 is then presented to the surgeon for final mixing and administration. The portion of automatic gas filling consumable 26 that remains on console 11 will be removed and discarded when the case is complete.
From the above, it may be appreciated that the present invention provides improved apparatus and methods for helping to fill a syringe with gas and helping to perform fluid/gas exchanges in vitreoretinal surgery. The system allows a scrub nurse to fill a gas syringe single handed, allows the nurse to maintain the integrity of the sterile field, eliminates the waste of expensive gas, provides an early warning when gas bottles are near depleted, and saves time lost due to mistakes.
It is believed that the operation and construction of the present invention will be apparent from the foregoing description. While the apparatus and methods shown or described above have been characterized as being preferred, various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the following claims.
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An ophthalmic surgical system for filling a syringe with a retinal tamponading gas is disclosed. The system includes a surgical console having a user interface, a computer, first and second bottles containing pressurized retinal tamponading gases, and a port for fluidly coupling to an automatic gas filling consumable including a syringe. A user selects a particular retinal tamponading gas via the user interface, and the system fills the syringe.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of invention relates to toy apparatus, and more particularly pertains to a new and improved projectile toy apparatus wherein the same is arranged to effect spreading of wings to provide for a glide and return relative to projection of the toy structure.
2. Description of the Prior Art
Toy apparatus simulating aircraft structure is indicated in U.S. Pat. No. 4,294,032 wherein a miniature rocket is mounted within a fuselage to open the cover relative to a body member directed therefrom.
U.S. Pat. No. 4,076,006 to Breslow sets forth a toy rocket with a pneumatic launcher associated therewith.
U.S. Pat. No. 3,465,472 sets forth a slingshot type rocket member having a parachute associated therewith.
U.S. Pat. No. 3,831,315 to Gilbert sets forth a toy rocket launching system employing a balloon member.
The instant invention attempts to overcome various components of the prior art in addressing a toy rocket structure to simulate an aircraft shuttle structure employing extensible wings opened subsequent to launching of the aircraft structure and in this respect, the present invention substantially fulfills this need.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of projectile toy apparatus now present in the prior art, the present invention provides a projectile toy apparatus wherein the same is arranged to provide for a toy structure having wing members opened subsequent to launching of the toy projectile structure. As such, the general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new and improved projectile toy apparatus which has all the advantages of the prior art projectile toy apparatus and none of the disadvantages.
To attain this, the present invention provides a projectile toy including an elongate body having an internal cavity, to include wing plates that are arranged for pivotment from a first position positioned within the cavity to a second position directed exteriorly of the cavity in a timed relationship to project the wings from the body upon directing the toy from a catapult alone or in combination with a propulsion member.
My invention resides not in any one of these features per se, but rather in the particular combination of all of them herein disclosed and claimed and it is distinguished from the prior art in this particular combination of all of its structures for the functions specified.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto. Those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
It is therefore an object of the present invention to provide a new and improved projectile toy apparatus which has all the advantages of the prior art projectile toy apparatus and none of the disadvantages.
It is another object of the present invention to provide a new and improved projectile toy apparatus which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new and improved projectile toy apparatus which is of a durable and reliable construction.
An even further object of the present invention is to provide a new and improved projectile toy apparatus which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such projectile toy apparatus economically available to the buying public.
Still yet another object of the present invention is to provide a new and improved projectile toy apparatus which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is an isometric illustration of the invention in use.
FIG. 2 is an enlarged isometric illustration of the projectile toy structure.
FIG. 3 is an orthographic top view of the projectile toy structure indicating the wings directed into the cavity of the rocket structure.
FIG. 4 is an orthographic cross-sectional illustration of the projectile toy having the wings pivotally mounted therewithin.
FIG. 5 is an orthographic top view, partially in section, of the timing mechanism of the invention relative to the wing structure.
FIG. 6 is an enlarged view of section 6 as set forth in FIG. 5.
FIG. 7 is an isometric illustration of the projectile toy having a solid fuel canister mounted therewithin.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the drawings, and in particular to FIGS. 1 to 7 thereof, a new and improved projectile toy apparatus embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described.
More specifically, the projectile toy apparatus 10 of the instant inventionessentially includes use with a slingshot member having spaced slingshot legs 11 mounted to a handle 12. An elastomeric band 13 is mounted to the legs 12 to receive a projectile toy 14 having a cylindrical body 15. The body 15 includes a first end 16 spaced from a conical second end 21. The body 15 includes a plurality of stabilizer fins 17 arranged in a coextensive relationship relative to one another in diametrically opposed sides of the body 15, with a rudder fin 18 mounted medially of the stabilizer fins 17, with the stabilizer fins and rudder fin 17 and 18 respectively mounted adjacent the first end 16. The first end includes a cap member 20 received within the first end, having a plurality of cap member openings 19 for simulation of a rocket member. A body hook 22 is mounted medially of the stabilizer fins 17 diametrically opposed to the rudder fin 18, with a body hook 22 positioned adjacent the second end 21.
A plurality of parallel and coextensive slots 23 are directed into the cylindrical body 15 having wing plates 24, with a single wing plate 24 pivotally mounted in one of the slots 23, with each slot 23 positioned in alignment with one of the stabilizer fins 17. The body 15 includes a body cavity 15a receiving the wing plates, in a manner as indicated in FIG. 4. As to the FIG. 3, the wing plates 24 are pivotal from a first position received within the body cavity to a second extended position extending from the body cavity, wherein the wing plates in the first position are oriented at an acute included angle between the wing plates, wherein in a second position, the wing plates defined an obtuse included angle therebetween. Each of the slots 23 includes a wing plate pivot axle 25 pivotally mounting an associated wing plate within an associated slot. Each of the wing plate pivot axles 25 includes a wing plate pivot axle gear 26 (see FIGS. 5 and 6). A plurality of intermediate gear axles 27 areprovided in a parallel relationship relative to the wing plate pivot axles 25, with each of the intermediate gear pivot axles 27 positioned interiorly of the cavity 15a, and each mounting an intermediate gear 28 incooperation with an associated wing plate pivot axle gear 26. A central axle 29 is mounted medially of the intermediate gear axles 27 and the wingplate pivot axles 25, having a central gear 30 and a main spring 31 mountedto the central axles 29. The main spring is tensioned upon directing of thewing plates into the slots 23, and permits a slow released unwinding to project the wing plates from the slots to the second position, as indicated in FIG. 5, from the first position, as indicated in phantom.
Reference to FIG. 7 indicates the removal of the cap 20 from the second end16, wherein the second end 16 within the cavity includes a plurality of recesses 34 arranged to cooperate with the end cap projections 33 of the end cap skirt 32. The same recesses 34 are arranged to subsequently receive canister projections 36 of an associated solid fuel canister 35 that is ignited by directing a fuse 39 into the fuse opening 38 that upon burning of the fuse 39 within the opening 38 permits propulsion and directing of fuel gases through the opening 38.
As to the manner of usage and operation of the instant invention, the same should be apparent from the above disclosure, and accordingly no further discussion relative to the manner of usage and operation of the instant invention shall be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner ofoperation, assembly and use, are deemed readily apparent and obvious to oneskilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents maybe resorted to, falling within the scope of the invention.
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A projectile toy includes an elongate body having an internal cavity, to include wing plates that are arranged for pivotment from a first position positioned within the cavity to a second position directed exteriorly of the cavity in a timed relationship to project the wings from the body upon directing the toy from a catapult alone or in combination with a propulsion member.
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FIELD OF THE INVENTION
This invention relates to apparatus for the continuous strip casting of aluminum sheet material and, more particularly, to a belt-type caster apparatus which may be used independently to convert molten aluminum material into a continuous strip of aluminum sheet material and in combination with a roll-type caster apparatus to reduce the thickness of the formed continuous strip of aluminum sheet material.
BACKGROUND OF THE INVENTION
There are several types of prior art apparatus for continuous strip casting of aluminum sheet material. A first type is a roll caster such as that disclosed in U.S. Pat. No. 2,790,216 to J. L. Hunter which comprises flowing molten aluminum into the nip between chill rollers which function to solidify the molten aluminum and form it into a continuous strip. A second type is known as a block caster such as that disclosed in U.S. Pat. No. 4,238,248 to Gyongyos comprising continuously casting an aluminum melt into strip form and hot rolling the continuous strip at a casting speed in a temperature range of between 300 degrees C. and the non-equilibrium solidus temperature of the melt with a total reduction in thickness in excess of 70% and coiling the hot strip and allowing it to cool. A third type is a belt caster such as that disclosed in U.S. Pat. No. 3,933,193 to Baker et al. which comprises feeding a continuous supply of molten aluminum material between moving upper and lower continuous belts and cooling the material while between the moving upper and lower belts to form a continuous strip of aluminum sheet material. Other variations of belt-type casters are disclosed in U.S. Pat. No. 3,036,348 to Hazelett et al. and U.S. Pat. No. 4,190,103 to Silvilotti et al.
Each of the foregoing apparatus and processes have certain advantages and disadvantages. For example, a roll-type caster operates at low speed whereas block and belt casters can accommodate high alloy and harder metals.
SUMMARY OF THE INVENTION
This invention provides a belt-type caster for forming a continuous strip of aluminum sheet material and a roll-type caster for immediately reducing the thickness of the continuous strip of aluminum sheet material wherein the continuous loop belt means used in the belt-type caster are driven by the rollers in the conventional Hunter horizontal cast roll-type caster.
In the preferred embodiment of the invention, the belt-type caster comprises an upper and a lower roll means, an upper and a lower guide arcuate guide means, an upper and a lower continuous loop belt means journalled around associated rolls and arcuate guide means and having opposed spaced apart straight sections each extending between the roll means and the arcuate guide means, dam means are provided to cooperate with the straight sections of the continuous loop belt means to form a rectangular cavity between the straight portions of the upper and lower continuous loop belt means. Means are provided for moving the upper and lower continuous loop belt means. The dam means comprise a plurality of short length individual dam means connected to a sprocket chain with means being provided to connect each individual dam means with one of the continuous loop belt means so that the dam means provide an outwardly directed force to each side of one of the continuous loop belt means to remove any buckling therein. A supply of molten aluminum material is fed between the upper and lower continuous loop belt means adjacent to the upper and lower arcuate guide means for movement with the upper and lower continuous loop belt means and the dam means through the straight portions. Cooling means associated with the straight portions of the upper and lower continuous loop belt means functions to cool the molten aluminum material to form a continuous strip of aluminum sheet material. In a preferred arrangement, the upper and lower rolls around which the upper and lower continuous loop belt means are journalled also form a roll-type caster so that the continuous strip of aluminum sheet material form by the belt-type caster moves with the upper and lower continuous loop belt means between the nip between the upper and lower rolls so that the thickness of the continuous strip of aluminum sheet material is reduced.
The cooling system in the preferred embodiment comprises a plurality of rows of high pressure and high velocity cooling water spray means each of which extends across the width of each belt and which rows are spaced apart in the direction of movement of the belt means. Low pressure plenum means are located between adjacent rows of the high pressure and high velocity cooling water spray means. Each row of the high pressure and high velocity cooling water spray means is mounted for linear movement toward and away from an associated belt means. A low pressure plenum removes the heated water with means being provided to control the rate of heated water removed out of the low pressure plenum means to create a vacuum on the associated one of the continuous loop belt means. This allows for maximum heat extraction and helps the continuous loop belt means to conform to the profile of the rows of high pressure and high velocity cooling water sprays defining a mold cavity and to reduce water leakage. Also, hydrostatic means provide bearing surfaces on the arcuate guide means and which hydrostatic means may include steam to preheat the upper and lower continuous loop belt means. In addition to the foregoing, the preferred embodiment has means associated with the upper and lower continuous loop belt means and the dam means to compensate for the shrinkage of the molten aluminum material as it cools, during passage through the straight portions.
It is an object of this invention to provide a belt-type caster with moving upper and lower continuous loop belt means cooperating with moving side dam means to form a rectangular cavity in combination with cooling means for the upper and lower continuous loop belt means adjacent to the rectangular cavity so as to convert a continuous supply of molten aluminum material fed between the upper and lower continuous loop belt means into a continuous strip of aluminum sheet material during passage through the rectangular cavity.
It is another object of this invention to provide a combination of a belt-type caster and a roll-type caster wherein the continuous loop belt means of the belt-type casters are driven by the rollers of the roll-type caster so that the continuous strip of aluminum sheet material formed by the belt-type caster is immediately fed into the nip between the rollers of the roll-type caster to be reduced in thickness.
Other objects and advantages of the invention will be apparent from the following more particular description of the preferred embodiments as illustrated in the accompanying drawings in which like reference characters refer to the same part throughout the various views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic, side elevational view of the apparatus of the present invention showing a portion of a conventional roll-type horizontal caster apparatus in combination with a belt-type caster apparatus;
FIG. 2 is a partial, cross-sectional view taken along line 2--2 in FIG. 1;
FIG. 3 is a partial top plan, view with parts in section of the dam means;
FIG. 4 is an enlarged, partial cross-sectional view illustrating the arcuate guide means and the cooling means; and
FIG. 5 is an enlarged partial view of alignment means for guide means shown in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
In general, as shown in FIG. 1, the invention comprises a pair of continuous loop steel belt means 20, 22 having front end portions 24, 26 mounted on and driven by a pair of roll means 28, 30 of a conventional roll-type caster. Rear end belt portions 32, 34 are supported by semi-circular guide means 36, 38. Outer intermediate belt portions 40, 42 extend inwardly and rearwardly between roll means 28, 30 and guide shoe means 36, 38. Inner intermediate elongated straight portions 44, 46 extend forwardly between guide means 36, 38 and roll means 28, 30 in spaced, generally parallel relationship to define an elongated cavity 48 of rectangular, cross-sectional configuration therebetween. As explained below, the cavity 48 will have a slight taper with the smallest portion adjacent to the rolls 28 and 30.
Dam means 50, 52 are located on opposite sides of the cavity 48 for confining the molten material therebetween. The dam means comprises a plurality of individual short length dam members 54, 55, 56, 58, etc., FIG. 1 mounted on a continuous loop chain means 60 for movement about sprocket means 62, 64 to provide an innermost intermediate length portion 66, FIG. 3, extending approximately between the vertical axes of rotation of sprocket means 62, 64, along which adjacent ones of the individual dam members 68, 70, 72, FIG. 3 are held in abutting side-by-side relationship to form a continuous side surface dam means 74 extending along a forming area 76, FIG. 1. The individual dam members 68, 70, 72 are in contact with the upper and lower straight belt portions 44 and 46 during movement through the distance defined by the forming area portion 76 of the elongated cavity 48. Lower belt means 22 is driven by drive roll means 30 in a fixed path. Upper roll means 28 is driven by the lower roll means 30 so as to drive the upper belt means 20. The central axis 80 of the upper roll means 28 provides a pivot axis whereby the upper belt means 20 and associated apparatus including guide means 36 may be upwardly and downwardly pivotally displaced relative to the lower belt means 22 between a lowermost operating position shown by solid lines in FIG. 1 and an uppermost non-operating position shown by dotted lines in FIG. 1. Guide and support means 82 in the form of an arcuate track and roller means are provided in concentric relationship to pivot 80. Guide means 36, 38 are mounted on slidably movable support structure means 84 connected to pivotally mounted cylinder means 88, 90 for causing movement of the guide means between a non-tension and a tension position whereby the tension in the belt means may be varied.
Cooling means 92, 94 are associated with the inner surfaces 93, 95, FIG. 2, of each of the belt means in the forming area 76. Each of the cooling means comprises a high pressure plenum means 96 having a coolant inlet chamber 97 for receiving cooling water at relatively high pressures (e.g. 20 to 40 psi), a plurality of individual rectangular-shape conduit (channel) means such as 98, 100, 102, etc., FIGS. 2 and 4, for enabling flow of water from high pressure plenum means 96 to the inner surface of the belt means and across the belt surface with return of heated water through return conduit (channel) means 104, 106, 108, etc. to low pressure water plenum means 110, having a coolant outlet chamber 118, FIG. 2, and then to exhaust conduit means 112, 114, 116, etc.
The cooling means is divided into the high pressure plenum 96 and the low pressure plenum 110 by a rectangular-shape plate 120 having a plurality of transverse slots 122 formed therein. As illustrated in the drawings, the high pressure plenum and the low pressure plenum extend across the width of the belt and for substantially the complete length of the forming area 76. The individual conduit means 98, 100 and 102 are mounted in the slots 122 for linear sliding movement toward and away from an associated continuous loop belt means 20 and 22. Sealing gaskets 124 are seated in grooves 126 to form a seal between the individual conduit means 98, 100 and 102 and the plate 120. Each of the individual conduit means 98, 100 and 102 comprises a generally rectangularly shaped member 127 having longitudinally spaced parallel side walls 128 and transversely spaced parallel opposite end walls 130 with an open end 132 of a central rectangular passage 133 in fluid communication with the chamber 97 of high pressure plenum 96. A bar 134, extends across passage 133 and is secured in a fluid tight relationship to the inner surfaces of the side walls 128 and end walls 130. The bar 134 is provided with a plurality of transversely spaced nozzle-type apertures 136 and the bar is spaced a predetermined distance from the other open end 137 of the side walls 128 and end walls 130 and located adjacent to an associated continuous loop belt means 20 or 22. An edge flange 138 secured to each side of the upper end of the side walls 128 and end walls 130 limits the linear movement of the member 127 toward the continuous loop belt means 20 or 22. A plurality of laterally spaced cross openings 140 are provided in the side walls 128 adjacent to the edge surfaces 142 thereof to provide for passageways through which water flowing through the apertures 136, as described below, may escape into return channel means 104, 106, 108 and return plenum chambers 118.
The low pressure plenum means 110 comprises a pair of opposed side walls 144 extending along the side edge portions of the belt means and end walls 146 secured to the surface 148 of the support plate 120. A plate 150 is secured to the side walls 144 and end walls 146 so that an outer surface 152 thereof is adjacent to the side edge portions of an associated continuous loop belt means 20 or 22. The plate 150 each side of the belt means is provided with a plurality of slots 153 having a chamferred bottom surface 155 for slidably receiving and supporting the bottom side surfaces 157 of the sidewalls 128 and the end walls 130. This holds the members 127 in position. The plate 150 is provided with a plurality of openings 154 FIGS. 2 and 4, beneath and between inlet channel means 127 so that a portion of the cooling water flowing out of the orifices 136 onto the associated continuous loop belt means 20 or 22 will absorb heat from the molten material and pass laterally outwardly through the side edge openings 154 into the low pressure plenum 110. A plurality of exhaust conduits, such as 112, 114 and 116 are connected to the side wall 144 and are connected at their ends (not shown) to suitable pump means so as to draw the water from the low pressure plenum means 110. In this way, the heated water is induced to flow through channels 104, 106, 108 and the openings 154 into the low pressure plenum means 110. The pump means function at a rate sufficient to create a vacuum so that the continuous loop belt means 20 and 22 are urged toward the adjacent side surfaces of the slab of metallic material 155, FIG. 2, by edges 142 of the members 127 because of the pressure differential between the relatively high pressure inlet coolant acting against members 127 and the relatively low pressure outlet coolant while the coolant is rapidly removed without significant leakage because of the low pressure condition. As illustrated in FIG. 2, the upper and lower plates 150 are provided with sealing gaskets 156 which function to keep the coolant water confined between the chambers 118 and the associated continuous loop belt means 20 or 22.
The dam means is illustrated more specifically in FIGS. 2 and 3 wherein each of the individual dam members 68, 70, 72 comprise an upper L-shaped member 158 and a lower L-shaped member 160. Adjacent to the edges 162 and 164, the L-shaped members 158 and 160 are provided with a pair of spaced apart openings 166 and 168 which receive rods 170 associated with the links 172 of the continuous loop chain means 60. This mounting of the L-shaped members 158 and 160 functions to keep the individual dam members 68, 70, 72 in side-by-side abutting relationship as they move through the forming area 76. An upper rotatable cam follower 174 and a lower rotatable cam follower are mounted on the opposite ends of each rod 170 for a purpose to be described below.
A support block 176 is located between the upper L-shaped member 158 and the lower L-shaped member 160 and is located to provided supporting surfaces 177 for the edge portions of the continuous loop belt means 20 and 22 engaging the side surfaces of members 158, 160 to ensure sealing engagement of the continuous loop belt means and the sealing gaskets 156. Each support block 176 is provided with a generally cylindrical opening 178 in which is located a pin 180 which is mounted for reciprocal movement in the cylindrical opening 178 and is normally urged outwardly by spring means 182. A shoulder 184 on each pin 180 retains the pin 180 in the cylindrical opening 178. The upper continuous loop belt means 20 is provided with a plurality of openings 186 adjacent the opposite side edges 187 thereof. Although only one side of the apparatus is illustrated in FIGS. 2 and 3, it is understood that the opposite side of the continuous loop belt means 20 is provided with similar structures and functions as described in relation to FIGS. 2 and 3. The openings 186 are spaced at locations so that as the continuous loop belt means moves around the arcuate guide 32, the pins 180 move through the openings 186 and remain therein during passage of the continuous loop belt means through the forming area 76.
A cooperating pair of upper cam blocks 188 and 190 are mounted on the side wall 144 of the upper chamber 118 and a cooperating pair of lower cam blocks 192 and 194 are mounted on the side wall 144 of the upper and lower chamber 118. The upper cam blocks 188 and 190 are slidably adjustable relative to each other so as to move the bearing surface 196, FIG. 3, of the cam block 190 toward or away from the side wall 144 of the upper chamber 118. Similarly, the lower cam blocks 192 and 194 are slidably adjustable relative to each other so as to move the bearing surface 198 of the cam block 194 toward or away from the side wall 144 of the lower chamber 118. As illustrated in FIG. 3, the leading and trailing portions 195, 197 of the bearing surface 196 are inclined. Although not shown, the bearing surface 198 is similarly structured. The cam blocks 188 and 190 and 192 and 194 function to apply outwardly directed forces to the edges of upper continuous loop belt means 20 as as to insure that there are no buckles in the upper continuous loop belt means 20 as it is moved into contact and travels along with the molten material. This is to ensure intimate flat surface belt contact with the molten material. Thus, after the pins 180 have moved through the openings 186, the cam followers 174 contact the inclined lead end portions 195 of the bearing surfaces 196 and 198. The upper cam blocks 188 and 190 and the lower cam blocks 192 and 194 have been adjusted to space the bearing surfaces 196 and 198 a distance from the associated side wall 144 so that, when the cam followers 174 are in contact with the bearing surfaces 196 and 198, sufficient force is being applied to the upper continuous loop belt means 20 so as to stretch the continuous loop belt means 20 so that there are no buckles therein. A wheel 200 FIGS. 1 & 3, with a horizontal axis of rotation is rotatably mounted at a location spaced a short distance from the end of the cam block 188. The outer surface 202 of the wheel 200 is located so as to contact each pin 180 and move it downwardly so as to disengage each pin 180 from its associated opening 186.
The lip portion 204, FIG. 2, on the flexible cantilevered end portion of the upper L-shaped member 158 is nested within the lip portion 206 on the flexible cantilevered end portion of the lower L-shaped member 160 so that the outer surface of each lip portion 206 is in contact with the side edge surface of the molten material. The lip portions 204 and 206 are dimensioned so as to permit limited relative movement of the upper L-shaped member 158 and the lower L-shaped member 160 toward each other. This structure cooperates with the upper and lower continuous loop belt means 20 and 22, as described below, to accommodate for the shrinkage of the molten material as it is cooled during passage through the forming area 76.
As described above, the upper and lower continuous loop belt means 20 and 22 are driven by conventional drive means associated with the upper and lower rolls 28 and 30 and the rear end portions 32 and 24 are supported by semi-circular guide means 36 and 38. The upper guide means 36 is illustrated in FIG. 4 and comprises a hollow member 208 having concentric outer and inner walls 210 and 212 closed by appropriate end walls 214. The outer wall 210 is provided with a plurality of openings 216 which are spaced apart across the width of the hollow member 208 and along the length thereof in the direction of movement of the continuous loop belt means 20. The openings 216 are associated with tapered recesses 218 in the outer surface of the outer wall 210. Sealing means (not shown) are provided along each outer edge of the outer wall 210 so as to provide a seal between the continuous loop belt means 20 and the outer wall 210. Steam is fed into the hollow member 208 and moves through the openings 216 and recesses 218 to provide a low friction hydrostatic bearing surface for the continuous loop belt means 20 and to raise the temperature of the continuous loop belt means 20 prior to its contact with the molten material as described below. While only the upper continuous loop belt means 20 and the associated structures have been discussed, it is understood that similar structures are associated throughout relative to the lower continuous loop belt means 22.
In FIG. 1, there is illustrated a belt welding fixture 220 comprising two adjacent members 222 and 224 each of which have means for holding an end of the continuous loop belt means 20 in a fixed location so that the ends of the continuous loop belt means 20 are positioned relative to each other so that they may be welded together. After the weld has been completed, the same fixture is used to finish grind the weld. The members 222 and 224 are supported by beams 226 and 228 which are secured to a slidable support means 230 which are operatively connected to a piston 232 by clevis means 234. The piston 232 moves in and out of a hydraulic cylinder 88 which is secured to a fixed support 236. The guide means 36 is connected to the slidable support means 230 so that movement of the piston 232 out of the hydraulic cylinder 88 moves the guide means 36 to apply tension to the upper continuous loop belt means 20. As illustrated in FIG. 5, a plurality of adjusting screws 238 on a bracket 239 are used to adjust the alignment of the guide means 36 with the continuous loop belt means 20. As stated above, similar structures are associated with the lower continuous belt means 22.
The operation will be described generally with the apparatus in assembled relationship and the various moving parts in operational relationship. That is, the continuous loop belt means 20 and 22 have been welded together and aligned, the rolls 28 and 30 are rotating to drive the continuous loop belt means 20 and 22, water is being supplied to the high pressure plenum 96 and being withdrawn through the low pressure plenum 110 and the bearing surfaces 196 and 198 have been located to place the proper tension across the width of the upper continuous loop belt means 20. Steam is being fed into the hollow member 208 to form a hydrostatic bearing surface for the continuous loop belt means 20 and to heat such belt means 20 prior to its movement into contact with the molten material.
Molten material 25, such as aluminum, is fed into the forming area between the upper and lower continuous loop belt means 20 and 22 as they reach adjacent portions of the upper and lower arcuate guide means 36, 38 in a conventional manner. Then, upper and lower opposite surfaces of the continuous loop belt means 20 and 22 move into engagement with the upper and lower surfaces of the individual dam members 68, 70 and 72. The spring-urged piston 180 projecting from each individual dam member enters into an associated opening 186 in the upper continuous loop belt means 20 so that the dam means moves with and is driven by the upper continuous loop belt means 20. The dam members are moved outwardly by cam followers 174 in engagement with the bearing surfaces 196 and 198 so that the proper tension is placed across the width of the upper continuous loop belt means to remove any buckles therefrom. The pressure of the cooling water in the high pressure plenum is controlled so that the pressure on the bars 134 is in an amount to exert the desired pressure on the continuous loop belt means 20 and 25 so as to control the thickness of the molten aluminum located in the cavity formed by the upper and lower continuous belt means 20 and 22 and the dam members 68, 70, 72 and 74. Also, the rate at which the heated water withdrawn from the low pressure plenum 110 by the pump means is controlled so as to create a slight vacuum to assist in creating a sufficient pressure differential to hold the continuous loop belt means 20 and 22 in a desired continuous surface contacting relationship with the upper and lower slab surfaces by force exerted through the members 127 and so that the cooling water passing through the apertures 136 moves into contact with the adjacent surfaces of the continuous loop belt means 20 and 22 at relatively high velocity and is removed in a most efficient manner to effect cooling of the molten aluminum material. The pressure on the water in the high pressure plenum 96 is sufficient to move the water through the apertures 136 by a venturi effect at a relatively high velocity. It is understood that metals other than aluminum may be processed with the apparatus of this invention.
During passage of the molten material through the elongated forming area 76, the surfaces of the molten aluminum material are continually cooled by cooling water discharged under high pressure jet conditions across the entire inner surfaces of the continuous loop belt means. As the molten material cools there is some shrinkage so that the thickness of the material gradually decreases. The controlled pressures of the high pressure plenum 96 and the low pressure plenum 110 function to move the upper continuous belt means 20 and the lower continuous belt means 22 relative to each other to accommodate this shrinkage and keep the upper and lower continuous loop belt means 20 and 22 in contact with the associated surfaces of the aluminum. Since the weight of the slab material is usually sufficient to keep the lower surface of the material in full contact with the upper surface of the lower belt means, the apparatus may be constructed and arranged to only force the upper belt means downwardly toward the lower belt means to provide the aforedescribed relative movement between the belt means. Also, as described above, the L-shaped members 158 and 160 are also permitted to move toward each other to accommodate this shrinkage. As the individual dam means reach the end of the forming area 76, the wheel 200 contacts and depresses the piston 180 so that the upper continuous loop belt means 20 is disengaged from the individual dam members. The formed continuous strip of aluminum sheet material leaves the forming area 76 of the belt means caster and moves with the continuous loop belt 20 and 22 toward the rolls 28 and 30. If necessary, lubricating wick means 240 and 242 are provided to lubricate the upper and lower of surfaces of the continuous strip of aluminum just prior to entering the nip area between roll means 28, 30 whereat the thickness of the hot continuous strip of aluminum sheet material is reduced by a suitable amount by a hot rolling pressure and then discharged for further processing in a conventional manner. The temperature of any lubricating means must be such that the temperature of the strip is not cooled below the rolling temperature.
In the preferred embodiment of the invention, the continuous strip of aluminum leaving the forming area 76 has a width of about 60 inches and a thickness of about 0.280 inches. To obtain this, molten aluminum material is deposited between the upper and lower continuous loop belt means 20 and 22 at the rate of about 300 to 500 lbs./min. and at a temperature of about 1100 to 1200 degrees F. The width between opposed individual dam members at the beginning of the forming area is about 63 inches and the distance between the upper and lower continuous loop belt means 20 and 22 at the beginning of the forming area 76 is about 0.410 inches. The continuous loop belt means 20 and 22 move at a rate of about 12 ft./min. The pressure of the cooling water in the high pressure plenum is about 20 psi and the velocity of the water as it exits the apertures 136 is about 0.08 cu.ft/min./aperture. The pump means extracts heated water from the low pressure plenum at a rate to have a pressure of about 1 to 5 psi below atmospheric on the associated continuous loop belt means 20 and 22 to facilitate rapid removal of water without significant leakage along the edges of the belt means. The continuous strip of aluminum is fed into the nip between the rolls 28 and 30 and exits therefrom at a thickness of about 0.280 inches and at the rate of about 17.5 ft/min. At these flow rates the mold cavity can be around 9 inches long. The strip should be above 900 degrees F. at the entry to the rolls.
The illustrative embodiment of the invention may be variously modified for adaption to various apparatus and conditions of operation to achieve various results. Some of the features of this invention are alternative and may be selectively utilized only as necessary or desirable for under particular circumstances and conditions. Thus, it is intended that the appended claims be construed to include various alternative and modified constructions and arrangements except insofar as limited by the prior art.
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Apparatus for continuously forming a continuous strip of aluminum sheet material using a belt caster for forming a continuous strip of aluminum sheet material and a roll caster for immediately reducing the thickness of the continuous strip of aluminum sheet material wherein the continuous loop belt means used in the belt caster are driven by the rolls of said roll caster.
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BACKGROUND
Bicycles are a popular and efficient form of transportation, with a long history of invention and improvement. Many communities are developing an ever-growing matrix of bike paths, encouraging people to ride a bike to work as a way to both improve health and lower greenhouse gas generation. As bike riding has become more popular, so too has physical training and conditioning to improve one's bike riding performance. There are many products now available to measure a rider's performance, intended to provide motivation to perform better and/or improve conditioning, which may lead to better performance. There are many bike riding accessories and improvements in equipment to provide somewhat better performance. In some cases such equipment may not be permitted during competition but are used by riders to improve their performance when not using the equipment. Such equipment may be of interest to those that do not compete simply to improve their experience, perhaps enabling them to ride farther or faster than they otherwise may be able to do.
SUMMARY
A system for improving a person's pedaling efficiency is disclosed herein. The system couples rotation of a person's foot connected with a pedal on a human-powered vehicle with rotation of a corresponding thigh. When torque is applied by the foot with a plantar flexion, the system transfers the torque to a corresponding thigh. This results in hip extension, thereby adding force to assist in pushing the pedal downward. The system is a passive mechanical linkage, with all power provided by the legs of the rider.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate exemplary aspects of the invention, and, together with the general description given above and the detailed description given below, serve to explain features of the invention.
FIG. 1 is a perspective view of the system components.
FIG. 2 is a perspective view of the system as worn by a person.
FIG. 3 is a side view of the system on a person's leg with the hip flexed, knee bent, and foot parallel to the thigh.
FIG. 4 is a side view of the system on a person's leg with the hip, knee, and toes extended.
FIG. 5 is a side view of the system on a person's leg when in a standing position.
FIG. 6 relates geometric relationships between the various structural members of the disclosed system.
FIG. 7 is a view of the system as worn by a person riding a bicycle.
FIG. 8 is a detailed view of an optional shoe, adapted to cooperate with the system.
DETAILED DESCRIPTION
The various embodiments will be described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. References made to particular examples and implementations are for illustrative purposes, and are not intended to limit the scope of the invention or the claims.
To make the disclosure more clear, references relative to “left” or “right” are interchangeable. Also, elements that are referenced on one side of the system will carry the same reference number as the same element on the other side of the system. The plural may apply to the singular, and the singular may apply to the plural in all references and in the description.
The instant invention may be beneficial when used while operating any pedal-powered apparatus. Examples include rickshaws, basic electricity generators, pumps (such as emergency pumps), and of course bicycles providing for any number of riders.
FIG. 1 is a perspective drawing of the components comprising a system 100 . The system 100 comprises outer thigh linkages 102 , connected to a body harness 104 by hinged connectors 105 . The connectors 105 may allow rotation of the outer thigh linkages 102 relative to the body harness 104 . Cables 115 , 116 , sometimes collectively denominated as a “coupler”, connect outer thigh linkages 102 to shoes 112 . The coupler comprises one or two wires 115 , 116 .
An upper thigh brace 120 and a lower thigh brace 125 are connected to the outer thigh linkages 102 on the braces' 120 , 125 outside ends and inner thigh linkages 130 at the braces' 120 , 125 inner edges. Optionally, the thigh braces 120 , 125 may also be connected with each other by top connectors 135 . Straps 108 connecting the outer thigh linkages 102 to the inner thigh linkages 130 complete an encircling attachment, thereby capturing a rider's thigh 107 ( FIG. 2 ). A strap 140 , connected to the hinges 105 , may go under a rider's buttocks to secure the body harness 104 . In some embodiments only a single coupler ( 115 or 116 ) is provided, though providing both may provide better stability to the rider's foot and prevent rotation of the linkages 102 , 130 and thigh braces 120 , 125 about the longitudinal axis of the thigh 107 .
Looking to FIG. 2 , we see a perspective drawing of the system 100 as worn by a person 101 . In some embodiments the outer thigh linkages 102 extend past the wearer's knees, thereby providing clearance for the couplers 115 , 116 . In some embodiments pads 127 may be placed underneath the uppermost thigh braces 120 for comfort.
FIG. 2 further illustrates couplers 115 , 116 connecting the outer thigh linkages 102 and 130 to shoes 112 worn by a rider. A plate 122 under the rider's shoe 112 connects to the coupler 115 , 116 and thereby to the outer thigh linkages 102 . The plate 122 may be rigid, for example comprised of metal, or flexible.
FIG. 3 and FIG. 4 show an example of operation of the system. FIG. 3 is a side view of the system 100 attached to a rider's leg 107 while the hip is flexed. As viewed from the side, the system approximates a two-dimensional four-bar linkage or pantograph. The shoe 112 and outer thigh linkage 102 provide the rotating cranks. The shin 119 and coupler 115 , 116 provide the couplings, whereby movement of the shoe 112 causes rotation of the outer thigh linkage 102 .
FIG. 4 is a side view of the system 100 with the wearer's leg extended and the shoe 112 rotated with the toe downward, as may occur while pedaling a bicycle. Note that the shoe 112 and outer thigh linkage 102 may be rotated together in the plane of motion. The outer thigh linkage 102 is connected to the body harness 104 at the hip, such that the thigh 107 and outer thigh linkage 102 have a common axis of rotation.
FIG. 5 is a side view of the system 100 attached to a wearer's leg wherein the wearer is in a standing position. The coupler 115 , 116 is slack, thereby permitting a comfortable standing position. The standing position might be difficult if the coupler 115 , 116 were instead rigid.
FIG. 5 also illustrates the coupler 115 , 116 flexing to allow plantar extension (the shoe 112 approximately orthogonal to the longitudinal axis of the leg) while the hip is extended (the outer thigh linkage 102 nearly vertical). The flexible coupler 115 , 116 allows a bicycle rider to raise his toes to avoid small obstacles on the ground. This feature may be useful when the bicycle is leaning to one side for turning, since one pedal would be closer to the ground than the other.
FIG. 6 is a side view of the system 100 attached to one leg, illustrating lengths and adjustments of the various elements. Length 124 is the distance between the knee and coupler 115 , 116 . Length 125 is the distance between the ankle and coupler 115 , 116 . The relative rotation of the shoe 112 and the outer thigh linkage 102 depends on the ratio of length 124 to length 125 . Length 124 may be adjusted by attaching the coupler 115 , 116 to different points on the outer thigh linkage 102 . Length 125 may be adjusted by attaching the coupler 115 , 116 to different points on the shoe 112 .
Length 126 is the distance between a wearer's knee and ankle. Length 127 is the length of the coupler 115 , 116 . Length 126 and length 127 may be approximately equal, such that the ankle is extended when the hip is flexed. The length of the coupler 115 , 116 may be adjusted to provide an offset between ankle rotation and hip rotation.
Length 128 is the distance between the person's waist and the thigh linkage connector 105 . Length 128 aligns the outer thigh linkage 102 with the thigh, such that the thigh linkage and thigh are aligned, and move together comfortably. Length 128 may be adjusted to match the size and shape of the wearer.
FIG. 7 shows the system 100 on a bicyclist with a shoe 112 on a pedal 123 . The pedal 123 is approximately below the ankle. The coupler 115 , 116 connects to the shoe 112 near the ball of the foot, forward of the pedal 123 . Standard bicycle shoes typically place a pedal cleat under the ball of the foot. System performance is enhanced with the shoe 112 positioned relative to the pedal 123 as shown in FIG. 7 .
Bicycle riders may need to become accustomed to the new shoe position shown in FIG. 7 . For training purposes, a shoe could allow a range of pedal placement. Beginners could start with a standard pedal placement, and gradually adjust to the pedal position shown in FIG. 7 .
Looking now to FIG. 8 , a novel shoe 112 is shown in greater detail. In some embodiments a rider wears regular riding shoes with the plate 122 positioned under the ball of the foot. The coupler 115 , 116 may connect to the plate 122 directly or through hinges 121 . In some embodiments a novel shoe is worn, wherein the sole of the novel shoe includes a clipless connector 124 approximating the position of the ball of the foot with channels running front to back, and the plate 122 has fasteners 123 connected with the clipless connector 124 to rigidly connect the plate 122 to the connector 124 , and thereby to the shoe 112 . The connector 124 channel may be extended in the longitudinal direction of the foot, thereby providing the wearer the ability to increase of decrease the length of the moment arm between the plate 122 and a rider's ankle. The rigid plate 122 reinforces the shoe 112 to prevent bending under load. The shoe 112 may also include a cleat 126 for rigid attachment to a pedal 123 ( FIG. 7 ) on the bike. In some embodiments the cleat 126 is adjustable, to allow positioning to accommodate different pedaling styles and foot positions.
The connector 124 allows positioning of the plate 122 to accommodate different pedaling styles and foot positions. The connector 124 allows the plate 122 to be replaced with a standard clipless pedal cleat, giving the user the option of riding with the rigid plate 122 and the system 100 , or a clipless pedal cleat without the system 100 . That is, the shoe 112 is useful both with and without the other elements of system 100 .
The preceding description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the following claims and the principles and novel features disclosed herein.
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A system comprising structures connected to the rider of human-powered vehicles improves the force a rider may apply to the vehicle. The elements are primarily connected to the lower body and legs of the rider, with attachment to the rider's shoes, whereby a two-dimensional four-bar linkage is formed. Use of the system may permit a rider to go faster or farther with less effort. An optional novel shoe may be used with or without the other elements of the system.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an apparatus for regulating the traveling speed of a motor vehicle, comprising a regulator whose control unit is in operative connection with an element controlling the ratio of the fuel-air mixture fed to the vehicle engine, especially the throttle valve, and has means for deactivating the regulator when the foot brake is applied including a switch turning on the brake or stop light, and is provided with a safety circuit operative to deactivate the regulator in the event the switch turning on the stop light, and thus switching off the regulating device, fails to function.
2. Prior Art
With relation to an automatic speed regulating system, it is already known that when a switch turning on the stop light and also switching off the regulating device fails to function, a blocking circuit is provided that responds to a prespecified speed change and thereupon switches off the regulating device (DE-OS No. 20 06 367). Such safety circuits, however, entail the disadvantage that at the failure of the stop light switch, the regulating device acts at least momentarily against the effect of the brake. This may lead, especially with high-powered vehicles, to dangerous situations. The known disadvantages cannot be eliminated by the provision of particularly closely tolerated switch thresholds, since the regulating device otherwise would be needlessly switched off at small irregularities of the travel speed.
SUMMARY OF THE INVENTION
A principal object of the invention is, therefore, to provide a better and more reliable safety circuit which supplements an existing regulating device without substantial structural change and expense. Particularly, the device is to operate without additional and independent transmitters.
This object is achieved, in a device of the foregoing type, by modification of a regulating device which is disabled by a threshold value switch when a prespecified vehicle deceleration brought about by the foot brake is exceeded.
A special advantage of the invention consists in that the acceleration threshold, which is independent of the speed, can be adjusted to closer tolerances, so that the regulator can also be released by the actuation of the hand brake. The latter fact is particularly advantageous in the event of a failure of the foot brake circuit. Moreover, such an embodiment does not operate as sluggishly as the known solutions, which means that the regulating device cannot cause the engine to counteract the brake.
A particularly advantageous development of the invention consists in the switching-off device being also connected to a speed-independent electric signal that is provided for the adjustment of other operations since such signals are present anyway and can be utilized along with the aforementioned function.
A particularly reliable advantageous development of the invention consists of a threshold value switch with a switch threshold for switching off the regulating device when a vehicle deceleration of one meter per second square is being exceeded, since the effect of travel path changes, according to experience, remains below this threshold.
A further advantageous development of the invention consists in that the threshold value switch has further, more closely limited switch thresholds for the actuation of further safety devices, so that the signal of the threshold value switch can also be utilized for other systems, e.g., the blocking device of the safety belts.
A special advantage of the invention consists also in the fact that the switching-off device is independent of other switching-off systems which respond to a change in the number of revolutions or in the power of the engine. Other safety systems may remain and are effectively supplemented by the new circuit without having to replace them.
A particularly advantageous development of the invention is seen in the fact that the switching-off device consists of a sum-and-difference amplifier, to whose first input is applied a speed-dependent signal, and to whose second input is applied an electric signal dimensionable by means of a voltage divider chain, and whose output signal is fed via a condenser to a switching-off disconnect or memory. A particularly reliable switching-off or disconnect memory acts in this structure directly upon the current supply of the regulating device and prevents, by the storing of the switching-off signal, an immediate erroneous re-switching on.
BRIEF DESCRIPTION OF THE DRAWINGS
Further developments of the invention are explained in greater detail with the aid of the embodiments shown diagrammatically in the single FIGURE of the drawing, by way of example.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The regulating device shown is combined in block 1 to which a speed signal is fed via a line 2 from a vehicle speed signal generator 11. The operation of regulating device 1 is controllable from an operating unit 3 in which five switching positions are shown. The switching arm 4 of the control unit, which in this case is constructed as a rotary switch, is in position R wherein the speed prevailing at the instant concerned is stored in regulating device 1, which functions to minimize deviation in vehicle speed from the regulated speed by supply of an error signal to an engine throttle control device 12.
From operating unit 3 the regulated speed can also be manually decreased in position "-", and increased in position "+". It is also known to provide a position "WA" wherein the vehicle speed is by regulation increased or decreased to a stored value which, for technical reasons relating to traveling, could temporarily not be maintained. Finally, it is possible to switch off the entire apparatus by means of the operating unit in position O.
The regulating device is also to be switched off when the operating unit is in the position R shown for that instant, and the driver applies the foot brake 13 or the hand brake, or when a particularly abrupt change in the travel path occurs.
The mode of operation of the stop light switch cooperating with the foot brake, for switching off a regulating device is well known in the prior art as disclosed for example in U.S. Pat. No. 4,084,659. Where the stop light switch fails to function in such prior art systems, the regulating device 1 is switched off through a threshold value switch 6 and the memory 7 when a specific speed threshold is exceeded, as a function of a set rated speed. Such thresholds are established in known devices in the range of 15 kilometers per hour. On account of the known disadvantages of such a safety circuit, namely: dependency on the direction; inaccuracy; and sluggishness (inertia) with a chance of undesired counterregulation, the regulating device in accordance with the present invention provided with a switching-off device depending on vehicle acceleration (or deceleration). A speed signal of the vehicle is for this purpose transformed into an acceleration signal by means of a differentiator 5, which acceleration signal acts via the threshold value switch 6 upon the switching-off memory 7. In the threshold value switch 6 an acceleration threshold is prespecified, preferably within the range of one meter per second square, beyond which the switching-off memory 7 switches off the current supply 8 of the regulating device 1. Of course, the switching-off memory 7 can also deactivate regulating device 1 in another manner, e.g. by resetting the operating unit to position O. Switching-off memory 7 after switching off operation, also prevents switch-on of the regulator, for safety reasons, for a prespecified period of time.
A particularly simple development of the acceleration-dependent switching off by means of the threshold value switch 6 is set by means of sum-and-difference amplifier 9 and a condenser 10 connected thereto. The operation range of sum-and-difference amplifier 9 is adjusted with respect to the speed signal arriving in line 2, by means of a voltage divider circuit including resistors 14, 15 and 16 establishing a reference signal at one of the inputs of amplifier 9 for comparison with the acceleration dependent signal applied to the other amplifier input as shown.
The acceleration-dependent threshold can, in contrast to the speed-dependent threshold, be much more closely limited since, as a function of time, it switches also for particularly short periods, so that regulating device 1 has no longer any chance of having the engine operate possibly against the effect of the brake, and therefore can also respond to a delay by the application of the hand brake. Of course, the new safety circuit device may also be provided in addition to other safety devices, so that existing regulating devices can continue to be utilized and can be easily supplemented by the structural elements necessary for carrying out the invention. Finally, the general desire of securing a technical device in a multiplicity of ways can thereby be complied with.
A particular advantage consists in that the rated speed is no longer the reference value but an acceleration value suitably associated with the speed prevailing at the instant concerned.
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An apparatus for regulating the traveling speed of a motor vehicle has a regulating device connected to control the fuel-air mixture supplied to the vehicle engine, with a safety circuit including a switching-off device responsive to a prespecified deceleration of the vehicle to deactuate the regulating device.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus for reducing the vibrations of periscopes and other vessel devices which extend into a liquid medium when in use. More specifically, the present invention relates to an apparatus for reducing the vibrations of submarine's periscopes and other extended-in-use vessel devices, by means of a damping arrangement, wherein the vibrations are induced by the relative movement of the submarine or vessel with respect to the liquid medium.
2. Description of the Prior Art
When periscopes or other similar vessel devices, which are extended in use, are moved through water, the devices may have vibrations set up therein which impair that use. These vibrations may also render the use of the devices impossible. One cause of these vibrations has been determined to result from the separation of vortices. Under certain conditions, a Karman vortex path can form. The formation and magnitude of vortices depend upon parameters which may include the diameter of the periscope or tubular device, the approach velocity and the temperature-dependent viscosity of the water. Other factors influencing the formation of vortices include other contemporaneously extended apparatuses and turbulence produced by a submarine's other devices which extend into the water including, for example, turbulence produced by the submarine's conning tower. With increasing velocity of the periscope or other extended-in-use device with respect to the water, the frequency of the vortex will increase. As the natural frequencies, including the fundamental frequency, are approached, resonant vibrations will occur which may impair the functionality of the device. The resonant vibrations will persist as the relative velocity increases beyond that corresponding to the natural frequency. Thus, in the case of a periscope, its functionality will remain impaired over a wide velocity range for which its utilization is required.
Vibrations caused by vortices can be classified according to three general categories, as follows: (1) deflections parallel to the direction of travel; (2) lateral deflections perpendicular to the direction of travel; and (3) deflections intermediate between the directions of parallel to and perpendicular to travel. Lateral vibrations perpendicular to the direction of travel will generally be of a greater magnitude than vibrations parallel to the direction of travel, since the vortices alternately dissipate and reform on each side of the extended-in-use device. For example, for a periscope having an extended free length of about 4.2 meters and traveling at a certain speed, lateral deflections of ±40 mm were observed. The observed lateral deflections correspond to an acceleration of 10 g. Deflections parallel to the direction of travel of ±8 mm were observed. The frequency of the observed vibrations was between 7 and 8 Hz. Vibrations of the periscope, as just described, have a detrimental effect on the periscope optical system whereby accurate observations cannot be attained.
Proposals have already been made for the damping of tall, slender structures, such as smoke stacks or masts, where the vibration is due to wind. Such proposals include German Patent Publications DE-AS No. 28 06 757 and DE-PS No. 32 14 181, which disclose the installation of annular damping weights by means of spring elements or vibration-damping elements close to the top ends of the structures. These proposals are not transferable to periscopes or similar devices on submarines for which the vibrations are produced by the streaming of water and for which special conditions pertaining to submarines must be observed.
A proposal has also previously been made to reduce the vibrations of extendible antenna supports for submarines. In particular, German Patent Publication DE-AS No. 23 17 840 discloses a proposal providing a tubular antenna support with a similarly extendible, streamlined cover. An undesirable aspect of this proposal is that the cover impairs the provision of a rigid seating for the portion of the antenna extending above the tower. Therefore, in this example of background art, an additional provision was made to attach the antenna carrier upper support via a traverse or cross-tie rod to a fixed guide, wherein the traverse is located inside the extendible cover. The traverse moves along the fixed guide as the antenna is extended. Although the streamlined cover can exert a favorable influence on the vortex formation, it cannot prevent the occurrence of vibrations for all conditions encountered in the operation of a submarine. The drawbacks associated with this proposal are the high costs for the extendible cover, the traverse rod and the fixed guide assembly, the low stiffness of the upper support near the traverse, and the elevation of the center of gravity of the submarine resulting from the additional elements.
OBJECTS OF THE INVENTION
It is an object of this invention to provide an apparatus whereby the vibrations which occur in a periscope or other vessel device which is extended into a liquid medium when in use are significantly reduced or prevented.
It is also an object of this invention to provide an apparatus for reducing or preventing vibrations of a periscope or other device which extends from a submarine when in use, wherein the apparatus is of a simple construction whereby the apparatus can be mounted directly onto the periscope or other extended-in-use device.
It is a further object of this invention to provide an apparatus for reducing or preventing vibrations of a periscope or other device which extends from a submarine when in use, wherein the apparatus is of a simple design whereby the apparatus can be mounted as a subsequent addition to the periscope or other extendible device.
It is an additional object of this invention to provide an apparatus mounted on the periscope as described above which allows for the rotation, extension and retraction of the periscope or other extended-in-use device.
SUMMARY OF THE INVENTION
The present invention provides an apparatus for damping vibrations of a periscope or other device that, at least when in use, extends into a body of water from the superstructure of a submarine or other vessel and which accomplishes the aforementioned objects. Said damping apparatus is effective for damping vibrations resulting from vortices created due to movement of the periscope or other device through the water.
The damping apparatus, in essence, comprises a kinetic energy storing means and a potential energy storing means. The damping apparatus, preferably, comprises a damping mass suitably mounted on a periscope or other extended-in-use device in such a way that vibrational deflections of the damped device cause the damping mass to move. In this respect, the damping mass functions as a kinetic energy storing means. Means of mounting the damping mass preferably comprises a plurality of springy elements having elastic properties. The springy elements function as the means for storing potential energy. The springy elements may themselves be lossy, such that, energy transferred between the kinetic energy storing means and the potential energy storing means is dissipated during a transfer therebetween, or another means, such as, a damping oil or a friction pad, may provide the function of dissipating the energy transferred. Preferably, the damping apparatus is mounted at or near an upper end of the periscope. An optimal arrangement is one which provides for mounting the damping apparatus at the periscope's head, wherein the damping mass incorporates any devices which may be located at that position. Proportional to their respective masses, such incorporated devices can effectively function as part of the damping mass.
Other embodiments encompassed by the present invention include designs wherein the damping apparatus is mounted inside the periscope's head or inside an extendible tube which supports the periscope's head at a position immediately below the aforementioned head. Implementation of such embodiments would require considerable changes in the construction of the periscope in view of current designs. Consequently, for periscopes of conventional design, it is preferable to mount the damping apparatus below the periscope's head.
Appropriate means must be provided to support the portion of the periscope or other extended-in-use device which extends above the superstructure of the submarine. A plurality of support means may be employed.
The mass of the damping mass should preferably be between about 0.5% and 10% of the mass of the part of the periscope which extends above its uppermost support. An uppermost support comprising an annular bearing support which can be flush with, or can extend above, the superstructure of the submarine is typically provided. The damping mass is more preferably between about 1% and 5% of the mass of the part of the periscope which extends above its uppermost support and most preferably between about 1% and 3% of that mass.
Critical damping has been found to be an appropriate standard by which to measure the desired level of damping with respect to the present invention. It has been determined that the appropriate level of damping to be obtained is between about 10% and 30%, and preferably about 20%, of the critical damping. Subsequent adjustment of the apparatus to the disclosed damping levels optimizes damping over a frequency range which may include resonant frequencies produced by the damping apparatus itself in addition to the fundamental and natural frequencies of the damped device.
The external dimensions of the damping apparatus are chosen such that the apparatus can be drawn through the uppermost bearing located in the submarine's superstructure. Undesired impact between the damping mass and the periscope tube may occur when the damping apparatus is in an extended position due to radial motion of the damping mass relative to the periscope tube. Such radial motion may be induced by vortices or caused by other external forces. In order to limit this relative motion, bumpers may be provided between the periscope tube and the damping mass. The bumpers are designed to prevent the damping mass from damaging the periscope tube without increasing the diameter of the damping apparatus.
In preferred embodiments, the damping apparatus is of an external shape which minimizes the magnitude of the wake, or other turbulent water flow, which may extend from the water's surface down to the submarine's superstructure, behind the periscope when the submarine is traveling with the periscope in an extended position. Protective sheaths or jackets which surround the damping apparatus have been found to be useful for facilitating the flow of water past the apparatus and minimizing the magnitude of the wake. The protective sheaths or jackets simultaneously serve to protect the damping apparatus from damage. In one embodiment, the protective sheath forms a pressure-tight housing which contains a hydraulic damping medium such as silicone oil. Other damping mediums may also be used. In a second embodiment, the protective sheath contains openings through which ambient water may enter and exit. In this embodiment, the water itself acts as the damping medium.
In a third embodiment for facilitating the flow of water past the damping apparatus and minimizing the magnitude of the wake, the damping mass is rotatably mounted and constructed such that it automatically sets itself in the direction of travel independently of the rotation of the periscope. In descriptive terms, the damping mass can be said to operate like a vane.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a vertical cross-section of a damping apparatus mounted on a periscope wherein the damping apparatus has two attaching rings supporting a damping mass.
FIG. 2 shows a horizontal cross-section of an attaching ring corresponding to the II--II plane of FIG. 1.
FIG. 3 shows a vertical cross-section of a damping apparatus wherein the damping apparatus has one attaching ring supporting a damping mass and wherein damping is aided through the utilization of friction dampers.
FIG. 4 shows an expanded view of the friction damper denoted IV in FIG. 3.
FIG. 5 shows a vertical cross-section of a damping apparatus having a protective sheath which contains openings to facilitate the flow of water.
FIG. 6 shows a vertical cross-section of a damping apparatus having a pressure-tight protective sheath.
FIG. 7 shows a vertical cross-section having a pressure tight protective sheath for holding a liquid damping medium wherein a damping mass contains openings for facilitating flow of the damping medium.
FIG. 8 shows a vertical cross-section of a damping apparatus wherein the apparatus is housed within the periscope tube below the periscope's head.
FIG. 9 shows a vertical cross-section of a damping apparatus having a rotatably mounted damping mass shaped in the form of a vane.
FIG. 10 shows a horizontal cross-section of the damping mass corresponding to the X--X plane of FIG. 9.
FIG. 11 shows a vertical cross-section of a damping apparatus mounted on top of a periscope's head.
FIG. 12 shows a vertical cross-section of a damping apparatus mounted on top of a periscope's head additionally having a supplementary attachment mounted on top of the damping apparatus.
FIG. 13 shows a vertical cross-section of a damping apparatus having helical, metal springs mounted between the periscope tube and the damping mass.
FIG. 14 is a diagram which shows the frequency-dependent behavior of a periscope with a damping apparatus and a periscope without a damping apparatus.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The elements of a damping apparatus according to the present invention essentially comprise a damping mass, means for damping the damping mass, means for attaching the damping means to the damping mass and means for attaching the damping apparatus to a periscope or other extended-in-use vessel device.
Referring to FIG. 1, a conventional periscope is shown having a periscope's head 1 mounted on an upper periscope tube 2 which is of a cylindrical geometry. The upper tube 2 is rotatably connected to a lower periscope tube 12 which has a larger diameter than the upper tube 2. When the periscope is extended, it is rotatably supported by an upper bearing 11 located immediately below the upper surface 13 of a submarine's superstructure or conning tower. The lower tube 12 may optionally pass through additional bearings, not shown. When the periscope is lowered to a fully retracted position, the periscope's head 1 is drawn through the top bearing 11 until the periscope's head 1 lies below the upper surface 13.
Still referring to FIG. 1, a damping apparatus 10 is mounted on the upper periscope tube 2 immediately below the periscope's head 1. The damping apparatus 10 comprises an annular damping mass 3 which is disposed between a lower attaching ring 4 and an upper attaching ring 5 by means of a plurality of springy elements 6 such that the damping mass is movable in any direction perpendicular to the axis, A--A, of the upper tube 2. The springy elements 6 permit limited motion of the damping mass 3 while acting in conjunction with the damping mass 3 to dampen the motion.
The springy elements 6 should be made from a material which is elastic and which exhibits high internal friction upon deformation. Natural and synthetic rubbers are examples of materials found to be suitable for application as springy elements. In other embodiments the springy elements 6 are comprised of a plurality of narrow wire strands wound together to form straight or helical springs, or hydrodynamic damped spring elements may be used. All materials used in connection with the damping device 10 should be corrosion and sea water resistant. A heavy metal, such as a lead alloy, is a preferred material for the damping mass 3. Other suitable substances include stainless steel and special metals such as bronze.
The springy elements 6 are set in recesses in the lower attaching ring 4, upper attaching ring 5 and damping mass 3 and held in place by a suitable securing means. Examples of the securing means include cementing the springy elements 6 in recesses 6a or pressing the springy elements 6 into recesses 6a which have slightly smaller diameters than the springy elements 6. Preferably, the springy elements 6 are cylindrical, have circular cross-sections and extend substantially parallel to the A--A axis of the periscope tube 2. Also preferably, the damping apparatus 10 has at least four (4) springy elements 6. However, in an alternate embodiment, the springy elements 6 could comprise a single springy element 6 which is disposed between the damping mass 3 and the upper periscope tube 2 and which is attached to both by a suitable securing means.
The damping mass 3 and the lower and upper attaching rings 4, 5 each comprises two parts to facilitate mounting and dismounting of the damping apparatus 10 for purposes of installation and maintenance. The two-part construction of an attaching ring 4 is exhibited in FIG. 2. The attaching ring shown comprises two halves held together by screws 14 which also clamp the attaching ring 4 firmly onto the upper tube 2.
Referring back to FIG. 1, below the top bearing 11 is an annular, impact-resistant support 15 which abuts the damping apparatus 10, or a part thereof, when the periscope is in a retracted position. The support 15, which is preferably made from an elastic material, dampens any vibrations of the retracted periscope. The support 15 may optionally be mounted in such a way that it can be swung into position against the damping apparatus 10 when the periscope is in a retracted position.
For all embodiments disclosed herein, the external dimensions of the damping apparatus at all angular positions should be less than the internal diameter of the top bearing 11, so that the damping apparatus can be retracted to a position below the upper surface 13 of the submarine's superstructure.
Referring to FIG. 3, disclosed is a damping apparatus 10 wherein a damping mass 3a is supported from below by a lower attaching ring 4. The damping mass 3a has a distinct top end 3a' and a bottom end 3a". The top end 3a' is conically designed to partially enclose a conically shaped section of the upper periscope tube 2'.
FIG. 3 also discloses a damping apparatus 10 wherein a friction damper 31 substituted for a springy element 6. Referring to the expanded view of the friction damper 31 in FIG. 4, a friction pad 42 is located on the lower attaching ring 4. The friction pad 42 may be made of a polytetrafluoroethylene, such as Teflon, a registered trademark, manufactured by the Dupont Company, or other substance having similar properties. A circular friction shoe 43 is pressed against the friction pad 42 by a pin 44 which is recessed into and perpendicularly extends up from the shoe 43. The pin 44 is recessed in the shoe 43 so as to prevent displacement. The pin 44 is acted on by a pressure spring 45 housed in a recess 46 in the damping mass 3. The pin 44 passes through a hole 47' in an annular plate 47 which covers the recess 46. Referring back to FIG. 3, the springy elements 6 are loaded in a tension-creating manner so as to draw the damping mass 3a toward the attaching ring 4. In addition to damping the movement of the damping mass 3a, the friction dampers 31 limit the damping mass 3a to movement in essentially radial directions. Alternatively, friction dampers which utilize permanent or adjustable magnets rather than helical springs to damp motion between the damping mass 3 and attaching ring 4 may be used.
FIG. 4 additionally discloses bumpers 49 made of thin rubber or leather inserts which are attached to the damping mass 3 next to the upper periscope tube 2. The purpose of the bumpers 49 is to prevent direct contact between the tube 2 and the damping mass 3.
Referring to FIG. 5, disclosed therein is an embodiment of a damping apparatus 10 provided with a divisible, rotation-symmetrical protective sheath 7. A plurality of lower orifices 51 and upper orifices 52 allow water to flow through an interior of the sheath 7'. The water which flows through the interior of the sheath 7' can exert an additional damping effect by dissipating kinetic energy to minimize vibrations, especially when the periscope is in an extended position. In an alternative embodiment wherein the damping apparatus 10 is located immediately below the periscope's head 1, the sheath 7 may be designed such that the lower orifices 51 and upper orifices 52 are located respectively below and above the surface of the water. By providing a means, not shown, for closing the lower orifices 51, the additional damping effect due to the water may be controlled. For example, a higher damping effect and a low fundamental frequency would be obtained when the sheath 7 is filled with water. A small damping effect and a high fundamental frequency would be obtained when the sheath 7 is empty. Intermediate levels of water would provide corresponding intermediate levels of damping.
FIG. 6 shows an embodiment in which an auxiliary apparatus 60, such as an antenna, is mounted on the periscope's head 1. The mass of the auxiliary apparatus 60 must be added to the mass of the periscope when determining the proper size of the damping mass 3. The total mass extending above the surface 13 of the submarine, as shown in FIG. 1, should be within the range previously discussed.
The upper periscope tube 2 in FIG. 6 has a diameter which narrows as the periscope's head 1 is approached. A protective sheath 7b is designed to account for the variable diameter of the tube 2 and the unsymmetrical location of the periscope's head 1. The sheath 7b is also designed to facilitate water flow and minimize wake and resistance caused by vertical or horizontal motion for all angular positions of the periscope.
The protective sheath 7b may also be designed to be pressure tight at the submarine's maximum submersion depth. The interior of the sheath 7b' can then be filled with an oil or other hydraulic damping fluid. Silicone oil is preferred.
Referring to FIG. 7, disclosed is a damping apparatus 10, similar to that disclosed in FIG. 3, which is further provided with a pressure-tight, protective sheath 7c. An interior of the sheath 7c' is preferably filled with silicone oil. A damping mass 3c is provided with a plurality of radial channels 71 which increase the damping effect of the silicone oil or other hydraulic damping fluid. The size and shape of the channels 71, together with the size and shape of the interior of the sheath 7c' determine the extent of damping.
Disclosed in FIG. 8 is an embodiment of a damping apparatus 10 wherein the damping mass 3 is housed within the upper periscope tube 2. The damping mass 3 is disposed between a top attaching ring 5 and a bottom attaching ring 4 by a plurality of springy elements 6. The attaching rings 4, 5 are securely clamped to an interior surface of the upper periscope tube 2". This embodiment is advantageous in that it does not require any changes in the external shape of the periscope. However, retrofitting a damping apparatus to fit within a periscope tube would require substantial changes in the design of the devices, including any optical devices housed therein.
FIGS. 9 and 10 show a streamlined damping mass 3d which is rotatably mounted on the upper periscope tube 2. The damping mass 3d is mounted on a single, annular attaching ring 4d by means of upper ball bearings 91 and lower ball bearings 92. Each ball bearing 91 and 92 are disposed respectively between annular ball bearing plates 91', 91", 92' and 92". A plurality of springy elements 6d exert downward directed pressure on a friction ring 94 which juxtaposes the ball bearing plate 91'. A plurality of springs 95 exert upward directed pressure on a friction ring 93 which is juxtaposed against the ball bearing plate 92'. The springy elements 6d and the springs 95 are respectively mounted in recesses 6d' and 95' in the damping mass 3d. This arrangement allows damped radial movements of the damping mass without impeding the rotation of the damping mass 3d around the periscope tube 2. An expanded view of the rotatable damping mass 3d is shown in FIG. 10, wherein a two-part construction of the damping mass 3d, which facilitates installation and removal of the damping apparatus, is disclosed. The damping mass 3d preferably has a streamlined shape in order to optimize the flow of water around it. The rotatable damping mass 3d will automatically set itself as shown in FIG. 10 in response to a submarine traveling in the direction indicated by arrow B.
In a further embodiment of the invention, not shown in the drawings, is a damping apparatus as disclosed in FIGS. 9 and 10 which can be height-adjustably mounted on the periscope tube 2 such that the damping apparatus will automatically adjust its position so as to break the surface of the water. The rotatable damping mass 3d will align itself in order to optimize the flow of water, as previously discussed.
FIG. 11 shows a damping apparatus 10 mounted on a top part of a periscope's head 1'. A damping mass 3e is supported by a plurality of springy elements 6, which in turn rest on an attaching element 4e. The attaching element 4e is securely affixed to the top of the periscope's head 1'. The attaching element 4e may be, for example, a ring or a plate. A protective sheath 7e is also provided. The protective sheath 7e may preferably contain orifices and have means to open and close the orifices. Also, preferably, the sheath 7e may be pressure tight and be filled with a hydraulic damping fluid. In another embodiment, the damping mass 3e may contain channels which further affect the overall damping characteristics.
Referring to FIG. 12, a damping apparatus 10 is mounted on a top part of a periscope's head 1' by means of an attaching ring 4f. A damping mass 3f is supported by a plurality of springy elements 6. Attached to and on top of the damping mass 3f is an auxiliary element 60, which may comprise, for example, a radar warning antenna. The auxiliary element 60 effectively functions as a part of the total damping mass which dampens the vibrations of the periscope. Therefore, the damping mass 3f should be made correspondingly lighter in order for the total damping mass to fall within one of the preferred damping mass ranges. Also shown is a protective sheath 7f which encloses the damping mass 3f and the attaching ring 4f and thereby forms an interior portion 7f' corresponding to the sheath 7f. In this particular application, the protective sheath 7f must be flexible and allow for the influx and exhaust of fluids responsive to vibrational damping movement of the damping apparatus 10. When the sheath 7f is watertight, the elements located in the interior 7f' need not be corrosion or sea water resistant.
Referring to FIG. 13, disclosed is a damping apparatus 10 having a plurality of helical metal springs 6g which serve as means for mounting a damping mass 3g onto the periscope tube 2. The springs 6g are located in a tubular shaped middle section 104 of the attaching ring 4g. The axis of each spring 6g is perpendicular to the axis A--A of the periscope tube 2. According to this embodiment, four springs 6g located 90° apart from one another around the periscope tube 2 are utilized. Each spring 6g is disposed between a damping mass plate 100 located on an inner surface portion of the damping mass 3g' and an attaching ring plate 101 which is in turn connected to the middle section 104 of the attaching ring 4g. Each spring 6g is secured by means of two (2) screws 102. Each screw 102 passes through a washer 103 that is securely attached to the spring 6g. Each screw 102 is rotatably fastened into a threaded channel, not shown, located in the attaching ring plate 101. Alternatively, each screw 102 can be rotatably fastened into threaded channels located in the damping mass plate 100. In response to radial movements of the damping mass 3g, the springs 6g are deflected out of their neutral positions and are alternately stressed in tension and pressure. This radial movement also subjects a circular cross-sectional area C of each spring 6g to deformation wherein the direction of movement comprises a vector at a right angle with an axis of the spring 6g which is perpendicular to the cross-sectional area C.
As previously mentioned, more than four springs may be employed according to this embodiment. Alternatively, a single, ring-shaped spring 6g which encircles the entire middle portion 104 of the attaching ring 4g may be provided.
The springs 6g should be made from materials which are resistant to sea water corrosion, e.g., stainless steel. When the springs 6g and other components of the damping apparatus 10 are also corrosion resistant, a protective sheath is not necessary to prevent corrosion. However, a protective sheath may still be useful for streamlining the damping mass.
The springs 6g are preferably comprised of a plurality of narrow wire strands wound together to form the spring. This type of construction results in good damping characteristics, due in part to friction between the individual wire strands. The springs 6g may alternatively be comprised of a unitary solid wire.
Further damping may be achieved by setting the damping mass 3g on top of a friction pad 106 which is horizontally positioned between the lower horizontal surface of the damping mass 3g and the corresponding horizontal surface of the attaching ring 4g. Pressure is applied from above the damping mass 3g by screws 109 which passes through the upper portion 105 of the attaching ring 4g and acts on a pressure ring 108. The pressure ring 108 is consequently pressed down on a friction pad 107 which juxtaposes the top horizontal surface of the damping mass 3g. The pressure applied to the friction pads 106, 107 is controlled with the screws 109, thereby controlling the degree of damping.
The damping mass 3g is constructed of two parts which are firmly held together and clamped on to the periscope tube 2 by means of screws 110. Cylindrical channels 111 are provided in the attaching ring 4g to allow water to exit the interior portion 104' between the damping mass 3g and the middle portion 104 of the attaching ring 4g.
The following example discloses an application of one particular embodiment of the present invention.
EXAMPLE
At the speed of the submarine during periscope use only one resonant frequency was observed. The periscope having an extended length of 4.2 meters, an upper support bearing of a submarine, was fitted with a damping apparatus immediately below the periscope's head. The particular damping apparatus embodiment is shown in FIG. 1. The mass of the extended portion of the periscope was 260 kilograms. The extended periscope tube had a natural frequency of about 8.8 Hz. The damping mass had a mass of about 6.2 kilograms and a natural frequency of about 8 Hz. The damping mass was supported by four rubber springy elements each having a diameter of 15 mm. The rubber hardness was 55 Shore. By computation, the effective damping was 16.8% of critical damping. FIG. 14 shows the TRANS factor, which is a factor indicating a degree of resonance, as a function of vibrational frequency for a periscope without damping C1 and with 16.8% effective damping C2. Without damping, the maximum TRANS factor was 60 at 8.8 Hz. With damping of up to 6.5, the TRANS factor at 8.8 Hz was about 3.5. Peak TRANS values were observed for the damped periscope at the frequencies of 7.8 Hz and 9.7 Hz. These values were higher than the TRANS values for the undamped system at corresponding frequencies. However, the resonant peaks at 7.8 Hz and 9.7 Hz were very much less than that of the original undamped system at 8.8 Hz.
For an undamped maximum deflection of 40 mm, which corresponds to a TRANS factor of 60, the damped system reduced the maximum deflection to about 4.5 mm. This reduction in maximum deflection represents a notable improvement in the vibratory behavior of the periscope. It should be noted, however, that the true optimum damping level and damping apparatus embodiment, for a particular application, will be dependent on various factors which may parameters, specifications, traveling conditions, include the design of the submarine or other vessel, the pressure and design of other equipment extending from the submarine or vessel and the particular travel conditions. Additional factors which should be considered include the capabilities of the manufacturer and any specific requirements of the user.
The invention is not to be taken as limited to all the details that are described hereinabove, since modifications and variations thereof may be made without departing from the spirit or scope of the invention.
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The invention relates to an apparatus for damping vibrational deflections of periscopes or other vessel devices, which periscopes or other vessel devices extend into an aqueous medium when in use. Particular uses for the damping apparatus include application to periscopes, antennas and the like, for submarines. The damping apparatus preferably comprises a damping mass suitably mounted on a periscope or other extended-in-use device by damping elements. The damping elements may include, for example, elastic springy elements having a high internal friction, friction dampers, and coil springs which dissipate vibrational energy. The damping mass moves in response to vibrations of the damped device, thereby functioning as a kinetic energy storing device. The damping elements interact with the movement of the damping mass and thereby function as potential energy storing means. The damping apparatus damps the vibrational deflections of the device, which extends into the aqueous medium during movement of a vessel therethrough, thereby improving the performance of the extending device.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the field of wheel rims for pneumatic tires of a vehicle. More particularly, the present invention relates to the field of wheel well obstructor bands for wheel rims of a vehicle.
2. Description of the Prior Art
Specifically, pneumatic tires are commonly mounted on a wheel rim. The wheel rim has an annular narrow wheel well which effectively reduces the diameter of the wheel well all around its circumference. Such a wheel well, sometimes called a drop-center type wheel rim, facilitates the mounting of a pneumatic tire on the wheel rim. When it is desired to install the tire onto the wheel rim, one side of the bead can be placed around the bead retaining flange and into the wheel well, thus enabling the diametrically opposing side of the bead to be placed over the bead retaining flange on the other side of the wheel rim. Removal of the tire is accomplished in the reverse manner.
After the tire is installed and the tire inflated with its bead seated against the flanges, the wheel well serves no purpose. The presence of the wheel well, however, has been found to pose safety problems. When pressure is unintentionally lost from the tire due to a blow out or puncture during operation, the wheel well becomes available to the bead of the tire. If the bead of the tire falls into the wheel well, it is possible for the diametrically opposite sides of the bead to unintentionally fall off the bead retaining flange, and thereby the entire bead can fall off the flange. When the bead of the tire is lost from the bead retaining flange, serious loss of control of a vehicle upon which the tire is mounted can result.
Prior art band-type well obstructors have been proposed for obstructing this wheel well so that, in the event of deflation of the tire during operation, the interior of the wheel well will not be available to the bead of the tire, thereby insuring that the tire will remain on the wheel rim. However, wheel well-fillers of current designs have to be made individually for different types of wheels of different diameter and especially for wheel wells of different effective depths. None of the known prior art wheel well obstructors is adjustable in depth.
The following two (2) prior art patents are found to be pertinent to the field of the present invention:
1. U.S. Pat. No. 4,694,874 issued to White on Sep. 22, 1987 for “Wheel Well Obstructor For A Wheel Rim” (hereafter the “White Patent”); and
2. U. S. Pat. No. 5,435,368 issued to Lüst on Jul. 25, 1995 for “Tire-Retention Device And Wheel Rim” ((hereafter the “Lüst Patent”).
The White Patent discloses a wheel well obstructor for a wheel rim for obstructing the well of the hub of a wheel rim. The wheel obstructor has an inextensible band with integral circular protrusions mechanically extruded onto the band. The circular protrusions extend radially inwardly to abut against the base of the wheel well to retain the band in position surrounding the wheel well, and to resist crushing under the weight of the vehicle in the event of deflation of the tire.
The Lüst Patent discloses a well-filler of variable width for a drop-center wheel. The well filler has a band for circumposing the wheel rim in the well in engagement with a plurality of segments and mutually engageable connectors at first and second ends of the band. The connector means is adjustable for tightening of the band in the well around the rim. Engagement of the band with the segments is such that when the band is tightened in the well of a wheel rim, the segments are urged in directions transverse to the band so that the width of the well-filler matches that of the well.
It is desirable to provide an improved wheel well obstructor band with the capability of rapidly adapting to a plurality of different types of wheels of different diameter and especially for wheel wells of different effective depths. It is also desirable to provide a unique tightening hand tool for installing the improved wheel well obstructor band to a plurality of different types of wheels in a much more efficient way than prior art hand tools.
SUMMARY OF THE INVENTION
The present invention is an improved removable wheel well obstructor band which serves as a stable platform for supporting the beads of a flat tire, thereby resulting in a controlled run-flat tire capability.
The removable band-type wheel well obstructor is used for obstructing the interior of an annular wheel well of a wheel rim, wherein the wheel well has a predetermined radial depth. The obstructor includes a two-piece annular band of inextensible material of a predetermined axial width, a thickness which is substantially less than the depth of the wheel well and is adapted to circumferentially surround the wheel well, and is provided with an opening through its circumference. A plurality of radially and inwardly projecting adjustable snap-on frusto-cone shaped shims of a predetermined height are attached to and spaced around the circumference of the band and are adapted to be received into the wheel well. A plurality of height adjusters are respectively attachable to the plurality of snap-on shims for accommodating a plurality of different depths of wheel well. Means are also provided for tensionably retaining the wheel well obstructor band on the wheel rim.
It is an object of the present invention to provide an improved removable wheel well obstructor which includes a plurality of removable and attachable shims for adapting to the depth of a wheel well.
It is also an object of the present invention to provide an improved removable wheel well obstructor which includes a plurality of different thicknesses of a height adjuster that are attachable to the shims so that the plurality of shims can be adapted to a plurality of different depths of a wheel well.
It is an additional object of the present invention to provide an improved removable wheel well obstructor which includes a fastener assembly for drawing together spaced apart adjacent ends of the band portions.
It is a further object of the present invention to provide an improved removable wheel well obstructor wherein the plurality of shims provide positive resistance to movement of the wheel well obstructor into the wheel well of the wheel rim under the weight of the vehicle, and they also reduce the incidence of slippage or rotational movement of the obstructor with respect thereto.
It is still a further object of the present invention to provide a tightening hand tool to be used with the improved removable wheel well obstructor to draw the two ends of the band of the wheel well obstructor together so that tension is released, thereby allowing the installer to tighten the fastener to secure the wheel well obstructor to the wheel rim.
In the preferred embodiment of the present invention, the improved removable wheel well obstructor is a two-piece type band.
In an alternative embodiment of the present invention, the improved removable wheel well obstructor is a unitary type band.
Further novel features and other objects of the present invention will become apparent from the following detailed description, discussion and the appended claims, taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring particularly to the drawings for the purpose of illustration only and not limitation, there is illustrated:
FIG. 1 is a perspective view of the present invention wheel well obstructor installed within a wheel well of a wheel rim;
FIG. 2 is a perspective view of a two-piece wheel well obstructor in accordance with the present invention shown in FIG. 1;
FIG. 3 is a perspective view of the two-piece wheel well obstructor with a plurality of frusto-cone shaped shims installed thereto;
FIG. 4 is an enlarged partial cross-sectional view taken along line 4 — 4 of FIG. 1;
FIG. 5 is an enlarged cross-sectional view through one of the plurality of frusto-cone shaped shims and one of the plurality of height adjusters installed on the band of the wheel well obstructor;
FIG. 6 is a perspective of one of the plurality of frusto-cone shaped shims;
FIG. 7 is a perspective of one of the plurality of height adjusters;
FIG. 8 is a perspective of the height adjuster installed on the shim;
FIG. 9 is a cross-sectional taken along line 9 — 9 of FIG. 8;
FIG. 10 is a cross-sectional view of a portion of the wheel well obstructor and one of the plurality of frusto-cone shaped shims, assembled within the wheel well of the wheel rim, and the tire fitted with its beads seated against the flanges of the wheel rim;
FIG. 11 is a cross-sectional view of a portion of the wheel well obstructor and one of the plurality of frusto-cone shaped shims and one of the plurality of height adjusters, assembled on a deep wheel well of the wheel rim, and the tire fitted with its beads seated against the flanges of the wheel rim;
FIG. 12 is a perspective view of an alternative embodiment of a one-piece wheel well obstructor with a plurality of shims installed thereto;
FIG. 13 is a perspective view of a tightening hand tool used with the present invention removable wheel well obstructor;
FIG. 14 illustrates the tightening hand tool attached to the removable wheel well obstructor, showing the tightening tool in the uncompressed or untorqued condition or position; and
FIG. 15 illustrates the tightening hand tool attached to the removable wheel well obstructor, showing the tightening tool in the compressed or torqued condition or position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Although specific embodiments of the present invention will now be described with reference to the drawings, it should be understood that such embodiments are by way of example only and merely illustrative of but a small number of the many possible specific embodiments which can represent applications of the principles of the present invention. Various changes and modifications obvious to one skilled in the art to which the present invention pertains are deemed to be within the spirit, scope and contemplation of the present invention as further defined in the appended claims.
Described briefly, the present invention is a removable annular wheel well obstructor for obstructing a plurality of different inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth.
Referring to FIG. 1, there is shown at 10 a preferred embodiment of the present invention removable wheel well obstructor installed on a wheel well 2 of a wheel rim 4 . This wheel well obstructor 10 has at least two semicircular annular band portions 12 and 14 that are fabricated of a sturdy and relatively inextensible material, such as steel or other suitable material and coated with zinc plate.
Referring to FIGS. 1, 2 , 3 , 4 and 5 , the band portions 12 and 14 are interconnected at its adjacent ends 24 to form an annular band member 30 of inextensible material of a predetermined axial width “W” and having an opening 50 through its circumference. The annular band member 30 has a thickness “T” that is substantially less than the predetermined radial depth “RD” of the wheel well 2 and being adapted to circumferentially surround the wheel well 2 of the wheel rim 4 and linear with the bottom surface 5 of the wheel rim 4 (see FIG. 4 ).
Referring to FIGS. 1, 2 and 3 , each of the band portions 12 and 14 are substantially identical, and to the extent they are, only one will be described in detail. The band portion 12 includes a plurality of radial apertures 28 that extend therethrough and are equally spaced apart circumferentially around the band portion, and a pair of a plurality of slotted apertures 32 which are equally spaced apart around the circumference of the band portion and parallel to each other and the plurality of radial apertures 28 . The band portion 12 includes flanges 26 at opposite ends 24 which are bent inwardly, and preferably are bent partially around in the form of a semi-circular loop. Each flange 26 is adapted to receive and hold one end of a typical fastener 34 . These typical fasteners 34 are used with the present invention removable wheel well obstructor 10 for securing the adjacent ends 24 of the band portions 12 and 14 together as shown and since the parts of the fastener 34 are well known in the art, the description thereof will only be described in general terms. Because of these fasteners 34 , assembly and disassembly of the annular band member 30 is thereby simplified. When tightened, the ends of the fastener 34 will bear snugly against the flanges 26 to tensionably draw together the adjacent ends 24 of the band portions 12 and 14 to hold the well the band member 30 in tension surrounding the wheel well 2 of the wheel rim 4 .
Referring to FIGS. 2 and 3, the band portions 12 and 14 have holes 38 which are used so that the fastener 34 can be conveniently installed onto the flanges 26 from the outside circumference of the band member 30 after loosening the fastener. When the band portions 12 and 14 are urged apart by imparting tension to the band member 30 , the ends of the fastener 34 will be securely held in position by the flanges 26 as long as this tension exists.
Referring to FIGS. 4, 5 , 6 , 8 and 9 , there is shown at 40 one of the plurality of attachable and detachable shims or means used with the present invention removable wheel well obstructor 10 . Each of the plurality of shims 40 is substantially identical, and to the extent they are, only one will be described in detail. The shim 40 has a predetermined height “H” and is rigid and lightweight and easy to form, thereby making the removable wheel well obstructor 10 less prone to being crushed under the weight of the vehicle tending to press the bead of the tire against the band member 30 . The shim 40 has a generally receivable distal frusto-cone shaped body 42 and an attachable proximal stem 44 which is integrally formed at the bottom of the body 42 . The frusto-cone shaped body 42 has a round shaped distal end surface 52 with a bore 54 for respectively receiving a plurality of height adjusters or means 16 as shown in FIGS. 8 and 9. The round shaped surface distal end 48 of the shim 40 significantly increases the coefficient of friction between the shims 40 and the base 3 of the wheel well 2 of the wheel rim 4 when the wheel well obstructor 10 is installed. This helps to prevent undesirable rotation of the wheel well obstructor 10 with respect to the wheel well 2 of the wheel rim 4 . The shims 40 are attachable to the band portions 12 and 14 , wherein the proximal stem 44 of each shim is respectively snapped onto the plurality of radial apertures of the band portions 12 and 14 of the annular band member 30 . The proximal stem 44 of each shim 40 may have an annular groove 46 for securing it to the band portions 12 and 14 (see FIGS. 4 and 5 ). The frusto-cone shaped body 42 of the shim 40 may have an annular groove 48 located at the bottom for reducing material used and cost of the shims 40 .
Referring to FIGS. 5, 7 , 8 and 9 , there is shown at 16 one of the plurality of attachable and detachable height adjusters or members used with the present invention removable wheel well obstructor 10 . Each of the plurality of height adjusters 16 are substantially identical, and to the extent they are, only one will be described in detail. The height adjuster 16 has a generally round distal end 18 and an attachable proximal stem 20 which is integrally formed at the bottom of the distal end 18 . The proximal stem 20 is press-fitted to the bore 54 of the shim 40 for further increasing the height “H” of the shim 40 so that the shim 40 can match the radial depth of a plurality of different radial heights “RD” of wheel well. The thickness T 1 or height of the distal end 18 of the height adjuster 16 can vary depending on the radial height of the wheel well 2 (see FIG. 9 ).
Referring now to FIG. 10, a portion of the wheel well obstructor 10 of the present invention is illustrated in cross-section installed surrounding the wheel well 2 of the wheel rim 4 . The round shaped distal end surface 52 of the shim 40 abuts against the wheel base 3 of the wheel well 2 . A pneumatic tire 6 is installed with its bead 7 seated against the bead retaining flanges 8 of the wheel rim 4 in the normal position.
In FIGS. 4 and 10, the shims 40 are approximately equal in height to the radial depth “RD” of the wheel well 2 . It is not necessary, however, that the height “H” of the frusto-cone shaped body 42 of the shim 40 be equal to the radial depth “RD” of the wheel well 2 . Due to the height adjusters 16 , a plurality of different radial depths of wheel well 2 can be accommodated as shown in FIG. 11 . The present invention can be installed in a deeper wheel well, as shown in FIG. 11, with the aid of the height adjusters 16 , where the distal end 18 of the height adjuster 16 abuts against the wheel base 3 of the wheel well 2 . A pneumatic tire 6 is installed with its bead 7 seated against the bead retaining flanges 8 of the wheel rim 4 in the normal position. Therefore, it can be seen that the present invention provides a band-type well obstructor which is sturdy, easy to form and to install, and which is adaptable to a wide variety of well depths.
Referring to FIG. 12, there is shown at 100 an alternative embodiment of the present invention removable wheel well obstructor 100 . In this embodiment, the at least two semicircular annular band portions 12 and 14 shown in FIGS. 2 and 3 are substituted with a single band member 130 with its ends interconnected together by a fastener. Since it assembles and functions the same as previously described above, the description thereof will not be repeated. Height adjusters 16 are not shown attached to the shims 40 in this figure, but can be used in this alternative embodiment of the present invention removable wheel well obstructor 100 .
The present invention conforms to conventional forms of manufacture or any other conventional way known to one skilled in the art, and is of simple construction and is easy to use. The shims 40 and height adjusters 16 can be made from several materials. The manufacturing process which could accommodate the construction of the shims and height adjusters may be injection, therefrom, etc. or other molding process. By way of example, the shims and height adjusters can be made of polyurethane material, nylon material, plastic material or any other suitable material.
FIG. 13 shows a tightening hand tool 60 . FIG. 14 shows the tightening hand tool 60 in a released or relaxed condition. FIG. 15 shows the tightening hand tool 60 in a compressed or torqued condition. Referring to FIGS. 13, 14 and 15 , there is shown at 60 a tightening hand tool to be used in conjunction with the present invention removable wheel well obstructor 10 . The tightening hand tool 60 allows a user to draw the adjacent ends 24 of the pair of band portions 12 and 14 closer together to impart tension to the annular band member 30 , thereby allowing the user to tighten the fasteners 34 to secure the wheel well obstructor to the wheel well of the wheel rim.
The hand tool 60 comprises a lever member 61 and a pair of movable linkage arms 66 and 68 . The lever member 61 has a hand portion 62 and an attachment portion 64 . The first linkage arm 66 has a hook end 70 or connecting end and an attachment end 72 which is pivotably connected to the attachment portion 64 . The second linkage arm 68 also has a hook end 74 or connecting end and an attachment end 76 which is pivotable connected to the attachment portion 64 and located above the attachment end 72 of the first linkage arm 66 .
In operation, the hook end 70 of the first linkage arm 66 is inserted into one of the plurality of slotted apertures 32 on the band portion 14 while the hook end of the second linkage arm 68 is inserted into one of the plurality of slotted apertures 32 of the band portion 12 (see FIG. 14 ). The hand portion 62 is pulled or pushed forward as indicated with arrow 80 shown in FIG. 14, thereby allowing the adjacent ends 24 of the band portions 12 and 14 to draw closer together as indicated with arrows 82 and 84 in FIG. 15, so that tension is released, where the installer or user can tighten the fastener 34 .
The tightening hand tool 60 conforms to conventional forms of manufacture or any other conventional way known to one skilled in the art, and is of simple construction and is easy to use. By way of example, the hand tool is made of steel or any other rigid material.
Defined in detail, the present invention is a removable annular wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) a pair of semicircular band portions being interconnected at its adjacent ends to form an annular band of inextensible material of a predetermined axial width and having an opening through its circumference and a plurality of equally spaced apart radial apertures extending therethrough, the annular band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of attachable and detachable frusto-cone shaped shims of a predetermined height, each frusto-cone shaped shim having an attachable proximal end and a receivable distal end, wherein each attachable proximal end is respectively snapped onto a respective one of the plurality of radial apertures of the annular band and projecting radially and inwardly of the annular band, where the plurality of frusto-cone shaped shims match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of frusto-cone shaped shims are received into the wheel well; (c) a plurality of attachable and detachable height adjusters, each height adjuster having a predetermined height and attachable to the receivable distal end of the each frusto-cone shaped shim to further increase the height of the predetermined height of the each frusto-cone shaped shim for matching the radial depth of another wheel well of another wheel rim; and (d) means for tensionably retaining the wheel well obstructor on the wheel well of the wheel rim. Defined broadly, the present invention is a removable annular wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) at least two band portions being interconnected at its adjacent ends to form an annular band of inextensible material of a predetermined axial width and having an opening through its circumference, the annular band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of attachable and detachable shims of a predetermined height, each shim having a proximal end and a distal end, wherein each proximal end is respectively attached onto and spaced apart around the circumference of the annular band and projecting radially and inwardly of the annular band, where the plurality of shims match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of shims are received into the wheel well; (c) a plurality of attachable and detachable height adjusters, each height adjuster having a predetermined height and attachable to the distal end of the each shim to further increase the height of the predetermined height of the each shim for matching the radial depth of another wheel well of another wheel rim; and (d) means for tensionably retaining the wheel well obstructor on the wheel well of the wheel rim.
Defined more broadly, the present invention is a removable wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) at least two band portions being interconnected at its adjacent ends to form a band of inextensible material of a predetermined axial width and having an opening through its circumference, the band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of fixed members of a predetermined height respectively attached to and around the circumference of the band and projecting radially and inwardly of the band, where the plurality of fixed members match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of fixed members are received into the wheel well; (c) a plurality of adjustable members, each adjustable member having a predetermined height and attachable to the each fixed member to further increase the height of the predetermined height of the each fixed member for matching the radial depth of another wheel well of another wheel rim; and (d) means for tensionably retaining the wheel well obstructor on the wheel well of the wheel rim.
Defined even more broadly, the present invention is a removable wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) at least two band portions being interconnected at its adjacent ends to form a band of inextensible material of a predetermined axial width and having an opening through its circumference, the band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of fixed members of a predetermined height respectively attached to and around the circumference of the band and projecting radially and inwardly of the band, where the plurality of fixed members match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of fixed members are received into the wheel well; (c) means for further increasing the height of the predetermined height of the each fixed member for matching the radial depth of another wheel well of another wheel rim; and (d) means for tensionably retaining the band on the wheel well of the wheel rim.
Defined still even more broadly, the present invention is a removable wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) at least two band portions being interconnected at its adjacent ends to form a band of inextensible material of a predetermined axial width and having an opening through its circumference, the band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of fixed members of a predetermined height respectively attached to and around the circumference of the band and projecting radially and inwardly of the band, where the plurality of fixed members match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of fixed members are received into the wheel well; and (c) means for tensionably retaining the band on the wheel well of the wheel rim.
Further defined in detail, the present invention is a removable annular wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) an annular band of inextensible material of a predetermined axial width and having an opening through its circumference and a plurality of equally spaced apart radial apertures extending therethrough, the annular band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of attachable and detachable frusto-cone shaped shims of a predetermined height, each frusto-cone shaped shim having an attachable proximal end and a receivable distal end, wherein each attachable proximal end is respectively snapped onto a respective one of the plurality of radial apertures of the annular band and projecting radially and inwardly of the annular band, where the plurality of frusto-cone shaped shims match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of frusto-cone shaped shims are received into the wheel well; (c) a plurality of attachable and detachable height adjusters, each height adjuster having a predetermined height and attachable to the receivable distal end of the each frusto-cone shaped shim to further increase the height of the predetermined height of the each frusto-cone shaped shim for matching the radial depth of another wheel well of another wheel rim; and (d) means for tensionably retaining the wheel well obstructor on the wheel well of the wheel rim.
Further defined broadly, the present invention is a removable annular wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) an annular band of inextensible material of a predetermined axial width and having an opening through its circumference, the annular band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of attachable and detachable shims of a predetermined height, each shim having a proximal end and a distal end, wherein each proximal end is respectively attached onto and spaced apart around the circumference of the annular band and projecting radially and inwardly of the annular band, where the plurality of shims match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of shims are received into the wheel well; (c) a plurality of attachable and detachable height adjusters, each height adjuster having a predetermined height and attachable to the distal end of the each shim to further increase the height of the predetermined height of the each shim for matching the radial depth of another wheel well of another wheel rim; and (d) means for tensionably retaining the wheel well obstructor on the wheel well of the wheel rim.
Further defined more broadly, the present invention is a removable wheel well obstructor for obstructing a plurality of inwardly disposed annular wheel wells of a plurality of wheel rims, wherein each wheel well of each wheel rim has a predetermined radial depth, the wheel well obstructor comprising: (a) an annular band of inextensible material of a predetermined axial width and having an opening through its circumference, the band having a thickness substantially less than the predetermined radial depth of the wheel well and being adapted to circumferentially surround the wheel well; (b) a plurality of fixed members of a predetermined height respectively attached to and around the circumference of the band and projecting radially and inwardly of the band, where the plurality of fixed members match the radial depth of the wheel well and being adapted to abut against the well base when the plurality of fixed members are received into the wheel well; and (c) means for tensionably retaining the annular band on the wheel well of the wheel rim. Defined alternatively in detail, the present invention is a tightening hand tool used in conjunction with a wheel well obstructor having an annular band member with at least two adjacent ends for allowing a user to draw the two adjacent ends closer together to release impart. tension of the band member, thereby allowing the user to tighten a fastener to secure the band member to a wheel well of a wheel rim, the tightening hand tool comprising: (a) a lever member having a hand portion and an attachment portion; (b) a first movable linkage arm having a hook end and an attachment end pivotably connected to the attachment portion of the lever member; and (c) a second movable linkage arm having a hook end and an attachment end pivotably connected to the attachment portion of the lever member and located below the attachment end of the first movable linkage arm; (d) whereby the hook end of the first linkage arm being insertable into one slotted aperture at one of the two adjacent ends of the band member while the hook end of the second linkage arm being insertable into another slotted aperture at the other one of the two adjacent ends of the band member, and the hand portion being actuated thereby allowing the two adjacent ends of the band member to draw closer together, so that tension is released, and the fastener is tightened to secure the band member of the wheel well obstructor to the wheel well of the wheel rim.
Defined alternatively broadly, the present invention is a tightening hand tool used in conjunction with a wheel well obstructor having a band with at least two adjacent ends for allowing a user to draw the two adjacent ends closer together to release impart tension of the band, thereby allowing the user to tighten a fastener to secure the band to a wheel well of a wheel rim, the tightening hand tool comprising: (a) a lever member; (b) a first linkage arm having a connecting end and an attachment end pivotably connected to the lever member; and (c) a second linkage arm having a connecting end and an attachment end pivotably connected to the lever member and located adjacent to the attachment end of the first linkage arm; (d) whereby the connecting end of the first linkage arm being insertable into one aperture at one of the two adjacent ends of the band while the connecting end of the second linkage arm being insertable into another aperture at the other one of the two adjacent ends of the band, and the lever member being actuated thereby allowing the two adjacent ends of the band to draw closer together, so that tension is released, and the fastener is tightened to secure the band of the wheel well obstructor to the wheel well of the wheel rim.
Defined alternatively more broadly, the present invention is a tool used in conjunction with a wheel well obstructor having at least two adjacent ends for allowing a user to draw the two adjacent ends closer together to release impart tension of the wheel well obstructor, thereby allowing the user to tighten a fastener to secure the wheel well obstructor to a wheel well of a wheel rim, the tool comprising: (a) a lever member; and (b) a pair of linkage arms each having one end pivotably connected to the lever member and a connecting end; (c) whereby the connecting end of one of the pair of linkage arms being insertable into one aperture at one of the two adjacent ends of the wheel well obstructor while the connecting end of the other one of the pair of linkage arms being insertable into another aperture at the other one of the two adjacent ends of the wheel well obstructor, and the lever member being actuated thereby allowing the two adjacent ends of the wheel well obstructor to draw closer together, so that tension is released, and the fastener is tightened to secure the wheel well obstructor to the wheel well of the wheel rim.
Of course the present invention is not intended to be restricted to any particular form or arrangement, or any specific embodiment, or any specific use, disclosed herein, since the same may be modified in various particulars or relations without departing from the spirit or scope of the claimed invention hereinabove shown and described of which the apparatus or method shown is intended only for illustration and disclosure of an operative embodiment and not to show all of the various forms or modifications in which this invention might be embodied or operated.
The present invention has been described in considerable detail in order to comply with the patent laws by providing full public disclosure of at least one of its forms. However, such detailed description is not intended in any way to limit the broad features or principles of the present invention, or the scope of the patent to be granted. Therefore, the invention is to be limited only by the scope of the appended claims.
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The removable wheel well obstructor serves as a stable platform for supporting the beads of a flat tire, thereby resulting in a controlled run-flat tire capability. The obstructor is used for obstructing the interior of an annular wheel well of a wheel rim, wherein the wheel well has a predetermined radial depth. The obstructor includes a two-piece annular band of inextensible material of a predetermined axial width, a thickness which is substantially less than the depth of the wheel well and is adapted to circumferentially surround the wheel well, and is provided with an opening through its circumference. A plurality of snap-on frusto-cone shaped shims of a predetermined height are radially and inwardly attached to and spaced around the circumference of the band and are adapted to be received into the wheel well depth. A plurality of height adjusters are respectively attachable to the plurality of snap-on shims for further accommodating a plurality of different radial depths of wheel well.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation Application of U.S. patent application Ser. No. 13/456,704, filed Apr. 26, 2012 (now U.S. Pat. No. 8,459,523), which is a Continuation Application of U.S. application Ser. No. 13/352,716, filed Jan. 18, 2012 (now U.S. Pat. No. 8,186,559), which is a Continuation Application of U.S. patent application Ser. No. 13/251,309, filed Oct. 3, 2011 (now U.S. Pat. No. 8,118,208), which is a Continuation Application of U.S. patent application Ser. No. 12/960,892, filed on Dec. 6, 2010 (now U.S. Pat. No. 8,056,791), which is a Continuation Application of U.S. patent application Ser. No. 12/472,369, filed on May 26, 2009 (now U.S. Pat. No. 7,845,538) which is a Continuation Application of U.S. patent application Ser. No. 11/542,363, filed on Oct. 2, 2006 (now U.S. Pat. No. 7,537,602), which is a Division Application of U.S. patent application Ser. No. 10/761,492, filed on Jan. 20, 2004 (now U.S. Pat. No. 7,114,642), which is a Division Application of U.S. patent application Ser. No. 10/341,234, filed on Jan. 13, 2003 (now U.S. Pat. No. 6,698,643), which is a Continuation Application of U.S. patent application Ser. No. 09/873,682, filed on Jun. 4, 2001 (now U.S. Pat. No. 6,505,768), which is a Continuation Application of U.S. patent application Ser. No. 09/351,534, filed on Jul. 12, 1999 (now U.S. Pat. No. 6,264,087), each of which is expressly incorporated herein in its entirety by reference thereto.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to an attachment for an electromechanical device for use with anastomosing, stapling, and resecting surgical tools, and more specifically to a stapling and resecting device which can be attached to and serve as an extension of an electromechanical device driver, and most specifically to the expanding parallel jaws and the mechanisms thereof.
2. Description of the Prior Art
Upon identification of cancerous and other anomalous tissue in the gastrointestinal tract, surgical intervention is often prescribed. The field of cancer surgery, and more specifically, the surgical procedure by which a section of the gastrointestinal tract which includes cancerous tissue is resected, includes a number of uniquely designed instruments. In combination with a description of the present instrumentation and their functions, a description of the state of the art in this surgical procedure shall also be provided.
The first question which must be answered when determining how to treat gastrointestinal tract cancer relates to the specific location of the cancerous tissue. This is very important insofar as the instruments which are provided in the present art have limitations relating to how far they may be inserted into the gastrointestinal tract. If the cancerous tissue is too far up or down the gastrointestinal tract, then the standard instrumentation provided is unusable, thus requiring special accommodations. These accommodations generally increase the risk of contamination of the surrounding tissues with bowel contents, increase the length of the surgery and the corresponding need for anesthesia, and eliminate the benefits of precise anastomosing and stapling which comes from utilizing a mechanized device.
More specifically, in the event that the cancerous tissue is located at a position in the colon which is accessible by the present instrumentation, the patient's abdomen is initially opened to expose the bowel. The surgeon then cuts the tube of the colon on either side of the cancerous tissue, while simultaneously stapling closed the two open ends of the bowel (a distal end which is directed toward the anus, and the proximal end which is closest to the lower intestine). This temporary closure is performed in order to minimize contamination. The linear cutter and stapling instrument which is used in the prior art is provided in a perspective view in FIG. 1 .
More particularly, this temporary closure is achieved when the colon is placed between the scissoring elements at the tip of the linear cutter and stapling instrument. By squeezing the trigger in the handle of the device, the surgeon causes the scissoring elements to come together. A second trigger (or a secondary action of the same trigger) is then actuated to drive a series of staples and a cutting blade through the clamped end of the colon, thereby closing and transecting the ends.
After the sealing of the two exposed distal and proximal ends, the surgeon creates a small opening in the proximal end of the bowel and inserts the removable anvil portion of an anastomosing and stapling instrument. This step, as well as those of the remainder of the surgical procedure, are related to the functioning of this surgical instrument which is provided in a perspective view in FIG. 2 . More particularly, the surgeon begins by taking the instrument and manually turning the dial at the base of the handle which causes the anvil head at the opposite end to advance forward. The surgeon continues to turn the dial until the anvil head advances to its most extreme extended position. This manual turning requires nearly thirty full rotations. Once fully extended, the anvil head of the instrument is decoupled therefrom and is inserted into the exposed proximal end such that the coupling post extends outwardly therethrough. As described above, this proximal end is then stapled closed. The extending shaft of the anastomosing and stapling instrument is then inserted and advanced into the lower colon, transanally, until the coupling stem thereof extends through the stapled distal end. The surgeon then joins the coupling ends of the anvil and shaft together and begins to manually rotate the dial in the handle again, this time bringing the anvil head closer to the tip of the shaft.
Once the anvil head and shaft are brought close together, after the surgeon has manually rotated the dial another thirty times, a grip-style trigger in the handle is manually actuated. This actuation causes a circular blade to advance axially out from the tip of the shaft, and into contact with the opposing face of the anvil. The blade cuts through the stapled-closed ends of the proximal and distal ends of the colon, thereby also cutting a new pair ends of the proximal and distal portions of the colon. The tissue which has been severed is held in an interior volume at the end of the shaft.
In lock step with the cutting, the freshly opened ends are joined together by a series of staples which are advanced through holes in the perimeter of the tip of the shaft (being pressed against and closed by the opposing face of the anvil). The coupled shaft and anvil are then withdrawn from the patient.
More particularly with respect to the structural features of the linear stapling instrument of the prior art which is provided in FIG. 1 , the device comprises a pistol grip-styled structure having an elongate shaft and distal portion. The distal portion includes a pair of scissors-styled gripping elements which clamp the open ends of the colon closed. In fact only one of the two scissors-styled gripping elements, the anvil portion, moves (pivots) relative to overall structure; the other remains fixed. The actuation of this scissoring means (the pivoting of the anvil portion) is controlled by means of a grip trigger maintained in the handle. A number of different means have been disclosed for holding the tips of the scissoring arms closed, including snaps, clips, collars, et al.
In addition to the scissoring means, the distal portion also includes a stapling mechanism. The non-moving element of the scissoring mechanism includes a staple cartridge receiving region and a mechanism for driving the staples up through the clamped end of the colon, against the anvil portion, thereby sealing the previously opened end. The scissoring elements may be integrally formed with the shaft, or may be detachable such that various scissoring and stapling elements may be interchangeable.
More particularly with respect to the structural features of the anastomosing and stapling instrument of the prior art which is provided in FIG. 2 , the device comprises an anvil portion, a staple, blade and reservoir portion, a shaft portion, and a handle portion. The anvil portion, which is selectively removable from the tip of the shaft, is bullet shaped, having a blunt nosed top portion, a flat cutting support surface on the bottom, and a coupling post extending axially from the bottom surface.
The staple, blade, and reservoir portion (SBR portion) of the instrument is provided at the distal end of the instrument, and includes a selectively advanceable and retractable coupling stem for selectively receiving thereon the anvil portion. This action of the coupling stem is provided by a screw threaded shaft and worming mechanism mounted in the handle (described more fully below). The SBR portion is cylindrical in shape, forming a housing which has a hollow interior. It is this hollow interior which forms the reservoir. The blade is similarly cylindrical, and seats in the inside of the housing, against the inner wall thereof. The blade is selectively advanceable axially outward from the housing, in accordance with actuation of a trigger mechanism of the handle (again, described more fully below). On the axially outward facing surface of the cylindrical wall of the housing are a series of staple ports, through which the staples of the device are discharged. The same actuation which drives the blade forward similarly drive a series of staple drivers forward within the cylindrical walls. More accurately, the staple driver is a cylindrical component which has a series of protuberances on the axial end thereof, the protuberances being positioned in accordance with the distribution of staples and holes. The staples, prior to being discharged, are mounted in the holes; and they are advanced through the holes by the action of the staple driver and the protuberances thereof
The shaft portion of the instrument is a simple rigid extended structure which is intended as a sheath for a pair of elongate rods. The first rod is coupled to the worming mechanism introduced above, and described more fully below with respect to the handle portion, and is the means by which the anvil portion and the coupling stem of the SBR portion are selectively advanced and retracted. The second rod is coupled to the trigger of the handle at one end (also introduced above, and described more fully below) and to the blade and staple driver at the other end. The sheath protects the patient and the instrument when it is advanced into the colon transanally. The nature of the actuation mechanisms however, requires that the shaft be rigid. This rigidity limits the length of the shaft; and combination, i.e. the length and rigidity of the instrument, these features limit the sections of the colon which may be treated using this device.
The handle of this instrument of the prior art comprises a pistol grip styled structure having a turning dial at the butt (i.e. the end opposing the junction of the shaft portion which the handle) and a finger actuated trigger. The trigger includes a safety mechanism which physically prevents actuation unless moved out of the interference position. The turning dial is actionably coupled to a worming mechanism which is used to advance the first rod of the shaft portion (thereby advancing the coupling stem and the anvil). The trigger functions as a basic lever to push the second rod forward within the shaft, thereby advancing the blade and staple driver.
As with many such devices of the prior art, all of these devices are considered fully disposable, and are, in fact, thrown away after a single use. They are complicated devices, having multiple moving parts, requiring substantial structural integrity and, therefore, expense in manufacturing. The fact that they are used only once, and no part can be used again render the use of such devices expensive and wasteful of resources.
In addition to this failure, as can be readily observed from the preceding descriptions, the prior art devices suffer from numerous other limitations which would be desirable to overcome. These include the rigid and limited length shaft of the devices, as well as the requirement that the surgeon manually actuate all of the features and functions.
Therefore, it is a principal object of the present invention to provide an instrument for resecting and stapling gastrointestinal tissue during colon surgery, which reduces the waste of resources by permitting use as an attachment to an electromechanical device driver.
It is further an object of the present invention to provide an instrument assembly which reduces the requirements for the surgeon to manually actuate different components and mechanisms.
It is further an object of the present invention to provide a resecting and stapling mechanism that can be integrated with other electromechanical devices into an attachment for use with an electromechanical device driver.
Other objects of the present invention shall be recognized in accordance with the description thereof provided hereinbelow, and in the Detailed Description of the Preferred Embodiment in conjunction with the remaining Figures.
SUMMARY OF THE INVENTION
The preceding objects of the invention are provided by virtue of an electromechanical resecting and stapling attachment which is coupleable to and remotely actuateable by an electromechanical device driver. In particular, the attachment includes a pair of linearly spreading jaws for clamping the selected section of gastrointestinal tissue therebetween, said jaws expanding and closing in a parallel disposition. More particularly, the linear clamping mechanism of the attachment is used to first clamp the section of colon, and then to hold the colon in place as a blade extends along a track in the lower jaw of the clamping attachment to cut the section of bowel, and then drives a series of staples through the two opened ends so that the contents of the bowel are not permitted to empty into the surrounding region of the abdomen. This attachment, and others necessary to perform the remainder of the surgery, is coupled to an electromechanical driver which is described more fully hereinbelow.
More particularly, with respect to the electromechanical driver, the driver has a handle and a flexible drive shaft. The handle has a pistol grip-styled design, having a pair of finger triggers which are independently coupled to separate motors which each turn separate flexible drive shafts (described more fully, hereinbelow). The motors are each dual direction motors, and are coupled to a manual drive switch mounted to the top of the handle, by which the user can selectively alter the turning direction of each motor. This dual direction capacity may be most simply achieved by selecting motors which turn in a direction corresponding to the direction of current, and actuation of the drive switches alters the direction of the current accordingly. In this example, the power source supplying the motors must be a direct current source, such as a battery pack (and most desirably, a rechargeable battery pack). In the event that the device should be useable with an alternating current, either a transformer can be included, or a more sophisticated intermediate gearing assembly may be provided. In conjunction with the present description, the embodiments of the present invention which will be described utilize a rechargeable battery pack providing a direct current.
In addition to the motor components, the handle further includes several other features, including: (1) an remote status indicator; (2) a shaft steering means; and (3) at least one additional electrical supply. First, the remote status indicator may comprise an LCD (or similar read out device) by which the user may gain knowledge of the position of components (for example whether a clamping element is in the proper position prior to the driving of the staples). Second, the handle also includes a manually actuateable steering means, for example, a joystick or track ball, for directing the movement of the flexible shaft (by means of guidewires implanted in the shaft portion described more fully hereinbelow). Finally, the handle may include an additional electrical power supply and an on off switch for selectively supplying electrical power to the attachments.
More particularly, with respect to the flexible shaft, the shaft comprises a tubular sheath, preferably formed of a simple elastomeric material which is tissue compatible and which is sterilizable (i.e. is sufficiently rugged to withstand an autoclave). Various lengths of this shaft may be provided in conjunction with the present invention. In this case, the flexible shaft and the handle portions should be separable. If separable, the interface between the proximal end of the shaft and the distal end of the handle should include a coupling means for the drive components. Specifically regarding the drive components of the shaft, within the elastomeric sheath are a pair of smaller fixed tubes which each contain a flexible drive shaft which is capable of rotating within the tube. The flexible drive shaft, itself, simply must be capable of translating a torque from the motor in the handle to the distal end of the shaft, while still being flexible enough to be bent, angled, curved, etc. as the surgeon deems necessary to “snake” through the bowel of the patient. For example, the drive shafts may comprise a woven steel fiber cable. It shall be recognized that other drive shafts may be suitable for this purpose. In order for the distal end of the drive shaft to couple with an attachment, such as the clamping and stapling device of the present invention (as described more fully below), however, the distal tips of the drive shafts must have a conformation which permits the continued translation of torque. For example, the distal tips of the drive shafts may be hexagonal, thereby fitting into a hexagonal recess in the coupling interface of the attachment. As suggested above, in conjunction with the manually actuateable steering means mounted to the handle, the sheath further includes at least two guidewires which are flexible, but are coupled to the inner surface of the sheath near the distal end thereof. The guidewires may be axially translated relative to one another by actuation of the steering means, which action causes the sheath to bend and curve accordingly. Also, as suggested above, in conjunction with the LCD indicator of the handle, the shaft further contains an electrical lead for coupling to the attachments. This electrical lead channels a signal from the attachment to the handle for indicating the status of the attachment (for example, whether a clamping function is holding). Similarly, a second electrical lead may be provided to supply power to separate aspects of the attachment if so required (for example, as will be described more fully with respect to linear resecting and stapling attachment, the use of selectively engageable electromagnetic seal for ensuring continued clamping through the stapling process may be provided and require power selectively provided from the handle's power supply).
More particularly, with respect to the linear resecting, clamping, and stapling attachment which is the specific subject of this invention, the attachment is fitted with two drive extensions, which in operation function as extensions of the flexible drive shafts of the electromechanical driver. That is, when the attachment is mated to the electromechanical driver, the drive extensions are in mechanical communication with the flexible drive shafts such that the activation of the drive shaft motors activates the drive extensions within the linear clamping, cutting and stapling attachment. The first drive extension enables the parallel spreading and closing of the jaws of the device, which form a linear clamping mechanism, while the second drive extension enables a cutting and stapling mechanism. More particularly, the linear clamping mechanism comprises a separating jaw system whereby an upper jaw is raised to permit the bowel tissue to be placed therebetween, and subsequently the jaws are closed to meet to effect a clamping. In a first embodiment, the first drive extension engages a pair of threaded vertical shafts which raise or lower the upper jaw depending on the turning direction of the corresponding motor in the electromechanical driver. In a second embodiment, the first drive extension includes only a single angled gearing mechanism mounted at the end of the horizontally rotating shaft (which is coupled to one of the turning shafts of the electromagnetic driver). This gearing mechanism causes the vertically rotation of a threaded shaft on which the upper jaw is separately munted. In both embodiments, when the jaws are closed, a pair of sensor electrodes disposed on the jaws come into contact and thereby complete a sensor circuit which alerts the surgeon that it is safe or appropriate to activate the resecting and stapling mechanism and/or automatically activates the resecting and stapling mechanism.
In each of these embodiments, the second driver causes a blade to slide along a track in the lower jaw, which blade cuts the bowel, briefly leaving two open ends. Nearly simultaneous with the cutting, a stapling mechanism drives a series of staples upwardly through opening in the lower jaw, toward the upper jaw, through the open ends, thereby closing the bowel segments. This stapling action happens nearly simultaneous with the cutting in part because the blade is contiguous with a stapling mechanism of the present invention.
This stapling mechanism begins with a replaceable tray of open staples which is set within the lower jaw, the tray having two rows of staples separated along the long axis of the jaw so that the blade may track between the rows. The opposing upper jaw face includes a set of corresponding staple guides, such that when the linear clamping mechanism is in a closed position, the open staples immediately oppose the corresponding staple guides. This mechanism comprises a wedge pushing system whereby once the linear clamping mechanism is in a closed position, the blade and a wedge ride along together in a channel below the tray of open staples, and the staples are pushed up toward the staple guides, through the bowel. More particularly, as the wedge moves through the channel a sloping surface of the wedge pushes the open staples against the corresponding staple guides, thereby closing the staples. After the staples have been closed, the wedge is pulled back through the channel. It is the first drive mechanism which lifts the jaws apart in parallel; and it is the second drive mechanism which pushes or pulls the wedge and blade mechanism through the channel. The direction of the first and second mechanisms is related solely to the remote operation of the driver, and the corresponding turning direction of the shafts, of the electromechanical driver.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a linear clamping, cutting and stapling mechanism of the prior art;
FIG. 2 is a perspective view of an anastomosing and stapling mechanism of the prior art.
FIGS. 3 and 4 are side views of the closed and open dispositions, respectively, of a linear clamping, cutting and stapling attachment which is an aspect of the present invention;
FIGS. 5 and 6 are cutaway side views of the closed and open dispositions, respectively, of the linear clamping, cutting and stapling attachment shown in FIGS. 3-4 which is an aspect of the present invention;
FIGS. 7-14 are rear views in various cutaway planes of the linear clamping, cutting and stapling attachment shown in FIGS. 3-6 which is an aspect of the present invention;
FIGS. 15-19 are bottom, top cutaway, deep top cutaway, bottom cutaway, and top views, respectively, of the linear clamping, cutting and stapling attachment shown in FIGS. 3-14 which is an aspect of the present invention; and
FIG. 20 is a side cutaway of the linear clamping, cutting and stapling attachment shown in FIGS. 3-19 which is an aspect of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of the resecting and stapling attachment having expanding jaws which remain parallel, according to the present invention, is illustrated in FIGS. 3-20 . More particularly, referring now to FIGS. 3 , 4 and 15 , a linear clamping mechanism and a stapling and cutting mechanism according to the present invention are shown as part of a linear clamping, cutting and stapling attachment 20 . Referring now also to FIGS. 5 and 6 , in this preferred embodiment, the linear clamping mechanism comprises a parallel separating jaw system comprising a lower jaw 50 and an upper jaw 80 having a proximal end 100 . Referring now also to FIGS. 9 , 13 , 16 and 19 , the proximal end 100 of the upper jaw 80 has a pair of threaded vertical bores 90 , through which extend a corresponding pair of vertical shafts 130 . Inner threads 92 of the vertical bores 90 match outer threads 132 of the vertical shafts 130 . Referring now also to FIGS. 8 and 12 , the vertical shafts 130 engage a threaded upper horizontal shaft 150 at a distal end 140 of the upper horizontal shaft 150 . Outer threads 152 of the upper horizontal shaft 150 interlock with the outer threads 132 of the vertical shafts 130 . Referring now to FIGS. 5-7 and 11 , the upper horizontal shaft 150 has at a proximal end 170 an upper drive socket 180 .
Referring to FIGS. 5-8 , 11 , 12 , 16 and 19 , the linear clamping and cutting mechanism further comprises a first sensor electrode 182 electrically communicating via communication wires (not shown) with a first contact pad 187 (best shown in FIGS. 8 , 12 , 16 and 19 ) which in turn electrically communicates with a second contact pad 189 (best shown in FIGS. 14 and 17 ) via direct contact, which electrically communicates via communication wires (not shown) with a first contact node 188 (best shown in FIGS. 7 , 11 and 15 ). Similarly, the linear clamping mechanism further comprises a second sensor electrode 184 electrically communicating via communication wires (not shown) with a second contact node 186 (best shown in FIGS. 7 , 11 and 15 ). The contact nodes 186 , 188 electrically communicate with communication wires (not shown) in the electro-mechanical drive component (not shown) to form a sensor circuit, such that when the upper jaw 80 and the lower jaw 50 are clamped together, the sensor electrodes 182 , 184 are in contact, the sensor circuit is closed, and the surgeon is alerted via other circuit components (not shown) to the clamped position of the jaws 50 , 80 , and is therefore informed that it is safe and/or appropriate to active the stapling mechanism.
Further in this preferred embodiment, and referring now to FIGS. 5 , 6 , 10 , 14 , 18 and 20 , the cutting and stapling mechanism comprises a wedge pushing system comprising in the lower jaw 50 a replaceable tray 220 housing one or more fastening rods, or staples 230 , and in the upper jaw 80 one or more staple guides 240 corresponding to the staples 230 . Each of the staples 230 has a butt 232 protruding below the tray 220 , and a pair of prongs 234 extending to the top of the tray 220 . Referring now also to FIGS. 9 , 13 and 17 , the wedge pushing system further comprises a wedge guide, or channel 250 extending beneath the tray 220 . Within the channel 250 extends a threaded lower horizontal shaft 260 having outer threads 262 . Upon the lower horizontal shaft 260 travels a wedge 270 having a sloped top face 280 , a horizontal threaded bore 290 (best shown in FIGS. 9 and 12 ) coaxial with the channel 250 , having and inner threads 292 matching the outer threads 262 of the lower horizontal threaded shaft 260 , and an upwardly extending blade member 51 . Referring now to FIGS. 5 , 6 , 7 and 11 , the lower horizontal shaft 260 has at a proximal end 300 a second drive socket 310 .
In operation, after the surgeon has located the cancerous or anomalous tissue in the gastrointestinal tract, the patient's abdomen is initially opened to expose the bowel. Utilizing the remote actuation provided by the electromechanical driver assembly, the surgeon drives the upper and lower jaws of the linear cutting and stapling attachment into the open position. The surgeon then places the tube of the bowel on a side adjacent to the cancerous tissue between the parallel spread jaws. Again, by remote actuation, the surgeon causes the upper drive mechanism to engage in reverse, and the upper jaw closes, in a parallel alignment, onto the bowel and the lower jaw. Once the bowel has been sufficiently clamped, the surgeon engages the second drive mechanism, which causes the blade and wedge staple driver to advance simultaneously, thereby cutting and stapling the bowel. The surgeon then repeats this step on the other side of the cancerous tissue, thereby removing the section of bowel containing the cancerous tissue, which is stapled on either end to prevent spilling of bowel material into the open abdomen.
More particularly, the linear clamping, cutting and stapling attachment is mated to the attachment socket (not shown) of the electromechanical driver component (not shown) such that the upper drive socket 180 engages the corresponding flexible drive shaft (not shown) of the electromechanical driver component (not shown) and the second drive socket 310 engages the corresponding flexible drive shaft (not shown) of the electromechanical driver component (not shown). Thus, rotation of the upper horizontal shaft 150 is effected by rotation of the upper drive socket 180 which is effected by rotation of the corresponding flexible drive shaft (not shown) of the electromechanical driver component (not shown). Clockwise or counter-clockwise rotation is achieved depending on the direction of the responsible motor (not shown). Similarly, rotation of the lower horizontal shaft 260 is effected by rotation of the second drive socket 310 which is effected by rotation of the corresponding flexible drive shaft (not shown) of the electromechanical driver component (not shown). Again, clockwise or counter-clockwise rotation is achieved depending on the direction of the responsible motor (not shown).
In order to clamp the exposed ends of the bowel, the surgeon first activates the upper motor 400 corresponding to the upper flexible drive shaft 410 which engages the upper drive socket 180 at the proximal end 170 of the upper horizontal shaft 150 , thereby causing the upper horizontal shaft 150 to turn in a clockwise rotation. When the linear clamping and stapling attachment is in an initial closed state as shown in FIG. 3 , this clockwise rotation of the upper horizontal shaft 150 causes the outer threads 152 of the upper horizontal shaft 150 to engage the outer threads 132 of the vertical shafts 130 , thereby causing the vertical shafts 130 to turn in a clockwise rotation. This clockwise rotation of the vertical shafts 130 causes the outer threads 132 of the vertical shafts 130 to channel within the inner threads 92 of the vertical bores 90 , thereby causing the upper jaw 80 to rise in a continuous fashion, in a parallel alignment with the fixed lower jaw, and begin separating from the lower jaw 50 . Continuous operation of the motor in this manner eventually places the linear clamping and stapling attachment in an open state, providing a space between the upper jaw 80 and the lower jaw 50 , as shown in FIG. 4 . Once the linear clamping and stapling attachment is in this open state, the surgeon has access to the tray 220 of staples 230 , and can check to ensure that the staples 230 are ready for the procedure and/or replace the tray 220 with a more suitable tray 220 . Once the surgeon has verified that the tray 220 is ready and in place, the surgeon places the open distal end of the colon between the upper jaw 80 and lower jaw 50 . Thereafter, the surgeon reverses the upper motor 400 to effect a counter-clockwise rotation of the upper horizontal shaft 150 , which in turn effects counter-clockwise rotation of the vertical shafts 130 , which in turn effects a lowering of the upper jaw 80 , also in continuous parallel alignment. Continuous operation of the upper motor 400 in this manner eventually returns the linear clamping and stapling attachment to a closed state, where the distal end of the bowel is clamped between the upper jaw 80 and the lower jaw 40 , with a small portion of the distal end of the bowel extending laterally beyond the upper jaw 80 and the lower jaw 50 .
Once the distal end of the bowel is clamped as described above, the sensor electrodes 182 , 184 are in contact, and the surgeon is alerted via circuit components in the electromechanical drive component that it is safe and/or appropriate to activate the cutting and stapling mechanism. The surgeon then activates the cutting and stapling mechanism. It should be noted that the resistance afforded by the mechanical relationships between the upper jaw 80 , vertical bores 90 , vertical shafts 130 , horizontal shaft 150 , and upper drive socket 180 of the linear clamping and stapling attachment, and the upper flexible drive shaft and upper motor 400 of the electromechanical driver component, together ensure that the upper jaw 80 and lower jaw 50 remain clamped together during the operation of the stapling mechanism. To begin the stapling and cutting procedure, the surgeon activates the lower motor 420 of the electromechanical driver component corresponding to the lower flexible drive shaft 430 which engages the lower drive socket 310 at the proximal end 300 of the lower horizontal shaft 260 , thereby causing the lower horizontal shaft 260 to turn in a clockwise rotation. When the stapling and cutting mechanism is in an initial loaded state, the wedge 270 and the blade 51 associated therewith are in the channel 250 at a position closest to the proximal end 300 of the lower horizontal shaft 260 . The clockwise rotation of the lower horizontal shaft 260 causes the outer threads 262 of the lower horizontal shaft 260 to engage the inner threads 292 of the horizontal threaded bore 290 of the wedge 270 , thereby causing the wedge 270 to travel through the channel 250 in a direction away from the proximal end 300 of the lower horizontal shaft 260 . Continuous operation of the lower motor 420 in this manner will move the wedge 270 fully through the channel 250 . As the wedge 270 moves through the channel, the blade 51 mounted to the top of the wedge cuts through the bowel, transecting it. Simultaneously, the sloped top face 280 of the wedge 270 contacts the butts 232 of the staples 230 , thereby pushing the prongs 234 of the staples 230 through the tissue of the clamped distal end of bowel and against the staple guides 240 , which bends and closes the staples 230 . When the wedge 270 is moved fully through the channel 250 , all of the staples 230 are pushed through the tray 220 and closed, thereby stapling closed the distal end of the bowel. Thereafter, the surgeon reverses the lower motor 420 to effect a counter-clockwise rotation of the lower horizontal shaft 260 , which in turn moves the wedge 270 toward the proximal end 300 of the lower horizontal shaft 260 . Continuous operation of the lower motor 420 in this manner eventually returns the wedge 270 to its initial position.
Thereafter, the surgeon again activates the upper motor 400 to effect a clockwise rotation of the upper horizontal shaft 150 , which in turn effects a clockwise rotation of the vertical shafts 130 , which in turn effects a raising of the upper jaw 80 . Continuous operation of the upper motor 400 in this manner eventually places the linear clamping, cutting and stapling attachment into an open state. Thereafter, the surgeon replaces the empty tray 220 with a full tray 220 , and performs the same clamping, cutting and stapling procedure on the proximal end of the bowel. Once the proximal end of the bowel is also clamped, cut and stapled, the surgeon may separate the attachment from the electromechanical driver component, discard the attachment, and use the electromechanical driver component for additional procedures with other attachments.
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A cutting and stapling device for use as an attachment to an electromechanical device driver comprises an upper jaw and a lower jaw which separate and close against one another in a continuously parallel alignment. The upper jaw includes a series of staple guides corresponding to one or more staples in a removable staple tray disposed within a lower jaw, whereby a blade and wedge having a threaded bore travel upon a matching threaded shaft in a channel disposed in the lower jaw below the staple tray, such that rotation of the threaded shaft causes movement of the wedge through the channel while a sloped surface of the wedge contacts the staples to push the staples against the staples guides, closing the staples.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a glove or a mitt used for baseball, softball, and the like.
2. Description of the Related Art
As the above glove, there are gloves of an opening type having a large opening on a hand insertion opening portion side of an outer skin on a side corresponding to a back of the hand when viewed from behind and a totally-closed type in which the outer skin extends from a side corresponding to fingertips to a side corresponding to a wrist without having an opening. In use of these gloves, many users use them with their forefingers placed on an outside of the outer skin.
This is because placing the forefinger that is the most suitable to exact motions in respective fingers on the outside of the outer skin improves a balance of the glove to enable the user to easily catch a ball and allows a shock in catching the ball to be absorbed in the glove.
Incidentally, the glove of the opening type is used with the forefinger passed through the opening portion in the outer skin to the outside of the outer skin while the glove of the totally-closed type is used with the forefinger inserted through a forefinger insertion hole formed in the outer skin (see U.S. Pat. No. 5,457,819, for example).
Conventionally, the above glove of the opening type simply has a structure in which the forefinger can be passed through the opening portion to be placed on the outside of the outer skin as means for enabling the forefinger to be placed on the outside of the outer skin such that the forefinger can move freely in a width direction of the hand on the outside of the outer skin.
On the other hand, the glove of the totally-closed type is simply formedwith the forefinger insertion hole in the outer skin such that the forefinger is positioned in a fixed position on the outside of the outer skin as disclosed in the above U.S. Pat. No. 5,457,819.
According to the above conventional glove of the opening type, because the forefinger can move freely on the outside of the outer skin, the forefinger may be displaced from a position where the forefinger was placed before catching the ball by a shock of the catching motion to degrade ease of use of the glove.
A position of the forefinger (on the outside of the outer skin) that makes the glove easy to use is different for each user. For example, a user feels it easy to use the glove with his or her forefinger placed close to his or her middle finger while another feels it easy to use the glove with his or her forefinger placed close to his or her thumb.
According to a structure of the conventional glove of the totally-closed type, because the forefinger is positioned in a fixed position on the outside of the outer skin, some users feel that the gloveis difficult to use even if their forefingers are placed on the outside of the outer skin in use of the glove.
SUMMARY OF THE INVENTION
The present invention has been accomplished with the existing condition of the above prior art in view, and it is an object of the present invention to provide a glove in which differences in ease of use of the glove among users are suppressed and more users feel it easy to use the glove by enabling each user to choose an appropriate condition of use of the glove according to his or her habit, liking, and the like.
The above object is achieved by inventions stated in claims. In other words, in a characteristic structure of the invention, a forefinger can be placed on an outside of an outer skin corresponding to a back side of a hand and a forefinger support body for positioning and supporting the forefinger on the outside of the outer skin is provided to the outer skin such that a position of the forefinger support body can be adjusted in a direction corresponding to a width direction of the hand.
With this structure, the glove with the above structure is used in a state in which the forefinger is placed on the outside of the outer skin and positioned and supported on the forefinger support body. Thus, displacement of the forefinger in a catching motion can be prevented.
Because the position of the forefinger support body can be adjusted in the width direction of the hand, a user who feels that the glove is easier to use with his or her forefinger positioned close to his or her middle finger can use the glove with the above structure after adjusting the position of the forefinger support body such that his or her forefinger is placed close to his or her middle finger, for example.
A user who feels that the glove is easier to use with his or her forefinger positioned close to his or her thumb can use the glove after adjusting the forefinger support body such that his or her forefinger is placed close to his or her thumb. In other words, the forefinger that is the most suitable to exact motions in respective fingers can be placed in a desired position on the outside of the outer skin.
Therefore, according to this invention, it is possible to prevent displacement of the forefinger in the catching motion and to position the forefinger in the desired position on the outside of the outer skin, thereby providing the glove in which differences in ease of use of the glove among users can be suppressed and more users feel it easy to use the glove.
It is preferable that the forefinger support body is formed by forming a forefinger insertion hole through which the forefinger is passed on a forefinger support member.
With this structure, because the forefinger support body is formed by forming the forefinger insertion hole through which the forefinger is passed on the forefinger support member, it is possible to avoid complication of the structure of the forefinger support body, thereby further simplifying the structure.
Furthermore, it is preferable that a finger cover into which the forefinger passed through the forefinger insertion hole is inserted is provided to the forefinger support member.
With this structure, because the finger cover is provided to the forefinger support member, the forefinger can be supported more reliably and can be positioned easily. Moreover, an effect of protecting the forefinger in catching a ball that has flown to the vicinity of a fence of a ballpark can be obtained.
It is preferable that a size of the hand insertion opening on a side opposite to a side corresponding to fingertips can be adjusted by enlarging/reducing adjusting means and that the enlarging/reducing adjusting means is also used as position adjusting means of the forefinger support body in the width direction of the hand.
With this structure, because the size of the hand insertion opening can be adjusted by the enlarging/reducing adjusting means, it is advantageously easy to bring the glove with the above structure into close contact with the hand by reducing a diameter of the opening portion after inserting the hand into the hand insertion opening portion.
Because the enlarging/reducing adjusting means is also used as the position adjusting means of the forefinger support body in the width direction of the hand, it is possible to avoid increase in the number of parts and it is easy to carry out the enlarging/reducing adjustment and the position adjustment as compared with a case in which the enlarging/reducing adjusting means and the position adjusting means are formed separately.
Therefore, according to this invention, the glove is easier to use with the further simplified structure and it is possible to save the user time and trouble in putting on the glove.
Furthermore, it is preferable that the forefinger support body is formed by attaching a portion of the forefinger support body on the side corresponding to the fingertips to the outer skin and that a portion of the outer skin on the side of the hand insertion opening portion is split into two parts along a direction corresponding to a longitudinal direction of the hand.
Moreover, it is preferable that the enlarging/reducing adjusting means comprising a band material first insertion portion which is formed on one split part of the outer skin and into which band material is inserted, an end portion of the band material being attached to the one split part of the outer skin, a band material second insertion portion which is formed on the other split part of the outer skin and into which the band material from the band material first insertion portion side is inserted, a band material third insertion portion into which the band material from the band material second insertion portion side is inserted, a band material fourth insertion portion which is formed on the forefinger support body and into which the band material from the band material third insertion portion side is inserted, and a band material fixing portion for fixing a portion of the band material from the band material fourth insertion portion side to a portion of the band material on the one split part side of the outer skin.
According to this structure, it is advantageously possible to insert one hand through the hand insertion opening portion, position and support the forefinger of the hand by the forefinger support body, and to position the forefinger in a desired position in the width direction of the hand.
In other words, a user who feels that the glove is easier to use with his or her forefinger positioned close to his or her middle finger can place his or her forefinger in such a position while a user who feels that the glove is easier to use with his or her forefinger positioned close to his or her thumb can place his or her forefinger in such a position.
Because the forefinger support body is formed by attaching the portion of the forefinger support body on a fingertips side to the outer skin, a position of the forefinger support body can be changed freely in the direction corresponding to the width of the hand.
In this state, a tip end side of the band material is pulled and the strap portion from the band material fourth insertion portion side is fixed to the one split part of the outer skin or the band material portion on the one split part of the outer skin by using the other hand.
Thus, the band material can be tightened to fix the forefinger support body to a position in the hand width direction and both the split parts of the outer skin are drawn toward each other to reduce the diameter of the hand insertion opening portion and to bring the outer skin portion and the like constituting the hand insertion opening portion into contact with a wrist side.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a state in which a glove of an embodiment of the present invention is used.
FIG. 2 is a perspective view of an essential portion of the glove in FIG. 1 .
FIG. 3 shows the glove in FIG. 1 viewed from a side of a hand insertion opening portion.
FIG. 4 is a perspective view of an essential portion of a glove of another embodiment.
FIG. 5 is a perspective view of an essential portion of a glove of yet another embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The embodiments of the glove according to the present invention will be specifically described by reference to the drawings.
FIG. 1 is a baseball glove (corresponding to a glove) of a totally-closed type in which a first outer skin 1 on a side corresponding to a back of a hand extends from a side corresponding to fingertips to a side corresponding to a wrist W without having an opening.
As shown in FIGS. 1 to 3 , the glove is formed by joining the first outer skin 1 , a second outer skin 2 on a ball-receiving side, an inner skin 3 inside the second outer skin 2 , and the like to each other by using leather strap 4 and the like.
A portion of the first outer skin on a hand insertion opening portion 5 side that is opposite to the side corresponding to the fingertips is split into two parts along a longitudinal direction of the hand and the forefinger can protrude from the split portion on an outside of the first outer skin. A forefinger support body 6 for positioning and supporting the forefinger on the outside of the first outer skin 1 is provided to the first outer skin 1 such that a position of the forefinger support body 6 is adjustable in a width direction of the hand.
The forefinger support body 6 has a longitudinally elongated forefinger insertion hole 7 through which the forefinger is passed and which is formed on a forefinger support member 8 in a shape of a leather belt. A portion of the forefinger support member on a fingertips side of the forefinger insertion hole 7 is sewn on the first outer skin 1 . A reference numeral 10 designates a seam.
A size of the hand insertion opening portion 5 is adjustable by using enlarging/reducing adjusting means 9 . The enlarging/reducing adjusting means 9 is also used as position adjusting means for the forefinger support member 8 in the width direction of the hand.
Specifically, the enlarging/reducing adjusting means 9 is constituted in a manner described in the following [1] to [3].
[1] An end portion of a strap 11 (corresponding to band material) as band material is sewn on one split part 1 A of the first outer skin and a first insertion hole 12 (corresponding to a band material first insertion portion) into which the strap 11 is inserted from an outside to an inside is formed in the one split part 1 A of the first outer skin.
[2] A second insertion hole 13 (corresponding to a band material second insertion portion) into which the strap 11 is inserted from an inside to an outside and a rectangular ring 14 (corresponding to a band material third insertion portion) into which the strap 11 is inserted from a second insertion hole 13 side are provided to the other split part 1 B of the first outer skin.
[3] The forefinger support member 8 is formed with a fourth insertion hole 15 (corresponding to a band material fourth insertion portion) into which the strap 11 is inserted from an angular ring 14 side and hook and loop type fasteners 16 (corresponding to band material fixing portions) through which a strap portion from a fourth insertion hole 15 side is superimposed on and fixed to the strap portion on the one split part 1 A of the first outer skin are provided.
The angular ring 14 is supported by a ring-shaped leather band 17 sewn on the other split part 1 B of the first outer skin. The fourth insertion hole 15 is formed by bending and sewing a free end portion of the forefinger support member 8 .
The above glove is attached to the hand in the following manner.
One hand is inserted through the hand insertion opening portion 5 , the forefinger of the hand is passed through the forefinger insertion hole 7 , and the forefinger is allowed to be positioned in a desired position in the width direction of the hand.
In other words, a user who feels that the glove is easier to use with his or her forefinger positioned close to his or her middle finger can place his or her forefinger in such a position while a user who feels that the glove is easier to use with his or her forefinger positioned close to his or her thumb can place his or her forefinger in such a position.
Because the forefinger support body 6 is formed by attaching the portion of the forefinger support member on a fingertips side of the forefinger insertion hole 7 to the first outer skin 1 , a position of the forefinger support body 6 can be changed freely in the direction corresponding to the width of the hand.
In this state, a tip end side of the strap 11 is pulled and the strap portion from the fourth insertion hole 15 side is superimposed on and fixed to the strap portion on the one split part 1 A of the first outer skin through the hook and loop type fasteners 16 by using the other hand.
Thus, the strap 11 can be tightened to fix the forefinger support body 6 to a position in the hand width direction and both the split parts 1 A and 1 B of the first outer skin are drawn toward each other to reduce a diameter of the hand insertion opening portion 5 and to bring the outer skin portion and the like constituting the opening portion 5 into contact with a wrist W side.
[Other Embodiments of the Invention]
(1) As shown in FIG. 4, the glove of the present embodiment can be also applied to the glove of the opening type having the large opening on the hand insertion opening portion 5 side of the first outer skin 1 . This glove of the opening type is different from the glove of the above-described embodiment in that the opening type is formed with an opening 20 and other structures of the opening type are the same as those of the above embodiment.
(2) Furthermore, as shown in FIG. 5, a finger cover 18 into which the forefinger passed through the forefinger insertion hole 7 is inserted can be provided to the forefinger support member 8 constituting the forefinger support body.
(3) The enlarging/reducing adjusting means 9 is not limited to the above-described structure, but may be in other shapes. The forefinger insertion hole 7 is not limited to the above-described shape, but may be in a circular shape, a polygonal shape, or other shapes, for example.
(4) Although the portion of the forefinger support member on the fingertips side of the forefinger insertion hole 7 is sewn on the first outer skin 1 in the above embodiment, the portion of the forefinger support member may be riveted to the first outer skin 1 instead.
(5) The present invention can be also applied to a catcher's mitt and a first baseman's mitt. The invention can be also applied to a glove, a catcher's mitt, and a first baseman's mitt for softball.
(6) Although the examples of the glove for a right-handed user are shown in the above embodiments, the invention can be naturally applied to a glove for a left-handed user.
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A glove or a mitt comprising a first outer skin corresponding to a palm side, a second outer skin corresponding to a back side of a hand and joined to the first outer skin, a forefinger of the hand being able to be placed on an outside of the second outer skin, and a forefinger support body provided to the second outer skin for positioning and supporting the forefinger on the outside of the second outer skin, a position of the forefinger support body being able to be adjusted in a direction corresponding to a width of the hand.
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BACKGROUND OF THE INVENTION
The present invention relates generally to an improved scrubber for cleaning streams of gas laden with toxic solid, liquid or gas contaminants. Specifically, this invention relates to a circulating air scrubber.
Scrubbers for cleaning streams of gas, especially air, laden for example with toxic solid particles and with poisons in gas or liquid phase are known in various embodiments. In conventional scrubbers, a cleaning or scrubbing liquid in finely sprayed, vaporized or atomized form in added to the gas stream laden with contaminants. Generally water is used with the addition of an additive, especially one with a chemical absorbing action, such as alcohol, gas solvents, neutralizing substances, and the like.
After thorough mixing, for example by vortexing, the harmful materials are extracted from the laden gas stream, captured in a filter device and/or condensation arrangement, and removed. Disposal of the resulting accumulations of contaminated scrubbing liquid is a substantial problem with conventional devices.
In conventional air scrubbers, the gas is at 100% relative humidity because of the temperature in the condensation region. This can readily be seen from the known Mollier diagram. For example, at normal ambient temperatures, 3 m 3 of scrubbing liquid are needed for each 1,000 m 3 /h or air. In the continuous cleaning of a larger space, for instance, in a chemical plant in which toxic gases or dust particles arise on a larger scale, a correspondingly large quantity of contaminated scrubbing liquid is accumulated for disposal.
Operation of conventional scrubbers with circulating air is expensive because the gas stream to be cleaned must be cooled, in order to ensure condensation of the scrubbing liquid.
Furthermore, conventional air scrubbers can only remove solid materials to a particle size of about 10 to 50 μm. For smaller particle sizes an additional cleaning device is necessary, such as an electrostatically operated active carbon filter.
The object of the present invention is to provide a circulating air scrubber which requires relatively very little scrubbing liquid, is suitable for removal of very small solid particles in the range of 5 μm and below, and is suitable for operation with circulating air.
SUMMARY OF THE INVENTION
A circulating air scrubber according to the present invention includes means for supplying a scrubbing liquid in finely divided form into the air stream, a high-voltage ionizer for the air stream, means for removing the contaminated scrubbing liquid, means for propelling the air stream, and at least one circular brush, mounted for rotation along an axis substantially parallel to the air stream, positioned downstream stream from the ionizer. The brush has an electrical potential opposite to the ionizing potential and can be driven at so high a speed that, in addition to electrostatic removal, condensation of the contaminated scrubbing liquid occurs on or in the brush.
A plurality of drum or disc-shaped circular brushes can be used, one behind the other, on a common driving shaft. The speed of rotation is preferably controlled in response to the relative humidity of the contaminated gas stream monitored in the intake region by a humidity sensor.
In an alternate embodiment, a plurality of circular brushes supported on coaxial shafts and driven at different speeds may be used.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a sectional view of an air scrubber according to the invention, suitable for operation with circulating air.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The air scrubber according to the present invention requires only relatively very small quantities of scrubbing liquid and is therefore well suited for operation with circulating air. Particles in the size range below 1 μm can be removed and toxic gases will be absorbed and removed by the additional condensation effect.
In accordance with the present invention electrical removal or electrostatic absorbing action occurs because the brush(es) are at the opposite potential to the ionization. In addition, because of the relatively high rotational speed of the brushes, the vapor or particles of moisture of the contaminated scrubbing liquid are mechanically removed from the air stream by condensation caused by the extreme deflection and acceleration of the flow near the brush.
Downstream of the brush, the cleaned air is practically dry and additional condensation for removal of the scrubbing liquid is not needed even when there is a very high relative humidity present on the gas inlet side.
Further, an air scrubber according to the present invention uses only a relatively very small quantity of scrubbing liquid. Tests have shown that about 2 to 3 liters of scrubbing liquid per 1,000 m 3 /h of air are generally sufficient. This dramatically reduces disposal problems by reducing the volume of contaminated scrubbing liquid produced.
Referring now to the Figure, housing 1 of a circulating air scrubber according to the present invention may be constructed in the form of a tube with an axial, flange-like enlargement 2. Inlet air stream A laden with harmful material enters intake region 5, propelled by suction/compression fan 16. Cleaned air stream B exits at exhaust 20.
Conventional electrostatic ionization device 4 is stretched across air stream A in intake region 5, secured with insulation in housing 1, and are connected for example to the negative pole of a high-voltage source (not shown). The ionization voltage preferably lies in the region from 12 kV to about 30 kV. Experiments have shown that an ionization voltage in the region of about 15 kV provides good results for an air cleaning apparatus with a through-flow volume of about 1,000 m 3 /h.
Upstream of ionization device 4, nearer intake region 5, is a source of scrubbing liquid including the following parts and subassemblies: supply passage 13 for water with automatically operable supply valve 12, atomizer 6 (which may be a heater for generating a vapor of scrubbing liquid or an ultrasonic spray head), positioned below the surface of scrubbing liquid 8 in container 21 which is open towards inlet stream A, conventional control device 7 for atomizer 6, liquid surface detector 11 which may conveniently be a float sensor for inlet supply valve 12, and container 23 for additive 10 which is supplied in dispensed amounts into scrubbing liquid 8 via passage 9.
The dispensing rate is matched to the water supplied via passage 13, as determined by float 11. Scrubbing liquid 8, provided with additives 10, which may be absorbing toxic gases, reaches inlet air stream A, after having been atomized by atomizer 6.
The particles of scrubbing liquid 8 and the particles of harmful material in air stream A are ionized by ionization device 4 and then, under the action of fan 16, arrive in the axially enlarged region 2 which includes circular brushes 3. Circular brushes 3 are driven by driving motor 18 at high speed via common shaft 19 which is aligned substantially parallel to the air stream. The speed of shaft 19 and therefore of circular brushes 3 lies in the region of 1,000 to 20,000 rpm, preferably at an average speed of between 1,400 and 3,000 rpm or between 4,000 and 6,000 rpm.
This speed is preferably controlled in response to the relative humidity as measured by humidity probe 22 positioned in air inlet region A. It is also possible, and advantageous for condensation, to drive two circular brushes 3 at different speeds. In this case the downstream circular brush, that is the one lying nearer to driving motor 18, may be driven by a hollow axle or shaft, not shown, at a higher speed, while the upstream circular brush, nearer air inlet 5, is driven at lower speed by a solid shaft passing through the center of the hollow shaft, via a step-down gear arrangement, not shown.
Circular brushes 3 are subjected to an electrical potential opposite to the ionization potential at ionizer 4. This may be accomplished, for example, by connecting drive shaft 19 to the opposite pole of the high-voltage source, not shown, for example by grounding shaft 19.
Circular brushes 3 may conveniently be constructed from materials suited for high acceleration forces, especially certain polyamide plastics materials, which can behave on the surface at least slightly as a conductor. This last-mentioned requirement is satisfied by all brush materials tested.
The scrubbing liquid particles laden with harmful material, which have been condensed by the high-speed rotation of brushes 3 and/or have been accelerated outwards, are collected at funnel C in the lower region of axial enlargement 2, and are removed for disposal via collector 14 and discharge passage 15.
The action of the gas scrubbing arrangement according to the invention, which can also be called an "ultrasonic circulating air brush scrubber with ionization arrangement" is twofold. On the one hand, brushes 3 act with electrostatic attraction on the ionized air laden with harmful material and with scrubbing liquid. On the other hand brushes 3, driven at comparatively high speed, act as a condensation arrangement and as a centrifuge on the laden air particles or gases. By the sharp deflection of the flow in the region of brushes 3 and the acceleration, an extremely high g force is attained, so that the scrubbing liquid cloud or vapor, laden with particles of harmful material or with toxic gases, is condensed, with simultaneous unloading, and is moved radially outwards and led away.
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An ultrasonic circulating air brush scrubber with a supply of scrubbing liquid in finely dispersed form in the intake air stream, and a high-voltage ionizer, includes at least one circular brush downstream of the ionizer. The brush is driven at high speed and is at the opposite potential from the ionized air stream. The circulating air scrubber provides a high degree of cleaning action for particle sizes down to below 1 μm., low consumption of scrubbing liquid and dries the air on the output side.
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RELATED APPLICATIONS
The present invention was first described in a notarized Official Record of Invention on Feb. 28, 2008, that is on file at the offices of Montgomery Patent and Design, LLC, the entire disclosures of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to a bed frame and, more particularly, to an under bed barricade which easily attaches to said bed frame.
BACKGROUND OF THE INVENTION
The area under a bed is often used as a storage area for many items such as off-season clothing, screens or storm windows, extra table leaves and the like. This area offers a conveniently accessible storage area where such articles can be out of sight and out of mind. Disadvantageously, many times these articles are often visible under the bed leading to an unattractive and cluttered appearance to an otherwise neat bedroom guestroom. Such spaces are also prone to attracting dust, dirt and “dust-bunnies”. Cleaning this under bed storage area properly is often a time consuming and tedious task which requires the removal or shifting of any stored articles. This problem often means that the cleaning tasks are generally not undertaken as often as they should. Such under bed areas area a favorite spot for pets such as dogs and cats who often hide there in response to thunder storms, fire works, or other loud noises. Pets can also hide under the bed when sick or injured making their care even more difficult. This under bed space can also create a tempting hiding or play area for toddlers and small children. Many times the dirt and dust collected in this space is unhealthy for small children and the objects stored under the bed may create a safety hazard for unaware and unfamiliar children. Various solutions to solve these problems have been attempted such as modular storage compartments, drawers, and locker devices. Each of these solutions can create their own disadvantages; including limiting the usable under bed storage area, complicated installation procedures, and heavy and obtrusive construction.
Various attempts have been made in the past to overcome these disadvantages and provide an under bed storage and barricade means without the aforementioned problems. Among the relevant attempts to address these problems are several U.S. Pat. Nos. 3,082,435 and 5,095,566.
U.S. Pat. No. 3,745,596, issued in the name of Copeland, describe a combined bed frame with storage compartments comprising side rails and end bars which adapt to and secure to the bed frame, lateral supports which adjustable oppose one (1) another and provide a rigid support means to a plurality of storage drawers. The Copeland device is mounted to the underside of the bed frame which creates a combined structure.
U.S. Pat. No. 4,071,258, issued in the name of Wallace, describes a mobile under bed storage container which can be situated under the frame of a bed supported off of the ground. The Wallace container comprises a rigid body structure having a bottom, side walls, and an open top; a flexible top cover; and a plurality of caster assemblies for rolling the body structure. The dimensions of the container are less than the overall dimensions of the bed frame.
Additionally, ornamental designs for under bed storage and frame devices exist, particularly, U.S. Pat. No. D 264,889; D 342,393; and D 525,790. However, none of these designs are similar to the present invention.
While these devices fulfill their respective, particular objectives, each of these references suffers from one (1) or more of the aforementioned disadvantages. Accordingly, there is a need for a means by which access to the area under a bed can be controlled to address the situations as described above. The development of the present invention fulfills this need.
SUMMARY OF THE INVENTION
In view of the foregoing references, the inventor recognized the aforementioned inherent problems and observed that there is a need for an under bed security barricade and thus, the object of the present invention is to solve the aforementioned disadvantages.
To achieve the above objectives, it is an object of the present invention to provide an under bed security barricade, which provides a means for enclosing a storage area underneath a bed frame thereby providing a privacy guard to items stored under the bed having a pleasant appearance, preventing or hindering access by small animals, children, or the like and reducing the amount of dirt and dust which accumulates under the bed.
Another object of the security barricade is to provide a device generally comprising four (4) sides, each of which comprising two (2) interconnecting sections which provide a means of length adjustment to the sides in order to accommodate various sizes of bed frames and a length of floor stripping which provides a more effective seal between the barricade sides and an under bed floor surface.
Yet still another object of the security barricade is to provide a device comprising a first side, a second side, a head end, and a foot end. The first side comprises a first outer section and a first inner section which slidingly interconnected with one (1) another. The second side comprises a second outer section and a second inner section which slidingly interconnected with one (1) another. The head end comprises a third outer section and a third inner section which slidingly interconnected with one (1) another. The foot end comprises a fourth outer section and a fourth inner section which slidingly interconnected with one (1) another.
Yet still another object of the security barricade is to provide the first side, the second side, the head end, and the foot end comprising an attachment means which provide a rectangular barricade underneath the bed frame when each side is attached to each other side.
Yet still another object of the security barricade is to provide a means of adjusting the length of each side comprising a sliding interconnected outer section and inner section.
Yet still another object of the present invention is to provide an attachment means comprising a plurality of fastening features which provide a means of connecting the sides of the device to one (1) another. The fastening features comprise an insertable male end having a snapping feature and a corresponding receiving female end.
Yet still another object of the security barricade is to provide an attachment means comprising a plurality of connection features which provide a means of securing the device to the underside of the bed frame. The connection features comprise an adjustable connecting feature and corresponding connection aperture attached to a top surface of each outer section of each side of the device.
Yet still another object of the security barricade is to provide a floor strip which is attached to the bottom surface of the each inner and outer section of each side of the device.
Yet still another object of the security barricade is to provide a ventilation means to the under bed storage area comprising a vent located in the third outer section and a vent located in the third inner section which can be aligned as the length of the head end is adjusted to allow air flow and cooling to the inner area of the barricade.
Yet still another object of the security barricade is to provide a method of utilizing the under bed security barricade which provides multiple protections and benefits where under bed storage areas are utilized by people or pets in a manner which is quick, easy and effective.
Further objects and advantages of the security barricade will become apparent from a consideration of the drawings and ensuing description.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages and features of the present invention will become better understood with reference to the following more detailed description and claims taken in conjunction with the accompanying drawings, in which like elements are identified with like symbols, and in which:
FIG. 1 is an environmental view of an under bed security barricade 10 , according to a preferred embodiment of the present invention;
FIG. 2 is a perspective view of an under bed security barricade 10 , according to a preferred embodiment of the present invention;
FIG. 3 is a section view taken along section line A-A of an under bed security barricade 10 , according to a preferred embodiment of the present invention; and,
FIG. 4 is a close-up view of a fastening feature 40 of an under bed security barricade 10 , according to a preferred embodiment of the present invention.
DESCRIPTIVE KEY
10
under bed security barricade
20
first side
22
second side
24
head end
26
foot end
30
first outer section
31
first inner section
32
second outer section
33
second inner section
34
third outer section
35
third inner section
40
fastening feature
42
female end
44
male end
46
snapping feature
50
connecting feature
55
connecting aperture
60
first floor strip
65
second floor strip
70
first vent
75
second vent
80
ridge
85
slot
100
bed frame
105
mattress
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The best mode for carrying out the invention is presented in terms of its preferred embodiment, herein depicted within the FIGS. 1 through 4 . However, the invention is not limited to the described embodiment and a person skilled in the art will appreciate that many other embodiments of the invention are possible without deviating from the basic concept of the invention, and that any such work around will also fall under scope of this invention. It is envisioned that other styles and configurations of the present invention can be easily incorporated into the teachings of the present invention, and only one particular configuration shall be shown and described for purposes of clarity and disclosure and not by way of limitation of scope.
The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced items.
The present invention describes an under bed security barricade (herein described as the “device”) 10 , which provides a means for enclosing a storage area underneath a bed frame 100 , thereby preventing or hindering access thereto by small animals, children, or the like. The device 10 generally comprises four (4) sides, each of which comprises two (2) interconnecting sections which provide a means of length adjustment thereto the sides in order to accommodate various sizes of bed frames 100 . The device 10 is further secured thereto a lower surface of the bed frame 100 .
Referring now to FIGS. 1 and 2 , environmental and perspective views of the device 10 , according to the preferred embodiment of the present invention, is disclosed. The device 10 is preferably made of a light-weight, durable material such as acrylonitrile butadiene styrene, a vinyl polymer, fiberglass, or the like which provides a rigid means of enclosing the area under the bed frame 100 but also flexible such as to not injure a pet or child if either were to run or bump into said device 10 . The device 10 fits thereunder a lower end of a conventional bed frame 100 therebehind the legs of said frame 100 . The device 10 comprises four (4) inner rectangular sections and four (4) outer rectangular sections which connect theretogether to form a generally cuboidal shape approximately equivalent to the size of the bed frame 100 . A first side 20 and a second side 22 each comprise a first outer section 30 and a first inner section 31 . A head end 24 comprises a second outer section 32 and a second inner section 33 . A foot end 26 comprises a third outer section 34 and a third inner section 35 . The outer sections 30 , 32 , 34 and the inner sections 31 , 33 , 35 are slidingly interconnected and provide for a means of length and width adjustment thereto the device 10 . The outer sections 30 , 32 , 34 comprise an inverted “U”-shape through which the inner sections 31 , 33 , 35 are insertingly connected therein. The sections 30 , 31 , 32 , 33 , 34 , 35 are hingedly fastened together via a fastening feature 40 located thereon a free end of each section 30 , 31 , 32 , 33 , 34 , 35 . The first outer section 30 thereon the first side 20 attaches thereto the second outer section 32 , the first inner section 31 thereon said first side 20 attaches thereto the third inner section 35 , the first outer section 30 thereon the second side 22 attaches thereto the third outer section 34 , and the first inner section 31 thereon the second side 22 attaches thereto the second inner section 33 . The device 10 is secured thereto an underside of the bed frame 100 via a plurality of connecting features 50 . At least one (1) connecting feature 50 removably attaches thereto a top surface of each outer section 30 , 32 , 34 and is depicted here as an “L”-shaped member which may be placed therebetween the bed frame 100 and the mattress 105 . The connecting feature 50 is envisioned to be introduced in various forms depending on the type and material of the bed frame 100 to which connected; such as an eyelet which may be secured thereto a wooden bed frame 100 via a screw or other standard hardware, a clip or a clamp which may be secured thereto a metal bed frame 100 , an adjustable strap, or the like and as such should not be interpreted as a limiting factor of the present device 10 . The second outer section 32 comprises a first vent 70 and the second inner section 33 comprises a second vent 75 . The vents 70 , 75 are positioned such that when the second inner section 33 is insertingly attached thereto the second outer section 32 and adjusted to a desired length, said vents 70 , 75 align, thus providing a means of ventilation and allowing for air to circulate thereunder the bed frame 100 . The vents 70 , 75 are preferably a louvered design or a cross-hatched matrix made of the same material as that of the sections 30 , 31 , 32 , 33 , 34 , 35 , a screen, or the like which will not interfere with the sliding adjustability therebetween the second outer 32 and second inner 33 sections.
Referring now to FIG. 3 , a section view taken along section line A-A of the device 10 , according to the preferred embodiment of the present invention, is disclosed. Although FIG. 3 depicts the first outer section 30 and the first inner section 31 , the remaining outer sections 32 , 34 and remaining inner sections 33 , 35 are substantially similar in form and function to that which is depicted. The device 10 further comprises at least one connecting aperture 55 located therein a top surface of the outer sections 30 , 32 , 34 . The connecting aperture 55 comprises an internally threaded diameter and threadingly accepts the connecting feature 50 which further comprises a lower threaded end, thus providing interchangeability of said connecting feature 50 depending on the type and material of bed frame 100 . Each outer section 30 , 32 , 34 further comprise a length of first floor strip 60 which is attached thereto a bottom surface of the inverted “U” shape. Each inner section 31 , 33 , 35 further comprise a length of second floor strip 65 which is attached thereto a bottom surface of the same. The floor strips 60 , 65 are preferably a rubber material or the like which make contact therewith the floor thereunder the bad frame 100 , thus creating a more durable contact surface which will prevent dirt, dust, and the like from reaching the storage area thereunder the bed frame 100 . A ridge 80 is located thereon both sides of each inner section 31 , 33 , 35 and slidingly engage corresponding slots 85 located thereon opposing inner surfaces of the inverted “U”-shape of the outer sections 30 , 32 , 34 . The slot 85 provides a guide track to the ridge 80 which traverses thereinside as the inner section 31 , 33 , 35 is adjusted thereto a desired length.
Referring now to FIG. 4 , a close-up view of a fastening feature 40 of an under bed security barricade 10 , according to the preferred embodiment of the present invention, is disclosed. The fastening feature 40 is preferably molded thereinto a free non-slidingly engaged end of the sections 30 , 31 , 32 , 33 , 34 , 35 during the fabrication process. A male end 44 comprises a snapping feature 46 located thereon a distal end thereof. The snapping feature 46 is preferably an expanded portion of the male end 44 which provides for an interference fit therewith a female end 42 when inserted therein. The fastening feature 40 is depicted here comprising a insertingly connected hinge further comprising the female end 42 and the male end 44 , although it is understood that said fastening feature 40 may be introduced comprising various means of hingingly attaching the sections 30 , 31 , 32 , 33 , 34 , 35 , such as slots, snaps, or other similar interference fits and as such should not be interpreted as a limiting factor of the present device 10 .
It is envisioned that other styles and configurations of the present invention can be easily incorporated into the teachings of the present invention, and only one particular configuration shall be shown and described for purposes of clarity and disclosure and not by way of limitation of scope.
The preferred embodiment of the present invention can be utilized by the common user in a simple and effortless manner with little or no training. After initial purchase or acquisition of the device 10 , it would be installed as indicated in FIG. 1 .
The method of utilizing the device 10 may be achieved by performing the following steps: retrieving the four (4) outer sections 30 , 32 , 34 and the four (4) inner sections 31 , 33 , 35 ; inserting a first inner section 31 therein a first outer section 30 thereby making a first side 20 ; inserting the third inner section 35 therein the third outer section 34 thereby making the foot end 26 ; fastening a free end of said first inner section 31 thereto a free end of said third inner section 35 via engaging the fastening feature 40 ; inserting another first inner section 31 therein another first outer section 30 , thereby making a second side 22 ; inserting the second inner section 33 therein the second outer section 32 , thereby making the head end 24 ; fastening a free end of said first inner section 31 thereto a free end of said second inner section 33 via engaging the fastening feature 40 ; fastening a free end of said first outer section 30 thereto a free end of said second outer section 32 via engaging the fastening feature 40 ; fastening a free end of said first outer section 31 thereto a free end of said third outer section 34 via engaging the fastening feature 40 ; adjusting said device 10 to a desired size depending upon the size of the bed frame 100 by slidingly adjusting said inner sections 31 , 33 , 35 thereinside said outer sections 30 , 32 , 34 ; retrieving the appropriate type of connecting feature 50 depending on the type and material of said bed frame 100 ; threadingly inserting the connecting feature 50 therein a corresponding connecting feature aperture 55 ; engaging the connecting feature 50 thereto an underneath surface of said bed frame 100 ; and, benefiting from the increased safety, cleanliness, and peace of mind afforded a user of the present device 10 .
The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention and method of use to the precise forms disclosed. Obviously many modifications and variations are possible in light of the above teaching. The embodiment was chosen and described in order to best explain the principles of the invention and its practical application, and to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. It is understood that various omissions or substitutions of equivalents are contemplated as circumstance may suggest or render expedient, but is intended to cover the application or implementation without departing from the spirit or scope of the claims of the present invention.
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A guard-style device intended to prevent or hinder access to under bed storage areas is herein disclosed, comprising a series of interlocking panels providing an adjustable rectangular structure that is approximately the size of a bed. The device can be placed under a bed at its perimeter and is held in place to the bed frame by a plurality of connecting features. In such a position, the device reduces dust and dirt from accumulating under a bed, provides an element of increased security for objects that are stored under the bed, and prevents pets such as dogs, cats, and the like from running under the bed during storms or when seeking seclusion. The device also provides a unique visual element; however, it can easily be covered by a dust ruffle should its appearance not be desired.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of the filing date of Provisional Application Ser. No. 60/291,258, entitled METHOD FOR SYNTHESIS OF ALPHA-SULFONAMIDO CARBOXYLIC ACID AND HYDROXAMIC ACID DERIVATIVES, filed May 17, 2001 in the name of Campian et al.
FIELD OF INVENTION
[0002] The present invention relates to a novel method for solid phase synthesis of diverse sulfonamido amide, carboxylic acid and hydroxamic acid derivatives, and the use of such a method to create combinatorial libraries of diverse sulfonamido amides, carboxylic acids and hydroxamic acids.
BACKGROUND OF THE INVENTION
[0003] Sulfonamido carboxylic acids and their derivatives are widely used as building blocks in the design and synthesis of biologically active peptidomimetics, such as sulfonamide; peptoids. α-Sulfonamido carboxylic acids and the corresponding hydroxamic acid derivatives are also an important class of matrix metalloprotease inhibitors which have recently received great attention as therapeutic agents for the treatment of human diseases. Several α-sulfonamido hydroxamic acids are currently under clinical investigation against arthritis and cancer.
[0004] Conventional approaches to the preparation of the sulfonamido acid derivatives rely on the use of amino acids as the starting material followed by N-sulfonylation. However, the process can be tedious if the amino acids to be used are not readily available although a great deal of efforts have been made during the last three decades in the development of efficient methods for the synthesis of unnatural amino acid derivatives.
[0005] Based on the usefulness of the above-described compounds, if would generally be advantageous to have methods of rapidly and efficiently synthesizing structurally diverse derivatives of these compounds, as well as libraries containing large numbers of these compounds. The present invention meets these and other needs.
[0006] The importance of multi-component reactions (MCR) has been demonstrated in the synthesis of various classes of organic molecules, especially in the area of combinatorial synthesis. These reactions enable to assemble three or more different building blocks, in most cases, in a single chemical process. The Ugi condensation reaction employs four components including a carboxylic acid, an amine, an aldehyde and an isocyanide to construct an α-acylaminoamide which can be transferred into the corresponding amino acid, ester and etc. The versatility of the reaction has also been demonstrated in the solid phase synthesis of a variety of biologically interesting structures by post Ugi transformations.
[0007] The methods of the invention employ a multi-component condensation reaction for the construction of the key intermediates on solid supports.
SUMMARY OF INVENTION
[0008] The invention is generally directed to novel methods of synthesizing diverse α-sulfonamido amide, carboxylic acid and hydroxamic acid derivatives. Typically, the methods of the invention employ a multi-component condensation reaction for the construction of the key intermediates on solid supports. Instead of amines (e.g., alkyl amine or aniline), according to the invention sulfonamides are the first time employed in the four-component condensation reaction. This four-component reaction (a sulfonamide, an aldehydet or ketone, an isocyanide and an acid) enables one to generate a sulfonamido amide-type intermediate in one-step on solid support (FIGS. 1 and 2).
[0009] Either of the four components can be attached to the solid support, which reacts with other three reagents (FIG. 2). Further chemical manipulation, such as treatment with a base to remove the acyl moiety followed by N-alkylation, such as the Mitsunobu reaction, gives polymer-bound products, which are then cleaved on the solid support under various cleavage conditions.
[0010] The present invention also provides methods of preparing libraries of diverse α-sulfonamido amide, carboxylic acid and hydroxamic acid derivatives. The method of synthesizing a library of α-sulfonamido amide, carboxylic acid or hydroxamic acid derivatives comprising providing a set of polymer-bound reactant(s) (sulfonamide, aldehyde or ketone, isocyanide or acid) to react with three sets of the other three reactants to form an array of polymer-bound α-sulfonamido amide-type intermediates. Further chemical manipulation may be applied, which comprises the treatment with a base for removal of the acyl moiety and N-alkylation gives polymer-bound highly functionalized products. A library of the diverse products is then released from the solid support under various cleavage conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [0011]FIG. 1 illustrates the four components of the condensation reaction and corresponding polymer bound forms;
[0012] [0012]FIG. 2 illustrates the solid phase four-component condensation reaction utilizing one of the polymer-bound components;
[0013] [0013]FIG. 3 illustrates cleavage of the product without the acyl moiety where R 4 is attached to the solid support;
[0014] [0014]FIG. 4 illustrates cleavage of the product with the acyl moiety where R 1 , or R 2 , or R 5 is attached to solid support; and
[0015] [0015]FIG. 5 illustrates the preparation of α-sulfonamido carboxylic acids or the corresponding hydroxamic acids
DETAILED DESCRIPTION OF INVENTION
[0016] [0016]FIG. 1 illustrates the four components (sulfonamide of formula 1-1, aldehyde or ketone of formula 1-2, carboxylic acid of formula 1-3 and isocyanide of formula 1-4) utilized in the condensation reactions. The corresponding polymer-bound forms are presented as formula 1-5, 1-6, 1-7 and 1-8, respectively.
[0017] [0017]FIG. 2 illustrates the solid phase four-component condensation reaction utilizing one of the polymer-bound components (1-5 to 1-8). The newly formed product is described as formula 2-1, wherein R 1 , or R 2 , or R 4 , or R 5 is attached to the polymer.
[0018] If R 4 of formula 2-1 is attached to the polymer, the polymer-bound intermediate 2-1 is then treated with an appropriate base, such as amine, to cleave the product without the acyl moiety as illustrated in FIG. 3. A free carboxylic acid can be produced by acidic hydrolysis when a convertible isocyanide (R 5 NC) is used in the first step reaction.
[0019] If R 1 , or R 2 , or R 5 is attached to solid support, the polymer-bound intermediate 2-1 is then treated with an appropriate base, such as amine, to cleave the acyl moiety as illustrated in FIG. 4. An intermediate of formula 4-1 undergoes N-alkylation reaction, such as the Mitsunobu reaction in the presence of R 6 OH, to give a product of formula 4-2 which is then cleaved under an appropriate condition to afford a product of formula 4-3.
[0020] [0020]FIG. 5 illustrates the preparation of α-sulfonamido carboxylic acids or the corresponding hydroxamic acids. A polymer-bound intermediate 4-2 can be transformed to a carboxylic acid or a hydroxamic acid of formula 5-1 if R 5 is introduced from a convertible isocyanide. A subsequent cleavage gives the desired acid or hydroxamic acid of formula 5-2. Alternatively, a product of formula 5-2 can be obtained from an intermediate of formula 5-3 in which R 5 is attached to the solid support.
[0021] The solid support, represented by P, is intended to include the following:
[0022] a.) beads, pellets, disks, fibers, gels, or particles such as cellulose beads, pre-glass beads, silica gels, polypropylene beads, polyacrylamide beads, polystyrene beads that are lightly cross-linked with 1-2% divinylbenzene and optionally grafted with polyethylene glycol and optionally functionalized with amino, hydroxy, carboxy or halo groups; and
[0023] b.) soluble supports such as low molecular weight non-cross-linked polystyrene and polyethylene glycol.
[0024] The term solid support is used interchangeably with the term resin or bead in this invention and is intended to mean the same thing.
[0025] X is an atom or a functional group connecting the polymer and the linker L, having a structure such as but not limited to oxygen, ester, amide, sulfur, silicon and carbon;
[0026] L is a suitable linker, a multifunctional chemical monomer in which one functional group reacts with the polymer to form a covalent bond (X) and the other functional groups react with one of R groups (R 1 , R 2 , R 4 , or R 5 ) through a plurality of chemical reactions to provide the desired templates for further chemistry. Both X and R groups can be represented within a suitable monomer L, such as an amino acid; Commercially available resins, like Wang and Hydroxymethyl polystyrene, are useful in this method. The linkers present in these resins allow the cleavage of final products by a variety of mild chemical conditions that allow isolation of compounds of this invention. The hydroxymethyl polystyrene resin and the Wang resin are examples of solid phase supports used in the preparation of compounds of this invention. Other known or commercially available solid phase supports work in this method and are considered to lie within the scope of this invention.
[0027] Solid Support
[0028] Solid support is a substrate consisting of a polymer, cross-linked polymer, functionalized polymeric pin, or other insoluble material. These polymers or insoluble materials have been described in literature and are known to those who are skilled in the art of solid phase synthesis (Stewart J M, Young J. D.; Solid Phase Peptide Synthesis, 2nd Ed; Pierce Chemical Company: Rockford. Ill., 1984). Some of them are based on polymeric organic substrates such as polyethylene, polystyrene, polypropylene, polyethylene glycol, polyacrylamide, and cellulose. Additional types of supports include composite structures such as grafted copolymers and polymeric substrates such as polyacrylamide supported within an inorganic matrix such as kieselguhr particles, silica gel, and controlled pore glass.
[0029] Examples of suitable support resins and linkers are given in various reviews (Barany, G.; Merrifield, R. B. “Solid Phase Peptide Synthesis”, in “The Peptides—Analysis, Synthesis, Biology”. Vol 2, [Gross, E. and Meienhofer, J., Eds.], Academic Press, Inc., New York, 1979, pp 1-284; Backes, B. J.; Ellman, J. A. Curr. Opin. Chem. Biol. 1997. 1, 86; James, I. W., Tetrahedron 1999, 55, 4855-4946) and in commercial catalogs (Advanced ChemTech, Louisville, Ky.; Novabiochem, San Diego, Calif.). Some examples of particularly useful functionalized resin/linker combinations that are meant to be illustrative and not limiting in scope are shown below:
[0030] (1) Aminomethyl polystyrene resin (Mitchell, A. R., et al., J. Org. Chem., 1978, 43, 2845):
[0031] This resin is the core of a wide variety of synthesis resins. The amide linkage can be formed through the coupling of a carboxylic acid to amino group on solid support resin under standard peptide coupling conditions. The amide bond is usually stable under the cleavage conditions for most acid labile, photo labile and base labile or nucleophilic linkers.
[0032] (2) Wang resin (Wang, S. S.; J. Am. Chem. Soc. 1973, 95, 1328
[0033] -1333). Wang resin is perhaps the most widely used of all resins for acid substrates bound to the solid support resin. The linkage between the substrate and the polystyrene core is through a 4-hydroxybenzyl alcohol moiety. The linker is bound to the resin through a phenyl ether linkage and the carboxylic acid substrate is usually bound to the linker through a benzyl ester linkage. The ester linkage has good stability to a variety of reaction conditions, but can be readily cleaved under acidic conditions, such as by using 25% TFA in DCM.
[0034] (3) Rink resin (Rink, H.; Tetrahedron Lett. 1987, 28, 3787).
[0035] Rink resin is used to prepare amides utilizing the Fmoc strategy. It has also found tremendous utility for a wide range of solid phase organic synthesis protocols. The substrate is assembled under basic or neutral conditions, then the product is cleaved under acidic conditions, such as 10% TFA in DCM.
[0036] (4) Knorr resin (Bernatowicz, M. S., et al. Tetrahedron Lett., 1989, 30, 4645).
[0037] Knorr resin is very similar to Rink resin, except that the linker has been modified to be more stable to TFA.
[0038] (5) PAL resin (Bernatowicz, M. S., et al. Tetrahedron lett., 1989, 30, 4645).
[0039] (6) HMBA-MBHA Resin (Sheppard, R. C., et al., Int. J. Peptide Protein Res. 1982, 20, 451).
[0040] (7) HMPA resin. This also is an acid labile resin which provides an alternative to Wang resin and represented as:
[0041] (8) Benzhydrylamine copoly(styrene-1 or 2%-divinylbenzene) which referred to as the BHA resin (Pietta, P. G., et al., J. Org. Chem. 1974, 39, 44).
[0042] (9) Methyl benzhydrylamine copoly(styrene-1 or 2%-divinylbenzene) which is referred to as MBHA and represented as:
[0043] (10) Trityl and functionalized Trityl resins, such as aminotrityl resin and amino-2-chlorotrityl resin (Barlos, K.; Gatos, D.; Papapholiu, G.; Schafer, W.; Wenqing, Y.; Tetrahedron Lett. 1989, 30, 3947).
[0044] (11) Sieber amide resin (Sieber, P.; Tetrahedron Lett. 1987, 28, 2107).
[0045] (12) Rink acid resin (Rink, H., Tetrahedron Lett., 1987, 28, 3787).
[0046] (13) HMPB-BHA resin (4-hydroxymethyl-3-methoxyphenoxybutyric acid-BHA Florsheimer, A.; Riniker, B. in “Peptides 1990; Proceedings of the 21st European Peptide Symposium”, [Giralt, E. and Andreu, D. Eds.], ESCOM, Leiden, 1991, pp 131.
[0047] (14) Merrifield resin—Chloromethyl co-poly(styrene-1 or 2%-divinylbenzene) which can be represented as:
[0048] A carboxylic acid substrate is attached to the resin through nucleophilic replacement of chloride under basic conditions. The resin is usually stable under acidic conditions, but the products can be cleaved under basic and nucleophilic conditions in the presence of amine, alcohol, thiol and H 2 O.
[0049] (15) Hydroxymethyl polystyrene resin (Wang, S. S., J. Org. Chem., 1975, 40, 1235).
[0050] The resin is an alternative to the corresponding Merrifield resin, whereas the substrate is attached to a halomethylated resin through nucleophilic displacement of halogen on the resin, the attachment to hydroxymethylated resins is achieved by coupling of activated carboxylic acids to the hydroxy group on the resin or through Mitsunobu reactions. The products can be cleaved from the resin using a variety of nucleophiles, such as hydroxides, amines or alkoxides to give carboxylic acids, amides and esters.
[0051] (16) Oxime resin (DeGrado, W. F.; Kaiser, E. T.; J.Org. Chem. 1982, 47,
[0052] 3258).
[0053] This resin is compatible to Boc chemistry. The product can be cleaved under basic conditions.
[0054] (16) Photolabile resins (e.g. Abraham, N. A. et al.; Tetrahedron Lett. 1991, 32, 577). The products can be cleaved from these resins photolytically under neutral or mild conditions, making these resins useful for preparing pH sensitive compounds. Examples of the photolabile resins include
[0055] (a) ANP resin:
[0056] (b) alpha-bromo-alpha-methylphenacyl polystyrene resin:
[0057] (17) Safety catch resins (see resin reviews above; Backes, B. J.; Virgilio, A. A.; Ellman, J. Am. Chem. Soc. 1996, 118, 3055-6). These resins are usually used in solid phase organic synthesis to prepare carboxylic acids and amides, which contain sulfonamide linkers stable to basic and nucleophilic reagents. Treating the resin with haloacetonitriles, diazomethane, or TMSCHN 2 activates the linkers to attack, releasing the attached carboxylic acid as a free acid, an amide or an ester depending on whether the nucleophile is a hydroxide, amine, or alcohol, resepectively. Examples of the safty catch resins include:
[0058] (a) 4-sulfamylbenzoyl-4′-methylbenzhydrylamine resin:
[0059] (b) 4-sulfamylbutryl-4′-methylbenzhydrylamine resin:
[0060] (18) TentaGel resins:
[0061] TentaGel resins are polyoxycthyleneglycol (PEG) grafted (Tentagel) resins (Rapp, W.; Zhang, L.; Habich, R.; Bayer, E. in “Peptides 1988; Proc. 20 tth European Peptide Symposium” [Jung, G. and Bayer, E., Eds.], Walter de Gruyter, Berlin, 1989, pp 199-201. TentaGel resins, e.g. TentaGel S Br resin can swell in a wide variety of solvents and the bead size distribution is very narrow, making these resins ideal for solid phase organic synthesis of combinatorial libraies. TentaGel S Br resin can immobilize carboxylic acids by displacing the bromine with a carboxylic acid salt. The products can be released by saponification with dilute aqueous base.
[0062] (19) Resins with silicon linkage (Chenera, B.; Finkelstein, J. A.; Veber, D. F.; J. Am. Chem. Soc. 1995, 117, 11999-12000; Woolard, F. X.; Paetsch, J.; Ellman, J. A.; J. Org. Chem. 1997, 62, 6102-3). Some examples of these resins contain protiodetachable arylsilane linker and traceless silyl linker. The products can be released in the presence of fluoride.
[0063] Also useful as a solid phase support in the present invention are solubilizable resins that can be rendered insoluble during the synthesis process as solid phase supports. Although this technique is frequently referred to as “Liquid Phase Synthesis”, the critical aspect for our process is the isolation of individual molecules from each other on the resin and the ability to wash away excess reagents following a reaction sequence. This also is achieved by attachment to resins that can be solubilized under certain solvent and reaction conditions and rendered insoluble for isolation of reaction products from reagents. This latter approach, (Vandersteen, A. M.; Han, H.; Janda, K. D.; Molecular Diversity, 1996, 2, 89-96.) uses high molecular weight polyethyleneglycol as a solubilizable polymeric support and such resins are also used in the present invention.
EXAMPLES
[0064] The following examples (Schemes 6, 7 and 8) are by way of illustration of various aspects of the present invention and are not intended to be limiting thereof.
[0065] General Procedures-Reagent Systems and Test Methods
[0066] Anhydrous solvents were purchased from Aldrich Chemical Company and used directly. Resins were purchased from Advanced ChemTech, Louisville, Ky., and used directly. The loading level ranged from 0.60 to 1.0 mmol/g. Unless otherwise noted, reagents were obtained from commercial suppliers and used without further purification. Preparative thin layer chromatography was preformed on silica gel pre-coated glass plates (Whatman PK5F, 150 Å, 1000 μm) and visualized with UV light, and/or ninhydrin, p-anisaldehyde, ammonium molybdate, or ferric chloride. NMR spectra were obtained on a Varian Mercury 500 MHz spectrometer. Chemical shifts are reported in ppm. unless otherwise noted, spectra were obtained in CD 3 OD with residual CH 3 OH as an internal standard at 7.26 ppm. IR spectra were obtained on a Midac M1700 and absorbencies are listed in inverse centimeters. HPLC/MS analysis were performed on a Hewlett Packard 1100 with a photodiode array detector coupled to a Micros Platform II electrospray mass spectrometer. An evaporative light scattering detector (Sedex 55) was also incorporated for more accurate evaluation of sample purity. Reverse phase columns were purchased from YMC, Inc. (ODS-A, 3 μm, 120 Å, 4.0×50 mm).
[0067] Solvent system A consisted of 97.5% MeOH, 2.5% H 2 O, and 0.05% TFA. Solvent system B consisted of 97.5% H 2 O, 2.5% MeOH, and 0.05% TFA. Samples were typically acquired at a mobile phase flow rate of 2 ml/min involving a 2 minute gradient from solvent B to solvent A with 5 minute run times. Resins were washed with appropriate solvents (100 mg of resin/1 ml of solvent). Technical grade solvents were used for resin washing.
Example 1
t-Butyl 2-(4-aminocarbonylbenzenesulfonamido)-4-phenyl-butyramide
[0068] Preparation of Aminosulfonylbenzamide Rink Resin (9-1)
[0069] In a 250 mL reaction vessel of an ACT 90 peptide synthesizer, 5 g of Rink resin (4 mmol, 0.8 mmol/g) was introduced. The resin was treated with 50 mL of 20% piperidine in DMF (30 min, room temperature) to remove the Fmoc protecting group. The excess of the reagent was removed by filtration and the resin was washed with DMF (2×25 mL) then with methanol (1×25 mL) and DCM (3×25 mL). To the resin was added 24 mL (6 eq.) solution of 4-carboxybenzenesulfonamide (1.0M in DMF) containing equimolar amount (6 eq.) of HOBt. The resin suspension was then mixed for 2 h. The reagent solution was removed by filtration and the resin was washed and dried as previously mentioned. Negative Kaiser test indicated complete conversion. Loading of the obtained resin, determined by TFA cleavage of a resin sample, was 0.5 mmol/g.
[0070] As illustrated in Scheme 10, aminosulfonylbenzamide Rink resin (9-1) was used as amine component in Ugi reaction for the synthesis of substituted sulfonamides (Example 1). The resin (1 g, 0.5 mmol) in a 40 ml vial was swelled with 5 mL THF. Then 5 mL of 3-phenylpropanal (10
[0071] eq., 1.0 M solution in MeOH), 50 mL of acetic acid solution (10 eq., 1.0 M in THF), and 5 mL of t-butyl isocyanide solution (10 eq., 1.0 M in MeOH) were added. The suspension was mixed on an ACT Labmate at 60° C. for 24 h. Then, the excess of the reagent solution was removed by filtration and the resin was washed and dried. The acetyl group was removed by treatment with a mixture of 48% aqueous methylamine solution and THF (10 mL, 1:1) overnight at room temperature. The desired sulfonamide was cleaved by treatment with TFA (25% solution in DCM) for 30 minutes. The product was isolated by evaporation of the TFA solution. 1 HNMR (CD 3 OD): δ 7.94-8.11 (m, 4H), 7.10-7.32 (m, 5H), 3.78-3.85 (m, 1H), 2.73 (m, 1H), 2.61 (m, 1H), 1.94 (m, 1H), 1.86 (m, 1H), 1.15 (s, 9H).
Example 2
t-Butyl 2-(4-aminocarbonylbenzenesulfonamido)-2-cyclohexylacetamide
[0072] The same procedure described for the preparation of Example 1 was followed except that cyclohexanecarboxaldehyde was used instead of 3-phenylpropanal. LC-MS analysis showed that the purity of the final cleaved product was more than 80%.
Example 3
t-Butyl 2-(4-aminocarbonylbenzenesulfonamido)-2-phenyl-acetamide
[0073] The same procedure described for the preparation of Example 1 was followed except that benzaldehyde was used instead of 3-phenyl propanal. 1 HNMR (CD 3 OD): δ 7.95 (d, J=8 Hz, 2H), 7.88 (d, J=8 Hz, 2H), 7.23-7.26 (m, 5H), 4.94 (s, 1H), 1.14 (s, 9H).
Example 4
iso-Propyl 2-(4-aminocarbonylbenzenesulfonamido)-4-phenylbutyramide
[0074] The same procedure described for the preparation of Example 1 was followed except that isopropyl isocyanide was used instead of t-butyl isocyanide. 1 HNMR (CD 3 OD): δ 8.01 (d, J=8.5 Hz, 2H), 7.92 (d, J=8.5 Hz, 2H), 7.08-7.22 (m, 5H), 3.73-376 (dd,1H), 3.62-367 (m, 1H), 2.62-2.68 (m, 1H), 2.48-2.54 (m, 1H), 1.78-1.89 (m, 2H), 0.99 (d, J=6.5 Hz, 3H).
Example 5
n-Butyl 2-(4-aminocarbonylbenzenesulfonamido)-4-phenyl-butyramide
[0075] The same procedure described for the preparation of Example 1 was followed except that n-butyl isocyanide was used instead of t-butyl isocyanide. 1 HNMR (CD 3 OD): δ 8.01 (d, J=8 Hz, 2H), 7.91 (d, J=8 Hz, 2H), 7.06-7.22 (m, 5H), 4.21 (dd, 1H), 2.91(m, 2H), 2.60 (m, 1H), 2.50 (m, 1H), 0.87-1.80 (m, 9H).
Example 6
Cyclohexyl 2-(4-aminocarbonylbenzenesulfonamido)-4-phenylbutyramide
[0076] The same procedure described for the preparation of Example 1 was followed except that cyclohexyl isocyanide was used instead of t-butyl isocyanide. 1 HNMR (CD 3 OD): δ 8.00 (d, J=8.5 Hz, 2H), 7.86(d, J=8.5 Hz, 2H), 7.09-7.24 (m, 5H), 3.75-3.77 (dd, 1H), 3.28 (m, 1H), 2.63-2.68 (m, 1H), 2.49-2.55 (m, 1H), 0.90-1.90 (m, 12H).
Example 7
Benzyl 2-(4-aminocarbonylbenzenesulfonamido)-4-phenyl-butyramide
[0077] The same procedure described for the preparation of Example 1 was followed except that benzyl isocyanide was used instead of t-butyl isocyanide. 1 HNMR (CD 3 OD): δ 7.98 (d, J=8 Hz, 2H), 7.91 (d, J=8 Hz, 2H), 7.03-7.27 (m, 10H), 4.16 (d, J=12 Hz, 1H), 4.10 (d, J=12 Hz, 1H), 3.81 (m, 1H), 1.35 (m, 2H)., 0.92 (m, 2H).
Example 8
t-Butyl 2-benzenesulfonamido-4-phenylbutyramide
[0078] [0078]
[0079] The preparation of Example 8 is illustrated in Scheme 11, in an 8 mL vial carboxypolystyrene resin (11-1) (100 mg) was swelled in 2 mL of THF. Then 2 mL of benzenesulfonamide solution (10 equiv., 1.0 M in THF), 2 mL of 3-phenylpropanal solution (10 equiv., 1.0 M in MeOH), and 2 mL of t-butyl isocyanide solution (10 equiv., 1.0 M in MeOH) were added. The suspension was mixed on an ACT Labmate at 60° C. for 24 h. Then the excess of reagent solution was removed by filtration and the resin (11-2) was washed and dried. The desired product was cleaved by treatment with a mixture of 48% aqueous methylamine and THF (2 mL, 1:1) for 12 h at room temperature. 1 HNMR (CD 3 OD): δ 7.53-7.87 (m, 5H), 7.08-7.24 (m, 5H), 3.74 (t, 1H), 2.64(m, 1H), 2.48(m, 1H), 1.86 (m, 1H), 1.75 (m, 1H), 1.14 (s, 9H).
Example 9
t-Butyl 2-(4-nitrobenzenesulfonamido)-4-phenylbutyramide
[0080] The same procedure described for the preparation of Example 8 was followed except that 4-nitrobenzensulfonamide was used instead of benzenesulfonamide. 1 HNMR (CD 3 OD): δ 8.35-7.13 (m, 9H), 3.894 (m, 1H), 2.64(m, 1H), 2.69(t, 2H), 2.01 (m, 1H), 1.82 (m, 1H), 1.75 (m, 1H), 1.36(s, 9H).
Example 10
t-Butyl 2-(2-nitrobenzenesulfonamido)-4-phenyl-butyramide
[0081] The same procedure described for the preparation of Example 8 was followed except that 2-nitrobenzensulfonamide was used instead of benzenesulfonamide. 1 HNMR (CD 3 OD): δ 8.08 (d, J=8 Hz, 1H), 7.91(d, J=8 Hz, 1H), 7.74-7.83 (m, 2H), 7.13-7.25 (m,5H), 3.92 (m, 1H),2.71 (m, 1H), 2.58(m, 1H), 1.95 (m, 1H), 1.88 (m, 1H), 1.11 (s, 9H).
Example 11
t-Butyl 2-[2-(methylaminocarbonyl)benzenesulfonamido]-4-phenylbutyramide
[0082] The same procedure described for the preparation of Example 8 was followed except that 2-(methoxycarbonyl)-benzensulfonamide was used instead of benzenesulfonamide. 1 HNMR (CD 3 OD): δ 7.93 (d, J=8 Hz, 1H), 7.73(d, J=8 Hz, 1H), 7.55-7.62 (m, 2H), 7.09-7.23 (m,5H), 3.82 (t, 1H),2.71 (m, 1H), 2.94(m, 3H), 2.68 (m, 1H), 2.55(m, 1H), 1.90 (m, 1H), 1.83 (m, 1H), 1.11 (s, 9H).
Example 12
t-Butyl 2-(4-hydroxybenzenesulfonamido)-4-phenyl-butyramide
[0083] The same procedure described for the preparation of Example 8 was followed except that 4-hydroxybenzensulfonamide was used instead of benzenesulfonamide. 1 HNMR (CD 3 OD): δ 7.67-7.69 (m, 2H), 7.21-7.22 (m, 2H), 7.12-7.15 (m, 1H), 3.66 (t, 1H),2.64 (m, 1H), 2.49 (m, 1H), 1.85 (m, 1H), 1.74 (m, 1H), 1.17 (s, 9H).
Example 13
t-Butyl 2-(4-acetamidobenzenesulfonamido)-4-phenyl-butyramide
[0084] The same procedure described for the preparation of Example 8 was followed except that 4-acetamidobenzensulfonamide was used instead of benzenesulfonamide. LC-MS analysis indicated that the desired product was obtained in more than 80% purity.
Example 14
t-Butyl 2-(4-methoxybenzenesulfonamido)-4-phenyl-butyramide
[0085] The same procedure described for the preparation of Example 8 was followed except that 4-methoxybenzensulfonamide was used instead of benzenesulfonamide. LC-MS analysis indicated that the desired product was obtained in more than 80% purity.
Example 15
t-Butyl 2-[N-methyl-N-(4-aminocarbonyl)-benzene-sulfonyl]amino-4-phenylbutyramide
[0086] [0086]
[0087] Preparation of Example 15 is illustrated in Scheme 12, the resin intermediate (10 −2 ) was alkylated with benzyl alcohol under the Mitsunobu reaction conditions. The resin (10 −2 ) (200 mg) was introduced into an 8 mL vial. To it were added 1 mL of methanol solution (10 equiv., 1.0 M in THF), 1 mL of triphenylphosphine solution (10 equiv., 1.0 M in THF), and 1 mL of DIAD solution (10 equiv., 1.0 M in THF). The suspension was mixed on an ACT Labmate at room temperature for 5 h. Then the excess of the reagent solution was removed by filtration; the resin (12-1) was washed and dried. Sulfonamide (Example 15) was cleaved by treatment with 25% TFA in DCM for 30 min at room temperature. 1 HNMR (CD 3 OD): δ 8.04 (d, J=7 Hz, 2H), 7.89 (d, J=7 Hz, 2H), 7.11-7.38 (m, 5H), 4.38 (t, 1H), 3.00 (s, 3H), 2.50 (t, 2H), 1.97-2.01 (m, 1H), 1.70-1.74 (m, 1H), 1.21 (s, 9H).
Example 16
t-Butyl 2-[N-butyl-N-(4-aminocarbonyl)-benzene-sulfonyl]amino-4-phenylbutyramide
[0088] The same procedure described for the preparation of Example 15 was followed except that n-butyl alcohol was used instead of methonal. 1 HNMR (CD 3 OD): δ 8.00-8.02 (d, J=8.5 Hz, 2H), 7.83-7.85 (d, J=8.5 Hz, 2H), 7.03-7.25 (m, 5H), 4.21 (m, 1H), 3.55(m, 1H), 3.24 (m, 1H), 1.52-2.50 (m, 8H), 1.27 (s, 9H), 0.92 (t, 3H).
Example 17
t-Butyl 2-[N-(2-benzyloxyethyl)-N-(4-aminocarbonyl)-benzenesulfonyl]amino-4-phenylbutyramide
[0089] The same procedure described for the preparation of Example 15 was followed except that benzyloxyethyl alcohol was used instead of methonal. 1 HNMR (CD 3 OD): δ 8.00 (d, J=8 Hz, 2H), 7.88(d, J=8 Hz, 2H), 6.99-7.32 (m, 10 H), 4.45-4.53 (dd, J=11.50 Hz, 2H), 4.21-4.24 (m, 1H), 3.80 (m, 1H), 3.68 (m, 2H), 3.53-3.56 (m, 1H), 1H), 2.46 (m, 2H), 2.06 (m, 1H), 1.68 (m, 1H), 1.21 (s, 9H).
Example 18
t-Butyl 2-[N-cyclohexyl-N-(4-aminocarbonyl)-benzene-sulfonyl]amino-4-phenylbutyramide
[0090] The same procedure described for the preparation of Example 15 was followed except that cyclohexyl alcohol was used instead of methonal. 1 HNMR (CD 3 OD): δ 7.90 (d, J=8 Hz, 2H), 7.86(d, J=8 Hz, 2H), 7.001-7.25 (m, 5H), 3.99 (m, 1H), 3.54(m, 1H), 1.30-2.50 (m, 14H), 1.32 (s, 9H).
[0091] As will be understood by those skilled in the art, various arrangements which lie within the spirit and scope of the invention other than those described in detail in the specification will occur to those persons skilled in the art. It is therefor to be understood that the invention is to be limited only by the claims appended hereto. Accordingly, we claim:
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A method of synthesizing α-sulfonamido amide, carboxylic acid or hydroxamic acid derivatives comprising providing a set of polymer-bound reactant(s) (sulfonamide, aldehyde or ketone, isocyanide or acid) to react with three sets of the other three reactants to form an array of polymer-bound α-sulfonamido amide-type intermediates and use of such intermediates for the preparation of combinatorial libraries.
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This application is a continuation application of U.S. patent application Ser. No. 10/375,956, filed Feb. 28, 2003 now abandoned, which is a continuation application of abandoned U.S. patent application Ser. No. 09/825,371, filed Apr. 3, 2001, which is a continuation of U.S. patent application Ser. No. 09/624,745, filed Jul. 25, 2000, which issued as U.S. Pat. No. 6,211,133 on Apr. 3, 2001.
FIELD OF THE INVENTION
The present invention relates to novel solvent systems capable of dissolving bituminous buildup on paving and roofing equipment. These solvents are characterized in being non-hazardous, non-toxic, and environmentally safe. Mixtures comprising noncyclic monoterpenes and anionic detergents provide effective cleaning and conditioning.
BACKGROUND OF THE INVENTION
Bituminous products are widely used in the construction field, and constitute one of the major commodity products in building and road construction. These materials are derived from the residue remaining after crude oil is refined to remove various distillates. Over the past twenty years, there have been many innovations in bituminous materials used in roofing and paving. The principle objectives of these developments are to increase strength and durability, ductility, reduce “creep”, cracking, and surface wear. A typical asphalt shingled roof requires replacement after 12-18 years, and road damage to asphalt may be detected within even the first year of paving. New compositions have substantially extended the lifespan of these materials
Many of the new asphalt materials contain synthetic polymers to create chemical links (both covalent and non-covalent interactions) between the long chain hydrocarbons, thus providing molecular strength. U.S. Pat. No. 5,556,900 discloses a thermoplastic polymer-linked asphalt in which the asphalt is reacted with an epoxide polymer resulting in a composition with low gelation, high emulsion forming capacity, and improved rheology. Heat treatment at 135 degrees C., results in covalent bonding between the polymer and the asphalt. In other polymer-containing bitumens, there is typically non-covalent adhesion binding of components.
For example, U.S. Pat. No. 5,473,000 teaches a method for improving bitumen by adding to asphalt a thermoplast or thermoelastomer, and a wood resin, resulting in enhanced binding properties. A linear polyethylene modified asphaltic composition is disclosed in U.S. Pat. No. 4,868,233, which has improved storage stability and creep resistance. Another polymer additive approach is disclosed in U.S. Pat. No. 5,322,867 for a bituminous mixture containing a polymer comprising one block of a conjugated diolefin methacrylate and a block of a functionalized acrylic monomer, giving improved properties over neat asphalt.
Some of the most significant developments in asphalt and tar composition involve various strategies for combining the strength and resiliency of latex polymers with bituminous materials. U.S. Pat. Nos. 4,485,201 and 5,436,285 disclose incorporation of finely divided rubber into asphalt compositions. In a variation, U.S. Pat. No. 5,811,477 utilizes reclaimed rubber particles, latex rubber, preferably styrene butadiene, and an aqueous asphalt emulsion to achieve low temperature processing, thereby reducing environmental contamination from latex volatiles.
U.S. Pat. Nos. 5,451,621 and 5,973,037 teach the infusion of particular latex polymers characterized as styrene-ethylene-butylene-styrene block copolymers into bituminous products, including asphalt, to raise the softening point of the blend and increase resistance to ultraviolet radiation, ozone, and fatigue. In yet another application of rubber in the asphalt art, U.S. Pat. No. 5,704,971 discloses the pretreatment of crumb rubber with peroxide, adding the treated rubber to asphalt in the presence of a compatibilized binder to produce an asphalt having improved settling properties of the binder, and reduced tendency to ravel.
While the objectives of improved durability, ductility, strength, and other related performance improvements, modification of bituminous substances has brought about new problems. The same molecular interactions which achieve enhanced stability and binding efficiency of the asphalt components, especially in the class of latex polymer blends known as SuperPave, also render the material extremely difficult to remove from paving equipment such as asphalt distributors and oilers, spreaders and the like, roofing manufacturing equipment and applications equipment. The buildup of these materials on equipment, particularly painted and bare metallic surfaces, leads to uneven dispensing, plugged nozzles, and impaired release of asphalt from distributors and spreaders. In many instances uneven distribution of asphalt in pavement requires repaving at substantial cost to the industry.
Classically, equipment has been cleaned by the use of common petroleum distillates such as kerosene, diesel fuel, or more purified fractions, and wood resin compounds such as turpentine. Usually cleaning with these substances requires mechanical intervention as by brushing, rubbing with cloth or abrasives Use of such conventional substances has led to environmental contamination and exposure of cleanup personnel to toxic, and even carcinogenic substances. Moreover, the extreme intractability of the advanced polymer blended bitumens to conventional cleaning solvents increases the volumes needed to soften and remove them from machinery surfaces. Incomplete removal of the asphalt results from the difficulty of conventional solvents to penetrate the asphalt matrix. This increases costs of cleanup to the industry, in terms of time and materials, and machine efficiency.
Much attention has been given to development of asphalt release agents that preventing sticking of bituminous materials to machinery. U.S. Pat. No. 5,900,048 discloses a release composition combining lethicin with a dispersing agent such as propylene glycol ethers or ether acetates. Other release agents have been proposed such as a combination of polycycloaliphatic amines and polyalkylene glycols (U.S. Pat. No. 5,961,730), cleaning by hydrogen peroxide together with iron catalysts (U.S. Pat. No. 5,725,687), fatty acids, in combination with preferably an anionic surfactant (U.S. Pat. No. 5,494,502, and a water based solution of magnesium chloride, a phosphate ester, an anionic alcohol surfactant (U.S. Pat. No. 5,322,554).
All of the foregoing release technologies have as a common strategy, forming a slippery barrier coating on a metal surface to prevent adhesion of asphalt, thus allowing it to slide readily from the treated surface. None of these compounds can be expected to appreciably penetrate the asphalt itself, except as a softener at the immediate undersurface. Thus, effective removal of asphalt already set on machinery is not addressed. A need exists for an effective asphalt removal agent, especially for modern bituminous polymer-containing formulations.
SUMMARY OF THE INVENTION
Immediately after compounding, asphalt is ductile and somewhat flowable, but stiffens and becomes less compactable as it sets. When fully set, asphalt is a dense mass, made more cohesive and fibrous by inclusion of polymer strands and other additives. These asphalts provide a formidable barrier to penetration of water and organic solvents. Such compositions bind tightly to solid surfaces, and can be scraped off only with great difficulty.
It is therefore an object of the present invention to provide an agent capable of penetrating and dissolving bitumens in situ without recourse to mechanical interventions such as chipping, wiping, brushing, or grinding. It is a further object to provide an agent which is easily applied to tar and asphalt coated metal or plastic surfaces without damage to the surface. Such agent will be fast acting and result in effectively complete removal. Most importantly, it is an object of the invention to provide an essentially harmless agent which is environmentally safe, non-toxic to clean-up personnel, and biodegradable.
The present composition comprises a mixture of one or more monocyclic monoterpenes (preferably one or more para-menthane dienes) which act as a carrier solvent, and a non-ionic detergent having sufficient hydophobicity to penetrate the bitumen matrix, and sufficient hydrophilicity to be soluble in the carrier. The detergent is preferably selected from alkylphenol ethoxylates and alkyl alcohol ethoxylates, or combinations of these substances. The detergent content is at least 2% by weight (w/w) but may vary from about 2% (w/w) to about 12% w/w).
The alkylphenol ethoxylates of the present invention comprise linear hydrocarbon moieties of chain length 1-13 carbon atoms and ethoxy repeat units ranging linearly from 1 to 23 groups. The structure is defined by the following formula:
wherein R is a linear alkyl radical, n is an integer 1-12, and x is an integer 2-23.
The alkyl alcohol ethoxylates of the invention have a structure defined by the formula: CH 3 (CH 2 ) x —CH 2 —O(CH 2 CH 2 O) y H wherein x is an integer 2-16 and y is an integer 2-14.
According to the method of the present invention, bituminous material may be effectively removed from solid surfaces to which they are bound, by applying to such surfaces the compositions disclosed herein, allowing the solvent compositions to incubate at temperatures ranging from about 1 degrees Fahrenheit (F.) to about 150 degrees F. on the surface of the adherent bitumen for at least 2 minutes up to about 1 hour, and rinsing with water. The application step may be repeated one or more times prior to a final water rinse.
In other embodiments, the present invention provides methods for removing asphalt or tar from a solid surface comprising providing a solid surface having tar or asphalt thereon and an undiluted mixture of a para-menthane diene and at least 2% w/w of a surfactant selected from the group consisting of an alkylphenol ethoxylate and an alkyl alcohol ethoxylate and combinations thereof; and applying the undiluted mixture of a para-menthane diene and at least 2% w/w of a surfactant selected from the group consisting of an alkylphenol ethoxylate and an alkyl alcohol ethoxylate and combinations thereof to the surface under conditions such that the tar or asphalt is removed.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is rectilinear plot showing the extent of asphalt removal as a function of the detergent content of the removal composition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In bitumen removal from equipment surfaces, the principal challenge is to penetrate the adherent material. Since asphalt and tar are endogenous to and ultimately obtained from crude oil, it has been assumed that the lighter refined fractions of oil would be the solvents of choice in “resolubilizing” the asphalt and tar fractions; hence, the widespread use petroleum distillates in cleaning tar and asphalt laden machinery. In addition to kerosene, distilled spirits, fuel oil, and diesel fuel, a few commercially formulated products have been on the market. Most of these products contain petroleum distillates immisible in water, and Applicant believes that an aqueous based detergent system may have been used. None of these are fully effective.
The present composition contains neither petroleum distillates nor water. However, the carrier monocyclic monoterpenes are highly hydrophilic and miscible in water. Thus, the water rinse carries away the phase compatible carrier after the dissolved bitumen has been absorbed by the hydrophobic alkyl moiety of the surfactant. While Applicant does not wish to be bound by any particular theory, it is believed that the hydrophilic moiety of the surfactant serves to anchor the molecule bearing its hydrocarbon absorbed hydrophobic moiety to the carrier stream.
The monocyclic monoterpenes belong to the family of substances known as “essential oils”. These compounds were distilled from aqueous infusions of various plant tissues such as flowers, fruits and leaves. The monocylic monoterpenes have the general menthane structure:
Some fourteen diene isomers having the para-menthane skeletal structure are possible, but only six occur in nature. In the present invention, three of the naturally occurring isomers are preferred: limonene (either as d-limonene or d1-limonene (dipentene)), terpinolene, and gama-terpinene. The isopropenyl-1-methyl cyclohexenes as a class are highly preferred and are functionally equivalent in the present composition. Limonene (4-isopropenyl-1-methyl-cyclohexene) is most preferred because of its excellent handling and blending properties, pleasant fragrance, and commercially available quantities.
Although the carrier properties of all the naturally-occurring monocyclic monoterpenes are expected to be similar (they have similar boiling points, solvency characteristics, and chemical properties), the aliphatic, un-derivativized isomers (such as the preferred class, the isopropenyl-1-methyl cyclohexenes) are much preferred over those having side chains appended to the pentane ring. “Un-derivatized” isomer means an aliphatic chemical structurally characterized in having a para-pentane ring and two double bonds.
Also included in the scope of the present invention are mixtures of para-pentane diene isomers obtained by molecular rearrangments catalyzed by acids, bases, or absorption onto surfaces such as silica gel. Such catalytic rearrangments are well known in fatty acid chemistry and may favor predominance of conjugated isoforms. Any such mixtures are suitable for use in the present composition.
Of the dozens of potential surfactant candidates, the alkylphenol ethoxylates and alkyl alcohol ethoxylates were found in the present invention to have superior cleaning and stability properties. Being nonionic they are highly compatible with the non-ionic para-menthane diene carriers.
The preferred class of alkylphenol ethoxylates are linear molecules having a linear alkyl radical of 2 to 13 methylene groups, linked through a phenolic radical to an ethoxy chain of 2 to 23 linearly repeating units. The choice of alkyl and ethoxy chain length is influenced somewhat by the composition of the bitumen. The preferred surfactant is the 1-nonylphenol-6-ethoxylate having an average of 9.5 ethoxy groups. This material is readily available commercially, and known in the art as SURFONIC™ N-95, manufactured by the Huntsman Corporation.
A second class of preferred surfactants are the alkyl alcohol ethoxylates having a formula: CH 3 (CH 2 ) x CH 2 —O(CH 2 CH 2 O) y H wherein x is an integer from 2 to 16 and y is an integer 2 to 23. In a preferred compound x is 14 and y is 8, and is known in the art as L24-8. A series of compounds of different alkyl and ethoxy chain length are commercially available from Huntsman Corporation.
The surfactant may be added to carrier at concentrations up to 20% without appreciably altering viscosity and coating properties. However, the cleaning action is optimal between 2 and 6% w/w. Although cleaning efficacy has been tested up to 12%, no apparent advantage is served at the higher concentrations. Therefore, any concentration of surfactant is encompassed by the invention up to about 20%, a working range of at least about 2% up to about 10% is highly efficacious. Higher concentrations contribute little except higher costs of manufacture.
In the event that it is suspected that a surfactant of different alkyl or ethoxy chain length may improve performance, some minor experimentation may be carried out by those skilled in the art. In general, if a greater degree of hydrophobicity is desired, it is recommended that the ethoxy chain length be extended also. In a particular application, if a longer alkyl chain is employed, a 9.5 unit ethoxy chain should be tested first. If no clouding of the carrier is detected, the composition can be used directly. Such tests can readily be carried out in the field, or by adopting the laboratory scale assay set forth in the Examples. There will be no need of undue experimentation, as the tests are easy to perform, and a wide range of surfactants of the disclosed classes are commercially available.
Production of commercial quantities of the present composition is simple and straightforward. The carrier is placed in a mixing vessel, a predetermined amount of surfactant is added, and the components are blended to uniformity by mechanical agitation, or by a recirculating pump.
In the method of the present invention asphalt, tar or other bituminous material can be removed effectively from a solid surface by contacting the surfaces with the cleaning composition, incubating at 1-150 degrees F. for 3-10 minutes, applying a second or subsequent coating of the solvent, incubating for another or subsequent 3-10 minute period, and finally, rinsing with water. Contacting is most conveniently achieved a by simple spray, taking care to cover all exposed surfaces. An ordinary garden sprayer available at most ordinary hardware stores is quite adequate. Alternatively, application may be made by wiping, sponging, dipping or submerging small parts, tools, or pieces of machinery, and maintaining the exposure for commensurate periods, followed by a water rinse. Mechanical intervention as by rubbing, scrubbing, wire brushing, and the like is unnecessary, and may interfere with the solvent action. Another application contemplated by the invention is removal of crude oil buildup on oil rigs, and drilling parts.
The present composition is effective for removing bituminous residues, even in situations where machinery maintenance has been neglected and the deposits tar, asphalt, and oil have been allowed to build up over time. All manner of solid surfaces may be cleaned including metal, painted metal, certain plastics, glass, ceramics, wood, natural or synthetic fabric. It is safe for contact with skin since it is non-corrosive, non-toxic, and non-irritating Caution should be exercised in contacting certain plastics. It is safe for polyethylene or polyolefin plastics but it will dissolve polycarbonate and polystyrene plastics. In the water rinse step, immersion or rinsing by direct spray is adequate, although the use of a pressure spray 100-300 psi is recommended, and a high pressure spray of greater than 1000 psi is preferred.
Other advantages of the present invention will be apparent from the Examples which follow.
EXAMPLES
After numerous field tests of the present composition were conducted, and efficacy in tar and asphalt removal was reproducibly ascertained, a laboratory scale assay was designed to quantitate cleaning efficiency in comparison with conventional cleaning agents, and to optimize the amount of surfactant to be added to the carrier.
Example 1
A. Preparation of Test Strips
The assay utilizes test strips of stainless steel with dimensions 1.5 inches×2.0 inches× 1/32 inches. Immersions in solvents were carried out by placing the strips in clamps and immersing two thirds of the total area of the strip. This provides a total uniform area of exposure of 2.0 square inches (the 1/32 inch thickness of the strip was disregarded. The strips were desiccated and weighed with the clamp assembly, so that the strip itself would not be handled.
The asphalt used in these experiments was a standard commercially available material containing latex polymers called CRS28 manufactured by Patterson Oil Company, Sullivan, Mo. Upon procurement, each batch was cured by heating in a conventional laboratory oven for 7 days at 200 degrees F.
A bath of the cured latex polymer-containing SuperPave asphalt was heated to 175-180 degrees F. The strips were immersed in the molten asphalt to provide 2.0 square inches of exposure. Exposure time was 2-3 seconds. The strips were cooled to room temperature and desiccated for 24 hours, and weighed. Each data point is the arithmetic average of ten strips treated identically.
B. Assay
The strips were immersed in the test solvents so that the entire asphalt coated areas were exposed to the solvent. The strips were withdrawn from the solution after 60 seconds and drained for 2 minutes. They were again immersed for 60 seconds and withdrawn. The strips were allowed to dry at room temperature for 2 hours and desiccated overnight. Dissections were performed in an ordinary bell jar in the presence of a standard commercial desiccant. The test strips were then reweighed. The data expressed in percent by weight of removal was calculated by subtracting the weight of the treated strip from the weight of the untreated strip and dividing by the weight of the untreated strip.
In this series of test, varying concentrations of Surfonic™ N-95 in d-limonene carrier were assayed for percent asphalt removal. The results are as follows:
Concentration surfactant Percent Removal 0.0 26.10 2.0 30.74 2.5 32.63 3.0 33.84 3.5 34.96 4.0 35.75 4.5 36.21 5.0 37.16 5.5 38.02 6.0 40.70 12.0 42.68
The results indicate that at concentrations of surfactant as low as 2 percent, there is a consistent increase in the amount of asphalt removed up to about 40%. Doubling the concentration at 6% does not improve removal appreciably, so that a range of 2% to 6% is optimal. FIG. 1 is a rectilinear plot of the above data, indicating that a concentration greater than 2% significantly enhances penetration of the carrier into the asphalt.
Example 2
A control experiment was conducted according to the same test protocol. AT10 is a product manufactured by Smith Systems Manufacturing and is believed by its physical properties to be a mixture of petroleum distillates. This product was compared with kerosene, diesel fuel and naphthalene. The percents of asphalt removal were 9.99, 9.17, 9.42, and 9.37 respectively.
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A non-toxic, non-hazardous, environmentally safe composition provides an effective, fast acting cleaning solution for removal of tar, oils, asphalt and other bituminous materials from industrial equipment surfaces. The composition is a mixture of a carrier monocyclic monoterpene and a nonionic surfactant such as an alkylphenol ethoxylate. The mixture is applied directly to surfaces to be cleaned, and rinsed with water in the absence of mechanical intervention.
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The present application is a continuation-in-part application No. PCT/US98/00910, filed on Jan. 23, 1998, which is a continuation-in-part of application Ser. No. 08/785,316, filed on Jan. 23, 1997, now U.S. Pat. No. 5,813,859, the disclosures of which are hereby incorporated by reference in their entireties.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the restoration of teeth, and more particularly, to methods and devices for improving the accuracy and simplifying the process of performing such restorations by machining a prosthetic, such as a crown or bridge.
2. State of the Art
Presently, numerous methods exist for the restoration of teeth by dentists, including the use of artificial tooth material (such as gold or porcelain) to form a cast-restoration or a metal-ceramic restoration (i.e., dental prosthetics such as crowns). Prosthetic crowns are typically used to repair decayed tooth structure where support from the original tooth structure is either marginal, or unavailable.
Known techniques for preparing a tooth to receive a crown are described in allowed, copending U.S. application Ser. No. 08/785,316, now U.S. Pat. No. 5,813,859, and in published international application PCT/US98/00910, both entitled “Method And Apparatus For Tooth Restoration”, the contents of which are hereby incorporated by reference in their entireties. As described therein, previously known techniques of tooth restoration are susceptible to numerous variables, some of which are within the dentist's control and some of which are not. All of these variables can detrimentally influence the accuracy with which: (1) the tooth is prepared to receive the crown; (2) the crown is prepared for placement on the tooth; and (3) the manner by which the crown is fit to and fixed on the prepared tooth.
Further, the quality of the prosthetic crown will vary based on the skill of the person who actually produces the crown (e.g., laboratory technician). More particularly, after the patient's tooth has been shaped to receive the prosthetic crown, an impression is formed from the prepared tooth by placing impression material into the patient's mouth (i.e., to form a negative impression of the prepared and adjacent teeth). To accurately prepare the impression, all gingival bleeding must be stopped and the margin of the gum tissue must be retracted from the lower portion of the tooth. The impression material must then be properly injected into the sulcus area of the tooth. A tray which contains a combination of impression materials is then applied with pressure over the teeth in the area of the prepared tooth, including the prepared tooth.
Despite efforts by the dentist to obtain an accurate impression of the prepared tooth, many factors can detrimentally influence quality of the impression. For example, the ability of the dentist to maintain a dry field of operation in the area of the prepared tooth can inhibit accuracy of the impression. The retraction of the gingival tissue can also affect the accuracy of the impression, as can the dentist's technique in obtaining the impression (i.e., the general care in obtaining an accurate impression).
Once the impression has been produced by the dentist, a laboratory technician will set die pins in the impression and then form a master impression as a die (e.g., plaster models) of the patient's tell. The technician will set the occlusal bite registration and articulate the models of the patient's teeth. Afterwards, the laboratory technician will saw the die to remove the tooth of interest, then trim the die of the tooth and mark the marginal finish line. The sub-structure is then waxed for preparation of the prosthetic crown.
After a wax pattern has been formed, it is converted (i.e., cast or machined) into a sub-structure (e.g., coping) of the crown. It is a challenge to produce a coping that will comply with acceptable tolerances, given the variables associated with the quality of the impression, the skill of the technician and the proper selection of die materials.
For example, U.S. Pat. No. 5,135,393, assigned to Mikrona, describes a coping mechanism for producing parts such as non-metal copings. As described therein, a three-dimensioned pattern is sensed (e.g., traced) with a feeler pin, and then sensed deflections or displacements of the feeler pin are transferred to a motor driven machining tool. As the pattern is traced, the motor driven machining tool operates upon a blank to fabricate a matching three-dimensional coping. The coping is later used by the dental laboratory to build-up a finished crown.
That is, once the machined coping has been produced, it is processed with a porcelain build-up. The build-up material incorporates specific shading and color effects to simulate the enamel of the original tooth. The porcelain build-up is then vacuum fired.
The combination of producing a coping, followed by building-up the coping with porcelain, are thus required to produce the prosthetic crown. The final stages of crown preparation include finishing the porcelain buildup, after which the anatomy of the original tooth structure is carved therein. The porcelain crown is then glazed. Where the crown is formed of cast metal, the cast exterior of the crown is sand-blasted to remove external oxidation. The metal interior is then polished and the fit, shading and prosthetics of the crown are quality checked. The finished crown is then returned to the dentist for placement onto the prepared tooth structure.
Processes which involve using devices such as those described in U.S. Pat. No. 5,135,393 are not practical for widespread use in dentistry for a variety of reasons. These devices involve complex and timely processes for producing a finished prosthetic suitable for placement in a patient's mouth.
For example, to produce a finished crown, the process described in the '393 patent requires: (1) initially making a dental impression of the patient's teeth; (2) producing a hand made pattern (i.e., template), such as a template of a three-dimensional dental coping from the impression; (3) using an apparatus as described in the '393 patent to produce a non-metal coping by tracing the template and concurrently machining an oversized blank; (4) building-up the machined, non-metal coping in a dental laboratory with a crown material, such as porcelain; (5) sintering the crown material on the non-metal coping and returning the finished crown to the dentist for final adjustment and placement in the patient's mouth.
Thus, while an apparatus as described in the '393 patent is useful in machining dental parts, it does little to reduce the time and complexity associated with producing finished dental prosthetics such as crowns and bridges. The process of shipping an impression from the dentist's office to the laboratory technician, the preparation of the crown and the returning of the crown to the dentist typically involves a period of approximately two weeks. Upon receipt of the prosthetic crown from the laboratory, the dentist removes a temporary crown which had been placed over the prepared tooth of the patient following preparation of the impression. The permanent crown is then cemented into place. The dentist's skill is again called upon to ensure proper fit, occlusion bite registration and aesthetics of the prosthetic crown. While the dentist can modify the occlusion of the crown, inaccuracies in fit can require that a new crown be prepared and the entire process described above repeated, thus leading to increased time delays and patient discomfort due to prolonged use of a temporary crown. In some cases, if the crown does not accurately fit, the dentist will use a bur to grind the interior; however, the use of a bur to shape the crown interior alters the fit and therefore detrimentally affects the marginal seal.
The inaccuracies associated with preparation of conventional crowns also affect the preparation and fitting of bridges. For example, where a bridge is formed using a dummy tooth (i.e., a pontic) anchored between two crowns, the inaccuracies in preparing the two crowns will affect the fit of bridge to the prepared teeth of the patient. The difficulties in accurately preparing the pontic will also have an affect on patient comfort. For example, gaps between the pontic and the patient's ridge structure will allow debris (e.g., food) to be trapped in areas which are difficult to clean.
In the case of root canals, conventional dental prosthetics suffer another disadvantage associated with the use of metal, such as steel posts to anchor the crown. The steel posts are used to reinforce the crown, by anchoring the crown into the tooth structure of the patient's mouth. However, because the steel posts are typically round in cross-section, they are susceptible to rotation within a post hole drilled in the patient's bone. As such, the post can loosen, and the crown can fall out of the patient's mouth. In addition, the post acts as a wedge which is driven into the patient's tooth structure when pressure is applied to a top surface of the crown. This pressure can cause the root structure of the patient to fracture over time. With regard to root canals performed on visible teeth of the patient, such as the front teeth of the patient, the steel post can produce a visible discoloration of the dental prosthetic, which detracts from the aesthetics of the dental prosthetic.
Thus, it would be desirable to improve the accuracy with which tooth restorations are performed. Further, it would be desirable to reduce the skill-dependent tasks associated with tooth restoration, and to reduce the cost associated with such procedures, without compromising the quality of these procedures. Ideally, it would be desirable to provide a process which would enable a prosthetic to be completely produced in a dental office, within the course of a day, and yet provide a more accurate, aesthetically pleasing dental prosthetic.
SUMMARY OF THE INVENTION
The present invention is directed to enhancing the accuracy with which tooth restorations are performed, including the manner by which a tooth is prepared and fit with a dental prosthetic, such as a crown or bridge. Further, the present invention is directed to reducing the skill-dependent tasks associated with tooth restoration, including root canals, while at the same time, improving the precision with which these procedures are performed and the aesthetics of the prosthetic. By improving the accuracy of restoration procedures, any need to repeat these procedures for a given patient can be eliminated and patient comfort can be improved. In addition, by improving the precision with which a prosthetic is prepared for attachment to the prepared tooth of a patient, and/or fit to patient, durability and longevity of the prosthetic are improved.
For example, when the interior of a prosthetic is not precisely fit to the prepared tooth of a patient, as in a case where the coping is undersized relative to the prepared tooth, buckling of the coping can occur. As a result, the buckling of the coping can cause the porcelain exterior of the prosthetic to crack. Because exemplary embodiments of the present invention provide a precise and accurate fit, they avoid such buckling of the prosthetic's interior, and therefore, improve the longevity of the prosthetic.
Exemplary embodiments of the present invention relate to a method and apparatus for producing a dental prosthetic, such as a dental bridge, wherein a method comprises steps of: providing a prosthetic pontic model; providing a prosthetic pontic blank having exterior dimensions matched to those of said prosthetic pontic model; forming an exterior recess of said prosthetic pontic model as template; and matching an exterior recess of said prosthetic pontic blank to said prosthetic pontic model. Exemplary embodiments in accordance with the present invention can provide a bridge formed with two crowns accurately fit to prepared teeth of a patient, and an accurately prepared pontic which is precisely fit between the two crowns and firmly attached within the patient's mouth.
Exemplary embodiments of the present invention also relate to a method and associated apparatus for producing a dental prosthetic, such as a crown to be used in connection with a root canal, comprising the steps of: applying light through a light guide to cure a light-curable material; attaching a preformed prosthetic model to said light guide and said light-curable material to form an exterior of said prosthetic model as a template; and matching an exterior of a prosthetic blank to said exterior of said prosthetic model.
Exemplary embodiments of the present invention further relate to an apparatus for producing a dental prosthetic comprising: means for holding a dental prosthetic model and a dental prosthetic blank having exterior dimensions matched to those of said prosthetic model; and means for machining a surface of said dental prosthetic blank to match a surface of said dental prosthetic model, said apparatus providing five axes of motion of said holding means relative to said machining means.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments when read in conjunction with the accompanying drawings, wherein like elements have been designated by like numerals, and wherein:
FIGS. 1A, 1 B, and 1 C illustrate a prosthetic model crown in accordance with exemplary embodiments of the present invention;
FIGS. 2A-2B illustrate exemplary embodiments of a method and apparatus for registering orientation, and for removing a prosthetic model or blank from a prepared tooth which can be used in accordance with an exemplary embodiment of the present invention;
FIG. 3 illustrates an exemplary embodiment of a copy milling apparatus in accordance with the present invention;
FIGS. 4A, 4 B, 4 C, 4 D, and 4 E illustrate an exemplary bridge construction in accordance with the present invention;
FIGS. 5A, 5 B, and 5 C illustrate an exemplary embodiment of a holder which can be used in accordance with the FIG. 3 embodiment; and
FIGS. 6A, 6 B, 6 C, 6 D, and 6 E illustrate additional features of a holder in accordance with exemplary embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
To illustrate a process for fitting a patient with a dental prosthetic, exemplary embodiments will be described in the context of a prosthetic dental crown (that is, an artificial substitute for the crown of a tooth, including veneers) which can, if desired, be used in conjunction with preparation of a bridge. However, those skilled in the art will appreciate that exemplary embodiments of the present invention can be used to produce any type of finished dental prosthetic, including inlays and onlays. To illustrate significant features which can be realized in accordance with exemplary embodiments of the present invention, reference is made to FIG. 1 A and the fitting of a patient with a dental crown.
In FIG. 1A, a patient's tooth 102 is illustrated. To prepare the tooth for receiving a dental crown, the tooth is milled by the dentist in conventional manner. For example, the tooth is milled to remove the portion represented by dashed lines 104 using, for example, a diamond bur of a high speed hand tool.
In contrast to conventional techniques whereby an impression was necessarily taken of the prepared tooth for purposes of having a dental laboratory produce a coping which could be built-up using a finished crown material (such as porcelain), exemplary embodiments of the present invention avoid any need to take such an impression. Rather, in accordance with exemplary embodiments, a prosthetic model is provided. In the FIG. 1A embodiment, where a dental crown is to be prepared, the prosthetic model corresponds to a dental crown (i.e., a prosthetic model crown 106 ).
The prosthetic model crown 106 is selected from a series of such prosthetic models, which can be configured in a range of sizes, shapes, shades and types that cover the most common tooth sizes, shapes and shades. The prosthetic models can be substantially prefinished (e.g., seventy percent completed), and can be formed of any material, including any plastic, metal, or porcelain material. The range of sizes and types of prosthetic model crowns at the dentist's disposal correspond in size and type to a range of prosthetic blanks from which final dental prosthetics can be machined. In other words, the sizes and types of prosthetic model crowns correspond one-to-one with the range of sizes and types of prosthetic blanks used to provide finished dental crowns. As those skilled in the art will appreciate, the prosthetic model crowns can be formed of a first material (such as plastic), while the prosthetic blanks from which the finished dental crowns are machined can be formed of a second, finished material (such as porcelain). Alternately, both the prosthetic model crowns and the prosthetic blanks can be formed of the same material. Any material which can be machined to an accuracy deemed satisfactory to the dentist can, of course, be used.
In accordance with an exemplary embodiment, the prosthetic model crown 106 is hollow, and can include a core plug 108 . The core plug 108 can be inserted into a hole of the prosthetic model crown which extends from a biting surface of the prosthetic model crown to an interior thereof. The core plug 108 can be used to assist the dentist in removing the prosthetic model crown from the prepared tooth 102 of the patient after an accurate fit of the prosthetic model crown has been achieved.
Once the patient's tooth has been prepared to receive a dental prosthetic, and a prosthetic model crown 106 has been selected from the range of available sizes and types, the prosthetic model crown 106 is filled with a formable material that allows the dentist to achieve an accurate fit of the prosthetic model crown to the patient's prepared tooth and/or a duplicate model thereof. For example, the prosthetic model crown 106 can be filled with an ultraviolet light curing material 110 , such as the material traditionally used for making dental impressions. As mentioned above, the prosthetic model crown can be produced with a hollow interior. Alternately, where the prosthetic model crown is provided to the dentist without a hollowed interior, the dentist can mill an interior of the prosthetic model crown to receive the ultraviolet light curing material. Those skilled in the art will appreciate that the accuracy of the milling is not critical, since the light cured material, once inserted into an interior of the prosthetic model crown, will fill in any gaps therein to ensure an accurate fitting to the prepared tooth. It is only necessary that an interior of the prosthetic model crown be hollowed to such a degree that allows the prosthetic model crown to completely fit over the prepared tooth.
Further, those skilled in the art will appreciate that a shoulder 112 of the prosthetic model crown can be initially provided, or can be milled, to a length shorter than the necessary height of the prosthetic blank. That is, the overall height “h” of the prosthetic model crown 116 can be intentionally configured shorter than the intended height of a prosthetic blank from which a finished dental crown will be machined. The use of a slightly shorter height for the prosthetic model crown will allow a gap to exist in a contact area between the bottom of the prosthetic model crown and the shoulder 116 of the tooth. As such, the dentist can apply light curing material to an interior of the prosthetic model crown and can allow a portion 114 of the light curing material 110 to protrude from an interior of the prosthetic model crown. The portion 114 of light curing material can be used to fill in the contact area between the shoulder 112 of the prosthetic model,crown and the shoulder 116 of the prepared tooth so that an accurate template of the shoulder can be obtained with the light curing material.
Once the prosthetic model crown has been filled with the ultraviolet light curing material 110 , the prosthetic model crown can be pressed over the prepared tooth, and aligned with adjacent teeth. When the dentist is satisfied with placement of the prosthetic model crown over the prepared tooth, the ultraviolet light curing material can be cured (i.e., exposed to ultraviolet light), and any excess material can be trimmed off (e.g., using a dental instrument). Further, exterior sides of the prosthetic model crown can be peripherally milled to adjust contact between the prosthetic model crown and adjacent teeth. As those skilled in the art will appreciate, because the shoulder 112 of the prosthetic model crown was formed to establish a gap in the contact area between the prosthetic model crown and the shoulder 116 of the prepared tooth, additional trimming of the light cured material in the shoulder contact area is unnecessary. Rather, placement of the prosthetic model crown to achieve accurate registration of occlusion (i.e., bite) can be achieved prior to, or subsequent to, curing of the light cured material.
In addition to trimming excess light cured material and milling exterior sides of the prosthetic model crown to achieve appropriate contact with adjacent teeth, top surfaces of the prosthetic model crown can also be spot milled as necessary to achieve more exact occlusion. In alternate embodiments, the prosthetic model crown can, for example, be formed with a top surface material which is different in color than material used to form the remainder of the prosthetic model crown. Consequently, any spot milling or grinding of the top surface of the prosthetic model crown will be readily noticed, and can be accurately measured, to enhance the accuracy with which a final prosthetic blank is milled.
For example, a top surface of the prosthetic model can be formed with a uniform thickness (e.g., one millimeter) of material having a first color (e.g., red plastic). The remainder of the prosthetic model crown can, for example be formed of a clear plastic. Consequently, where any spot grinding of the top surface of the prosthetic model crown exceeds 1 millimeter in depth, this will be readily apparent because the red top surface will now be clear in that spot. As such, these spots can be given special attention during preparation of a final prosthetic dental crown which is produced using the prosthetic model crown.
Once the prosthetic model crown has been properly trimmed and milled to achieve an exact fit, it can be removed from the prepared tooth 102 for use as a template in milling a prosthetic blank to produce a final prosthetic dental crown. In accordance with exemplary embodiments, the final prosthetic dental crown is produced by milling a prosthetic blank which has exterior dimensions matched to those of the prosthetic model (i.e., prior to fitting of the prosthetic model crown to the prepared tooth in the manner described above).
To ensure that any modifications made to the prosthetic model crown can be made to the prosthetic blank which is a substantially prefinished prosthetic crown, a proper registration of the orientation of the prosthetic model crown to the prosthetic blank is provided. More particularly, both the prosthetic model crown and the prosthetic blank are formed with registration features, such as registration marks 118 (e.g., protrusions of approximately 2 mm). The registration marks allow the prosthetic model crown which has been prepared in the manner described above to be placed in a holder with an orientation which matches an orientation of a prosthetic blank placed in a corresponding holder. The ability to hold the prosthetic model crown and the prosthetic blank at an exact, registered orientation allows the prosthetic blank to be milled to exactly match a shape of the prosthetic model crown which has been prepared.
The dentist can remove the prosthetic model crown from the prepared tooth by hand. Alternately, to simplify removal of the prosthetic crown from the prepared tooth once it has been trimmed and milled, the dentist can push inward on the core plug 108 (i.e., toward the prepared tooth), while pulling an exterior of the prosthetic model crown away from the prepared tooth. To further assist the dentist, a dental tool can be used to grab and hold exterior surfaces of the prosthetic model crown, while pushing inward on the core plug 108 . Such a dental tool is illustrated in the previously cited U.S. application Ser. No. 08/785,316, now U.S. Pat. No. 5,813,859.
FIGS. 1B-1C illustrate another exemplary embodiment of a dental prosthetic produced in accordance with an exemplary embodiment of the present invention. The embodiment illustrated in FIGS. 1B-1C can be used where, for example, the patient's tooth has undergone a root canal preparation, or in any case where the dental prosthetic is configured to mate with a recess prepared in the tooth of a patient. For purposes of the following explanation, the embodiment illustrated in FIGS. 1B-1C will be discussed in the context of preparing a dental prosthetic for use in conjunction with a prepared tooth of a patient following a root canal.
In FIG. 1B, the patient's tooth 102 has been milled by the dentist in conventional manner following a root canal. In accordance with exemplary embodiments of the present invention, the pulp chamber 103 has been prepared to eliminate undercut areas. Once the pulp chamber has been prepared, a lubricant is placed within the pulp chamber (i.e., any conventional dental lubricant can be used). Afterwards, a formable material which is impressionable, such as a light-curable material, is placed into the pulp chamber. A light guide is then placed into contact with the formable material, and light can be applied through the light guide to cure the light-curable material. The light-curable material attaches with the light guide, and assumes a shape which corresponds to that of the prepared pulp chamber in a passive (i.e., non-tight, non-binding) fashion, such that the light guide and the now-cured formable material 120 can be easily removed from the pulp chamber. The light guide and formable material constitute an extender 124 that can be used to produce the dental prosthetic model 126 of FIG. 1 B.
In the FIG. 1B embodiment, the dental prosthetic model 126 can include a preformed prosthetic model 128 having a preformed surface 130 . Another layer of the formable material, similar to the formable material 120 , can be applied to the interior surface 130 to form a second layer 132 of the formable material. The preformed prosthetic model 128 having the layer of formable material 132 can be placed over the extender 124 located in the pulp chamber 103 . The prosthetic model 128 can, for example, be of a clear plastic so that the layer 132 can be cured by shining light through the prosthetic model 128 . Afterwards, the entire dental prosthetic model can be removed from the prepared tooth, trimmed and used as a traceable prosthetic model.
As was the case with the FIG. 1A embodiment, the prosthetic model can serve as a template in milling a prosthetic blank to produce a final prosthetic dental crown 134 of FIG. 1 C. Once the dental prosthetic crown 134 has been milled, it can be bonded into place in the prepared pulp chamber.
A dental prosthetic configured as shown in FIGS. 1B-1C avoids any need to use a steel post for purposes of stabilizing a crown used in conjunction with a root canal. Because the crown is shaped to match the pulp chamber, a stable, strong bond can be achieved once the crown in cemented into place. In addition, because a steel post is not used, there is no pressure applied to the patient's root structure, such that the potential for fracture of the root structure is eliminated. Moreover, because a steel post is not used, crowns configured according to the embodiment of FIGS. 1B-1C do not result in discoloration, and therefore provide a more aesthetically pleasing result.
As was the case with the prosthetic model crown of FIG. 1A, the prosthetic model crown and the prosthetic blank of FIGS. 1B and 1C can be configured with registration features. The prosthetic model crown, once formed, can be removed using, for example, a dental tool as was described with respect to removal of the FIG. 1A prosthetic model.
Referring to FIG. 2A, the dental tool can be configured to grab protruding, hemispherically-shaped elements 204 included on the prosthetic model crown. As those skilled in the art will appreciate, the hemispherically-shaped elements 204 (e.g., on the order of 0.5 to 2 mm or greater) can also serve as the registration marks 118 of FIG. 1 A. For example, as illustrated in FIG. 2B, the hemispherically-shaped elements 204 can be included at three locations on a periphery of the prosthetic model crown so that an exact orientation of the prosthetic model crown can be established.
As those skilled in the art will further appreciate, the elements 204 need not be hemispherically-shaped, but can be of any shape. Further, the elements 204 need not be formed as protrusions, but can be formed as recesses, such as the recesses 206 shown in FIG. 2B (e.g., recesses on the order of 0.5 to 2 mm or greater in depth). Of course, any modifications to the shape of the elements 204 can be accounted for in the shaped tips of the dental tool. Alternately, any form of registration mark, including optically detectable marks, can be used to provide the registration.
Because the prosthetic model crown has been formed as a template representing a desired fit of the prosthetic model crown to the prepared tooth, the prosthetic blank is matched to the prosthetic model crown.
An exemplary method and apparatus for matching a prosthetic blank to the prosthetic model crown is illustrated in FIG. 3 . The FIG. 3 apparatus includes a means for machining the prosthetic model crown, in conjunction with a holding means for holding the dental prosthetic model crown and the dental prosthetic blank such that they can be moved relative to one another in at least five axes of motion. In the exemplary embodiment illustrated, there are three linear axes designated X, Y and Z, the linear axes being in an orthogonal arrangement. Two rotary axes for each spindle are labeled B and C. In the FIG. 3 embodiment, the rotary axes are attached to machine elements which move in the X, Y and Z axes.
As shown in FIG. 3, the prosthetic model crown is placed into a holding means having a first holding fixture 302 and a second holding fixture 304 . The holding fixtures, or holders, can be symmetrically configured to allow placement of the prosthetic model crown and prosthetic blank in either an upright or an upside-down orientation. The prosthetic model crown can, for example, be initially placed upside down in the first holding fixture 302 so that the surface formed with the cured ultraviolet light curing material is readily accessible by a tracing stylus 306 and then inverted for exterior milling.
In accordance with exemplary embodiments, clamps are provided in each of the first and second holding fixtures. Locations of the clamps are matched to the registration marks of the prosthetic model crown and the prosthetic blank, respectively. In an exemplary embodiment, adjustable means are provided to allow the prosthetic model crown to be inserted into the holding fixture, and then retained in place. For example, an adjusting screw can be provided to apply pressure to an exterior of the prosthetic model crown via the clamps, to thereby fix the prosthetic model crown in place.
The dental prosthetic model crown 106 is placed in the first holding fixture 302 represented by a left hand spindle (as viewed in FIG. 3) that can be manually rotated about the “B” axis of the left hand spindle, while the dental prosthetic blank 312 to be milled is placed in the second, similar holding fixture 304 on a parallel right hand spindle that rotates about a parallel “B” axis of the right hand spindle. The left and right hand spindles are rotationally connected to each other by a synchronized drive means, such as a chain or belt 305 drivingly connected with gears 307 and 309 that are fixed to respective spindles of first and second fixtures. Thus, any rotary motion imparted by the machine operator to the dental prosthetic model crown in the first holding fixture can be duplicated by the second hold fixture with respect to the dental prosthetic blank to be milled.
In the exemplary FIG. 3 embodiment, the three registration marks can be used to hold the prosthetic model crown in place. However, as those skilled in the art will appreciate, any number of registration marks can be included on the prosthetic model crown to hold it in place within the holding fixture. As was the case with the prosthetic model crown, the prosthetic blank can be held in place via clamps and an adjusting screw.
The FIG. 3 apparatus further includes means for machining the prosthetic crown blank 312 to match a surface, such as an interior, of the prosthetic model crown 106 . For example, exemplary embodiments include a cutting tool 320 mounted to a motor driven shaft 322 , which in turn is driven by motor 324 . The cutting tool can, of course, be any milling device, such as diamond burs used as conventional dental tools.
In accordance with exemplary embodiments, the prosthetic crown blank 312 can include finished exterior surfaces, with the exception of the surface that is to mate with the prepared tooth. Due to the use of the registration marks and clamps being in identical positions in the prosthetic model crown and on the prosthetic blank, a tracing of the prosthetic model crown as a template can be used to match an interior of the prosthetic blank to the shape of the prepared tooth.
For this purpose, the stylus 306 can be traced over the prosthetic model crown, with motions of the stylus being used to control movement of the cutting tool over a surface of the prosthetic blank. Because the registration marks are used to locate the prosthetic model crown and the prosthetic blank in exactly the same orientation, exact alignment of outside contours between the prosthetic model crown and the prosthetic blank can be assured, such that exact machining of the prosthetic blank interior can be achieved. Such machining can be performed in known fashion, such as in the manner described in the aforementioned U.S. Pat. No. 5,135,393, the contents of which are hereby incorporated by reference in their entirety.
The tracing stylus 306 is mounted to a “C” rotary axis spindle on the left hand side (as viewed) in FIG. 3 and the motorized cutting tool 320 having a shape matched to that of the stylus is mounted to a parallel “C” rotary axis spindle on the right hand side of FIG. 3 . The left and right hand parallel “C” axis spindles are rotationally connected to each other by a synchronized drive means, such as a chain or belt 321 drivingly connected with gears 323 and 325 that are fixed to respective “C” axis spindles. Thus, any rotary motion imparted by the machine operator to the tracing stylus is exactly duplicated by the cutting tool.
In accordance with exemplary embodiments, a counterweight 327 and associated pulley 329 can be provided to offset the weight of the “Z” axis slide to which the “C” rotary axes are attached. As such, the “Z” axis slide can remain at rest in any position when the machine operator releases the stylus. A counterweight can also be attached to the “C” axes to offset the weight of the stylus, cutting tool and cutting tool motor. As such, rotations of the stylus and cutting tool about the “C” axis can be maintained in any position when the machine operator releases the stylus. Of course, those skilled in the art will appreciate that any mechanism for providing the counterweight features described can be used, such as any appropriately sized metal weights or spring biases or any other counterweight measure. Similarly, counterweights can be provided in any arrangement desired, which will ensure that the stylus and cutter remain motionless when the operator refrains from any motion thereof.
Once an interior (i.e., tooth mating surface) of the prosthetic blank has been achieved, exterior surfaces of the prosthetic model crown can be traced and used to achieve similar milling of an exterior of the prosthetic blank crown. That is, peripheral side surfaces and the top surface of the prosthetic crown can be spot milled, with particular attention being payed to any areas on the top surface where the 1 millimeter, differently colored portion of the prosthetic model crown has been removed.
In accordance with exemplary embodiments, the first and second holding fixtures for holding the dental prosthetic model and the dental prosthetic crown can be configured with symmetrical cavities. As such, the dental prosthetic model and the dental prosthetic blank can be placed into their respective fixtures in either the upright or in an inverted position so that all sides of the dental prosthetic model and the dental prosthetic blank can be accessed by the stylus and cutting tool. For example, the use of a T-shaped tang as will be discussed with respect to FIG. 5 can be used to permit inversion of the dental prosthetic model and/or dental prosthetic blank in their respective holding fixtures.
In addition, those skilled in the art will appreciate that the synchronized drive means associated with any or all of the axes of movement in the FIG. 3 embodiment can be connected with a spring loaded tension. For example, each of the spindles and associated gears rotatable about the “B” and “C” axes can be biased via springs, such as any known coil spring arrangement represented as coil spring arrangement 331 of the first holding fixture 302 . Such a feature can be used to eliminate backlash in the connections between the manually driven axes (that is, the axes associated with the dental prosthetic model and the stylus) and the automatically driven axes (that is, the axes associated with the dental prosthetic blank).
After all machining of the prosthetic blank has been completed, both the prosthetic model crown and the prosthetic blank can be removed from the holding fixtures. Locating features included on the prosthetic blank can then be ground or polished off or, in the case where they are formed as recesses, can be filled. Because all exterior surfaces of the prosthetic blank will be formed as finished surfaces, the prosthetic blank now constitutes a finished crown which requires no porcelain build-up or sintering, but which can be immediately bonded into place over the prepared tooth of the patient.
Thus, unlike the '393 patent wherein a hand made template is produced from an impression, after which a coping is machined that must be ultimately built-up and sintered, exemplary embodiments constitute a one step process for producing a final dental prosthetic from a prosthetic blank. As such, exemplary embodiments constitute a simple, quick and cost effective manner of providing dental prosthetics which achieve an extremely precise fit to even a poorly prepared tooth.
Of course, exemplary embodiments are not limited to the preparation of a prosthetic dental crown, such as any tooth veneer. For example, exemplary embodiments can also be used to produce a dental bridge. In an exemplary embodiment, a process and apparatus as described above with respect to the preparation of a prosthetic dental crown can be used to produce an entire dental bridge. In one exemplary embodiment, multiple prosthetic model crowns associated with a bridge can be produced in the manner described above. The multiple prosthetic model crowns can then be connected to one another using a light cure material and/or a connecting rod (such as a light cure cement) to form a template for a bridge. Multiple prosthetic blanks can then be connected to one another in a similar fashion, and subsequently machined by tracing the multiple prosthetic model crowns which form a bridge template.
Where multiple prosthetic crowns are connected using a connecting rod, such as a metal (e.g., stainless steel) rod, each of the individual prosthetic crowns in the bridge remains separate. As such, some tolerance of the bridge to bending is accommodated, such that the individual prosthetic crowns will not break due to stress in contacting one another when force is applied to the bridge.
A bridge template can be formed using multiple prosthetic model crowns which have been bound together using a light cure material and/or a connecting rod, such as a stainless steel rectangular rod supplied through a drilled channel within each of the prosthetic model crowns. The prosthetic dental bridge can be formed as multiple prosthetic dental crowns connected to one another in similar fashion.
FIGS. 4A-4E illustrate an exemplary embodiment of a bridge formed using multiple prosthetic blanks. FIG. 4A illustrates a top view of a bridge template formed in accordance with exemplary embodiments of the present invention, and FIG. 4B shows a side view of the template. In FIG. 4A, two dental prosthetic model crowns 402 and 404 are fit to prepared teeth of a patient. A dummy tooth, or pontic 406 is configured to be held in place within the patient's mouth using the prosthetic model crowns 402 and 406 .
More particularly, referring to FIG. 4B, the patient's teeth 408 and 410 are prepared in a manner similar to that described with respect to FIG. 1A to receive dental prosthetic model crowns 402 and 404 . The prosthetic model crowns 402 and 404 can be fit in accordance with the manner discussed with respect to FIG. 1 A. After the prosthetic model crowns 402 and 404 have been prepared, prefabricated protrusions, or extensions, 412 and 414 can be bonded to exterior surfaces of the prosthetic model crowns 402 and 404 , respectively. For example, the protrusions 412 and 414 can be protrusions of standardized size, configured of the same material used to produce the crowns (or any other material, such as plastic) and bonded to the prosthetic model crowns using any bonding material, such as cement used to bond a crown to a prepared tooth.
FIGS. 4D and 4E illustrate an exemplary protrusion which can be used in accordance with the present invention. As shown in FIG. 4D, the protrusion is configured in a side view to extend with a top surface 416 that is relatively straight and flat. A lower surface 418 is contoured with an angled slope 420 and a relatively straight portion 422 . However, those skilled in the art will appreciate that any design can be used for the protrusion. FIG. 4E illustrates a front view of the FIG. 4D protrusion. As shown in the exemplary FIG. 4E embodiment, side walls 424 and 426 of the protrusion are curved slightly, with the furthermost extending portion of the protrusion having a width greater than that of the sloped portion which is bonded to the dental prosthetic model crown. In an exemplary embodiment, the protrusions can extend on the order of 2.5 mm, or any other desired dimension.
Once the prosthetic model crowns have been formed and placed on the prepare teeth of the patient, and the protrusions 412 and 414 bonded thereto, a prosthetic pontic model 406 is prepared. The prosthetic pontic model 406 can be a standardized model formed, for example, of clear plastic, or any other material, and configured with two recesses 428 , one on either side of the pontic. These recesses allow the pontic to be placed downward over the protrusions 412 and 414 . To establish a proper orientation of the pontic, a layer of formable material (such as light-curable, impressionable material) 430 can be placed within each of the recesses 428 . Sleeves 433 , such as preformed plastic sleeves matched to mate with the protrusions, can then be pressed into the formable material 430 . The pontic, with the formable material and sleeves 432 , can then be placed over the protrusions 412 and 414 of the prosthetic model crowns, and oriented in place. Once a proper orientation has been achieved, the formable material can be cured (e.g., light cured), and the sleeves can be bonded (e.g., cemented) in the orientation in which they maintain proper registration with the protrusions. Additional light-curable material 434 can then be placed in a bottom portion of the pontic, along the ridge (i.e., the patient's bone structure) to properly contour an underside portion of the pontic to the patient's mouth. The formable material can then be cured in place (e.g., either allowed to set over time, or cured using, for example, a light-cure process).
When the entire bridge template structure has been formed, it can be removed from the patient's mouth, and the prosthetic model crowns 402 and 404 can be removed from the pontic. Because the protrusions 412 and 414 are precisely matched to the shape of the sleeves 432 , there was no need to bond the protrusions to the sleeves. As such, the crowns 402 and 404 can be removed from the sides of the pontic 406 . Each of the prosthetic model crowns 402 and 404 can then be used as a template to copy mill a prosthetic blank. In exemplary embodiments, the prosthetic blank used to produce a bridge in accordance with the FIG. 4 embodiment, can be configured with oversized protrusions in approximate areas where it is expected that the protrusions 412 and 414 will be bonded to the dental prosthetic models. During the copy milling process, the prosthetic blanks can be milled to have protrusions which replicate the orientation of protrusions 412 and 414 .
Similarly, the prosthetic pontic model can serve as a template for copy milling a prosthetic pontic blank. That is, the contour and orientation of the sleeves 432 within the prosthetic pontic model can be copy milled into a prosthetic pontic blank.
After the prosthetic blanks used to produce the prosthetic crowns have been prepared, such as is shown in FIG. 4C with respect to a prosthetic blank 436 that has been copy milled to match the prosthetic model crown 402 , the prosthetic crowns can be bonded to the prosthetic pontic. As shown in FIG. 4C, the prosthetic pontic 438 has been copy milled to include a recess 440 that exactly matches the shape and orientation of the sleeve 432 . The copy milled protrusion 442 of the prosthetic crown 436 can be bonded to the recess 440 of the prosthetic pontic using any conventional bonding material. This can be repeated on the right-hand side of the pontic with respect to a prosthetic crown copy milled using the prosthetic model 404 as a template. When the entire bridge assembly has been bonded together, it can be bonded to the prepared teeth of a patient.
An exemplary bridge construction as illustrated in FIGS. 4A-4E provides a strong bridge structure which is very accurately fit to a patient's mouth. In addition, the bridge construction avoids the need for using a multiple materials, such as steel rods or other interconnecting materials or copings. The integrity of the overall bridge structure is high, and its susceptibility to fracture is low.
In an alternate embodiment, the multiple prosthetic model crowns used to form a bridge template can be traced in order to machine a single prosthetic blank formed large enough to serve as a bridge. In this case, the entire bridge is machined as a single piece from a template.
In another alternate embodiment, rather than using multiple prosthetic blanks to produce a bridge template, the bridge template can be formed as a pre-made unit. A blank prosthetic bridge can subsequently be machined, in a manner similar to that described above with respect to other embodiments of the present invention, by tracing the pre-made bridge unit representing a bridge template, to produce the finished bridge prosthetic.
Those skilled in the art will appreciate that exemplary embodiments of the present invention can also be used to machine prosthetic blanks into prosthetic inlays and onlays. That is, in accordance with exemplary embodiments of the present invention, an impression material can be placed into the inlay or onlay area of the patient's tooth, and a prefabricated prosthetic can be placed in the impression material. The impression material can then be cured and any excess impression material removed to provide a template of the inlay or onlay. Afterwards, a machining of a blank inlay or onlay can be performed using the prepared template in the manner described previously with respect to the prosthetic crown. As such, only the interior (e.g., tooth mating surface) of a finished blank inlay or onlay is machined to match the blank to the template in a manner which will achieve an accurate and precise fit of the inlay or onlay.
Of course, those skilled in the art will appreciate that alternate embodiments of the present invention exist. For example, the FIG. 3 apparatus can be configured with adjustments to accommodate any size prosthetic model and/or prosthetic blank, or alternately, a separate apparatus can be configured for different types of teeth (e.g., one size for molars, one size for bicuspids and so forth).
Further, in accordance with exemplary embodiments, an interior of the prosthetic model crown and/or the prosthetic blank can be formed with a surface better suited to adhere with the prepared tooth. For example, the surface can be formed with annular serrations to improve the adherence of the prosthetic to the prepared tooth. Similarly, the prepared tooth can be formed with annular serrations about its exterior to enhance the adherence of the prosthetic thereto. Previously, the use of such features to enhance the adhesion of the prosthetic to the prepared tooth could not be exploited, because it was necessary to repeatedly remove the prosthetic dental crown from the prepared tooth to repeatedly make adjustments before finally connecting it to the prepared tooth.
In accordance with alternate embodiments of the present invention, the prosthetic blanks can be produced to include a first exterior material (e.g., porcelain or ceramic), and a second interior material (e.g., metal, such as gold). As such, exemplary embodiments of the present invention can be used to produce a template for milling the second interior material of the prosthetic blank (e.g., mill a gold coping included within the blank). The use of the metal interior in the prosthetic blank allows the finished prosthetic to be cemented into place on the prepared tooth of a patient. As those skilled in the art will appreciate, cement, or other similar bonding agents, allow enhanced tolerance in attaching a prosthetic to a prepared tooth of a patient. This increased tolerance is relative to that associated with the typical bonding agents used with materials such as porcelain or ceramic. These materials require the use of bonding agents that tend to be more temperamental and labor intensive in their application.
In accordance with yet another embodiment, the prosthetic blank can be formed of a first material, such as porcelain or ceramic, and milled in accordance with exemplary embodiments of the present invention. Afterwards, the prepared interior of the prosthetic blank can be milled a predetermined amount (e.g., approximately 0.2 mm), to accommodate a coating of the interior with a second material more suitable for cementing the prosthetic to the prepared tooth of a patient. For example, a second material, such as metal (e.g., gold) can be applied to the milled interior of the prosthetic through, for example, electroplating.
Those skilled in the art will appreciate that where it is desirable to produce blanks formed of two materials, any techniques readily available can be used. For example, the prosthetic blanks can be produced by building up the first material (e.g., porcelain), on a standardized metal coping having a predetermined size and shape. The exposed side of the coping can then be machined using techniques described in accordance with exemplary embodiments of the present invention to fit the built-up coping to a patient's prepared tooth.
FIGS. 5A-5C illustrate an exemplary embodiment of the present invention for configuring a prosthetic blank and/or prosthetic model crown, as well as a holding means which can be used in conjunction with the milling apparatus of FIG. 3 . In FIG. 5A, a removable fixture 500 is provided, which can be mounted to each of the “B” axis spindles in the FIG. 3 apparatus, and which has a general “L” shape in the FIG. 5 embodiment. The fixture 500 includes a nested opening 502 which can be used to positively locate a prosthetic blank and/or a prosthetic model crown. The prosthetic blank and/or prosthetic model crown 504 can be configured, as illustrated in FIG. 5 A. As illustrated therein, a registration mark is formed as a “T” shaped tang molded onto the periphery of the blank and/or crown as a male connector which can be mated to the nested opening 502 to positively register the blank/crown with the fixture 500 . Of course, those skilled in the art will appreciate that the tang can be configured in any is acceptable manner, provided a suitable mating can be achieved with respect to the fixture 500 .
The fixture 500 can be removably mounted into the FIG. 3 apparatus, via a rotatable shaft 508 which can be clamped into the FIG. 3 apparatus in a corresponding receptacle of the first or second holding fixture. Of course, similar fixtures 500 can be associated with either or both of the holding fixtures used in the FIG. 3 apparatus for the prosthetic blank and/or the prosthetic model crown.
FIG. 5B illustrates the mechanism which can be included with the locating fixture 500 to clamp the prosthetic blank or prosthetic model crown into the fixture. As illustrated in FIG. 5B, after the “T” shaped tang 506 has been inserted into the nested opening 502 , a clamping mechanism 510 , which is pivotable about a pivot 512 , can be displaced such that a clamping tip 514 is located over the “T” shaped tang 506 . A thumb screw 516 can then be used to lock the clamp 510 into place by, for example, rotating in a clockwise direction such that a screw 518 which passes through the clamp 510 can lock the clamp in a closed position.
FIG. 5C illustrates the clamp 510 in an open position. As illustrated in FIG. 5C, the thumb screw 516 has been rotated in a reverse, counterclockwise direction, thereby permitting the clamp 510 to be pivoted about axis 512 away from a position where the clamping tip 514 engages the “T” shaped tang 506 . As such, the prosthetic blank and/or prosthetic model crown can be removed vertically from the fixture 500 . As illustrated in FIG. 5C, the clamp 510 moves about the axis 512 within an opening 520 of 110 the fixture 500 .
In accordance with exemplary embodiments, the “T” shaped tang 506 can be formed of any suitable material. For example, the “T” shaped tang 506 can be configured of the same material used to produce the prosthetic blank and/or prosthetic model crown. After the prosthetic model crown has is been prepared, it can be removed from the fixture 500 and then the “T” shaped tang can be removed therefrom (e.g., milled in the same way that the elements 204 of FIG. 2A are removed) and polished.
Referring to FIGS. 6A-6E, an alternate embodiment of a holder which can be used in conjunction with the FIG. 3 apparatus is illustrated. The holder can accurately locate and hold a dental prosthetic blank or prosthetic model. The exemplary holder illustrated provides a repeatable, accurate locating of a registration feature, such as a tang, which is configured as a part of the dental prosthetic or prosthetic model. In addition, the holder as illustrated provides automatic ejection of the tang when the holder is opened. A clamping device is provided which automatically rotates into position when tightening the holder, and rotates out of the way (e.g., 90° out of the way) when the holder is loosened. As such, the operator has a clear view of the cavity into which the tang is placed, and the holder can be operated using one hand, leaving the other hand free to hold and position the tang within the holding device.
FIG. 6A illustrates a holder in a closed position. The FIG. 6A holder is designated 600 , and includes a rotatable, knurled knob 602 . The knob 602 can be rotated in a counterclockwise direction to close the holder, and rotated in a clockwise direction to open the holder or vice verse. As shown in FIG. 6B, the “T” shaped tang 506 of FIG. 5 is located between a clamp 604 and an upper surface 606 of a “T” shaped recess 622 in the holder 600 . In FIG. 6B, the clamping device has been rotated over and pulled down upon the tang 506 by rotation of the knob 602 about a threaded shaft 608 .
The operator places a dental prosthetic blank or prosthetic model crown with a tang above the cavity, and then rotates the knurled knob 602 counterclockwise. Upon rotation of the knurled knob, a coil spring 610 located between the knob 602 and a collar 612 , creates a drag which causes the clamp 604 to rotate in the same direction as the knob 602 . Clamp rotation is achieved via an extended clamp shaft portion 614 of the shaft 608 . Clamp rotation stops when a first end of the clamp 604 contacts a stop pin 616 shown in FIG. 6 A. At this point, the threaded shaft 608 on the clamp is drawn down by the threads in the knob 602 and the tang is forced into the cavity and clamped in place.
When the knob 602 is rotated in a clockwise direction, the clamp 604 is raised by the threads of the shaft 608 . When the clamp has raised sufficiently to release pressure on the tang 506 , the drag of spring 610 causes the clamp 604 to rotate a predetermined amount (e.g., 90°) until an opposite end of the clamp 604 contacts the stop pin 616 as shown in FIG. 6 C. As the operator continues to rotate the knob 602 clockwise, the clamp 604 is raised. When the clamp raises a predetermined distance, the collar 612 on the clamp shaft 614 contacts an ejection pin 618 (see FIG. 6 D), and begins to raise the ejection pin. The ejection pin pushes the tang 506 up and out of the cavity. FIG. 6C shows the holder with the prosthetic blank or prosthetic model removed.
FIG. 6E shows that the holder 600 can be mounted to the copy milling apparatus of FIG. 3 about an axis 620 using any conventional mounting means (e.g., a screw and nut). In FIG. 6E, the tang of a dental prosthetic blank or model has been removed from recess 622 .
According to the present invention, once the dental prosthetic has been formed, and the tooth or teeth upon which the prosthetic is to be placed, the prosthetic can be inserted into place. In accordance with exemplary embodiments, any technique used for cementing can be used. For example, a light cured cement can be used whereby the prosthetic is inserted into place and, after all adjustments have been made, is exposed to a relatively high intensity light to cure the cement. In addition, known techniques which improve seating of the prosthetic can be used, including techniques whereby small holes are inserted into the top of the prosthetic to allow cement to be released therefrom during placement of the prosthetic on the prepared tooth.
It will be appreciated by those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the invention is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced therein.
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The present invention is directed to enhancing the accuracy with which tooth restorations are performed, including the manner by which a tooth is prepared and fit with a dental prosthetic, such as a crown or bridge. Further, the present invention is directed to reducing the skill-dependent tasks associated with tooth restoration, including root canals, while at the same time, improving the precision with which these procedures are performed and by aesthetics of the prosthetic. By improving the accuracy of restoration procedures, any need to repeat these procedures for a given patient can be eliminated and patient comfort can be improved. In addition, by improving the precision with which a prosthetic is prepared for attachment to the prepared tooth of a patient, and/or fit to patient, durability and longevity of the prosthetic are improved. For example, when the interior of a prosthetic is not precisely fit to the prepared tooth of a patient, as in a case where the coping is undersized relative to the prepared tooth, buckling of the coping can occur. As a result, the buckling of the coping can cause the porcelain exterior of the prosthetic to crack. Because exemplary embodiments of the present invention provide a precise and accurate fit, they avoid such buckling of the prosthetic's interior, and therefore, improve the longevity of the prosthetic.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims priority from U.S. Provisional Patent Application Ser. No. 61/264,946 entitled “Patient Weight Bearing Monitor” filed Nov. 30, 2009. The disclosure of this provisional patent application is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates generally to a weight bearing monitor system for recuperating orthopedic patients and, more particularly, to a lower limb load monitoring device for measuring or detecting the amount of force applied to, or weight borne by, a lower limb or joint of the body (either natural or prosthetic) and providing a signal to the user when a predetermined weight threshold level is exceeded.
BACKGROUND
Numerous situations exist where it is important to limit the load or force applied to or borne by a lower natural or prosthetic limb or joint of the body during standing, walking, stepping, running or jumping activities or during rehabilitation therapy. Situations also exist where it is important that the lower limb or joint be exposed to a certain load or force, particularly during rehabilitation therapy. In both situations it is important to monitor such load or force and to provide a signal to the user when such force is exceeded or met. Examples include post-surgery or injury rehabilitation of hips, knees, ankles or any other portion of the body which is affected by force applied to or borne by at least one of the user's legs, or any other situation in which monitoring of the weight on a lower limb during standing, walking, jumping or other activities is desired.
Prior art systems for monitoring the load or force applied to joints in a patient's leg are found in U.S. Patent Application Pub. No. 2006/0282018 and in the following U.S. Pat. Nos. 3,702,999 (Gradisar); 3,791,375 (Pfeiffer); 3,974,491 (Sipe); 4,745,930 (Confer); 5,107,854 (Knotts et al); 5,253,654 (Thomas et al); 5,511,561 (Wanderman et al); 5,619,186 (Schmidt et al); 6,174,294 (Crabb et al); and 6,273,863 (Avni et al).
Prior art monitors are typically complex mechanically and/or electrically with the result that they are expensive and add significantly to a patient's cost of recuperation.
SUMMARY OF THE INVENTION
The present invention provides an inexpensive alternative to methods and apparatus utilized heretofore to monitor the load applied to a lower limb or joint by a patient's weight and to provide an alarm when a predetermined and selectable weight is applied or exceeded.
A sensor according to the present invention includes a pad of electrically insulative material, having top and bottom surfaces defining its thickness dimension, and provided with a through aperture communicating between those surfaces. First and second thin electrically conductive plates or sheets serve as electrodes and are secured to the top and bottom surfaces of the pad, covering or partially covering the ends of the aperture. A resilient electrical contactor secured to the underside of the top plate depends through a portion of the aperture toward the bottom plate. The resulting structure serves as an electrical switch that is normally open but closes when the compressive force applied across the pad thickness is sufficient to permit the contactor to contact the bottom plate through the pad aperture. Electrical lead wires secured to respective electrodes are connected to a circuit that permits an audible and/or visible alarm to be actuated when the switch is closed.
The pad is typically disposed between the sole of a patient's foot and the ground, preferably in a patient's sock, shoe or other footwear or foot-worn orthopedic structure. The stiffness or compressibility of the pad determines the applied weight or compressive force required to permit the contactor to close the circuit between the electrodes, resulting in the closure of the switch. By selecting pad material having appropriate compressibility characteristics, one can design the switch to close in response to different applied forces. Patients can use sensors of increasing stiffness as rehabilitation progresses and greater weight loads are permitted on the affected limb.
The above and still further features and advantages of the present invention will become apparent upon consideration of the following definitions, descriptions and descriptive figures of specific embodiments thereof wherein like reference numerals in the various figures are utilized to designate like components. While these descriptions go into specific details of the invention, it should be understood that variations may and do exist and would be apparent to those skilled in the art based on the descriptions herein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view in perspective of the sensor portion of a weight monitor assembly according to the present invention.
FIG. 2 is an exploded view in perspective of a sensor unit employed in the assembly of FIG. 1 .
FIG. 3 is a view in perspective of one form of an indicator portion of the weight monitor assembly of the present invention.
FIG. 4 is a view in perspective of a compressible pad employed in the sensor unit of FIG. 2 .
FIG. 5 is a view in perspective of one form of an electrode and contactor employed in the sensor unit of FIG. 2 .
FIG. 6 is a view an elevation view in section of the sensor of FIG. 2 .
FIG. 7 is an electrical schematic diagram of the weight monitor of the present invention.
FIG. 8 is a broken view in elevation showing the weight monitor assembly of the present invention deployed on a patient with the sensor located in the patient's shoe.
FIG. 9 is a view in elevation showing the sensor of the weight monitor assembly located in an orthopedic appliance worn by the patient during rehabilitation therapy.
FIG. 10 is a view in elevation showing the sensor of the weight monitor assembly attached by a hook and loop fastener to a sock worn by the patient during rehabilitation therapy.
FIG. 11 is a view in elevation showing the sensor of the weight monitor assembly inserted in a pocket of a sock worn by the patient during rehabilitation therapy.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following detailed explanations of the preferred embodiments reveal the methods and apparatus of the present invention.
Referring to FIGS. 1 through 7 , a weight sensor 17 comprises an electrically non-conductive pad 10 , preferably made of silicone or like material and typically approximately 0.25″ thick, is shown in a rectangular configuration with top and bottom surfaces and a centrally located aperture 13 defined through its thickness. Neither the pad 10 nor the aperture 13 is required to be rectangular and can be any shape, such as round, polygonal, irregular, etc., as may be consistent with the functional features described herein. Top and bottom electrically conductive electrode sheets or plates 11 and 12 , respectively, are disposed on respective top and bottom surfaces of pad 10 to partially or fully cover opposite ends of aperture 13 . In the illustrated embodiment sheets 11 and 12 have the same peripheral configuration, in this case rectangular, as pad 10 and overlie the entireties of respective top and bottom surfaces of the pad. A resiliently movable electrical contactor 15 , preferably made of resiliently bendable spring steel, is secured by soldering or other electrical connection to the underside of top plate 11 . Contactor 15 includes a short section extending along the underside of plate 11 and a bent section extending at an angle (e.g., 45°) into aperture 13 . It is to be understood that an angular configuration of contactor 15 , and the particular angle of 45°, are design choices, and that any electrically conductive contactor configuration that permits the contactor to move toward the opposing electrode plate under weight loading may be employed.
In the illustrated preferred embodiment each electrode sheet 11 , 12 is made of steel and is approximately 0.020″ thick, although other conductive materials (e.g., copper, aluminum) may be employed. Electrically conductive wire leads A and B are connected, by soldering or the like, to respective electrode sheets 11 and 12 . As illustrated in FIG. 2 , the opposite ends of wire leads A and B are connected to a plug 25 which is adapted to connect to respective terminals in a control box receptacle or jack 21 . The control box 20 contains a buzzer 22 , or other audible or visual alarm, and a voltage source such as a battery 28 (or batteries) connected in series between the terminals of jack 21 . Thus, when there is contact between electrode plates 11 and 12 by means of contactor 15 being forced further through aperture 13 , a circuit is closed across the batteries and alarm 22 as best illustrated in the schematic diagram of FIG. 7 . Such contact is made when the force applied across weight sensor unit 17 is sufficient to compress pad 10 to cause contactor 15 to contact bottom plate 12 and resiliently bend so that the circuit between plates 11 and 12 is closed. That force is the weight of a patient applied across the unit by the sole of a patient's foot urging the unit toward a floor or the ground through a sock, shoe or other footwear in which the sensor is located. It will be appreciated that contactor 15 may be secured instead to the bottom plate 12 and positioned to be forced into contact with top plate 11 when the pressure applied across the unit is sufficient to compress pad 10 to cause contactor 15 to contact top plate 12 and resiliently bend so that the circuit between plates is closed. In either case the resilience of the contactor permits the predetermined force to be exceeded without damaging the contactor.
As best illustrated in FIG. 4 , pad 10 may be a two inch square of molded silicone with a density selected to permit compression of the pad to effect contact between the electrode sheets in response to application of a predetermined force across the pad. Pads of different densities can be provided to permit different applied weights to actuate the alarm as a patient's rehabilitation progresses; that is, differently calibrated sensors can be provided to sound an alarm at different applied weights.
As illustrated in FIG. 2 , the electrode plates may be substantially identical except for the provision of contactor 15 on the underside of plate 11 . The wire leads A and B are preferably 22 gauge wire. As noted elsewhere herein, the electrodes need not be identical, and only one electrode is required to flex to permit contactor movement as the pad 10 is compressed under a weight load.
Referring to FIG. 6 , the sensor unit may be encased in an electrically insulative sleeve 18 that can be placed in footwear such as a sock, shoe or orthopedic appliance when used by a patient. Sleeve 18 may be made of cotton, polyester or any such deformable material that serves as a cover for the unit and does not interfere with its operation. Alternatively, sleeve 18 may be encapsulated about the sensor unit by dipping the sensor in molten encapsulation material (e.g., a rubber like compound) or brushing on the compound. That compound may be color coded to indicate the compression weight at which electrical contact is made between the electrodes of the unit. As assembled, the unit 17 typically weighs two pounds or less.
The weight sensor of the present invention may be used in several ways. One such way is illustrated in FIG. 8 wherein the sensor unit 17 is shown removably secured, by means of hook and loop fastener, or the like, to the interior sole of a patent's shoe 30 . The sole of the patient's foot applies the patient's weight to the top plate 11 ( FIG. 1 ) of the sensor, thereby compressing the sensor pad 10 and gradually moving the contactor 15 toward the bottom plate 12 . When the maximum permitted weight is applied across the sensor, contactor 15 contacts the bottom plate, closing the circuit and sounding or flashing an alarm at the control box 20 ( FIG. 7 ). The control box may be connected by means of a clip 40 , or the like, to the top of a sock or a belt, etc., worn by the patient.
An alternative manner of using the weight sensor is illustrated in FIG. 9 wherein an orthopedic appliance 50 or similar structure is shown being worn on a patient's foot. The sensor is removably secured to the interior sole of the appliance.
In another embodiment the sensor is removably secured to the bottom of a patient's sock 60 , as illustrated in FIG. 10 . Alternatively, as shown in FIG. 11 , the sock 60 may be provided with a pocket 61 on the bottom side of the sock sole to receive the sensor. The lead wires connect to the control box which may be attached to the pants or other garment worn by the patient.
The foregoing describes only a few of the many ways in which the sensor 17 may be deployed for use.
The dimensions described herein for the preferred embodiments are presented simply as examples and can vary as desired in order to provide a suitably functional and comfortable unit. For example, the pad 10 need not be square; instead it can be round, oval, rectangular, contoured to a portion of the patient's foot, or irregular in shape. The pad length and/or width can be adjusted as desired, although it is believed that 1.5″ and 3.0″ are practical limits on these dimensions. The thickness of the pad 10 can range from 0.100″ to 0.400″.
The material for the pad 10 is chosen to provide a desired compression versus applied weight characteristic and can be solid/dense and sponge-like material including neoprene, silicone, natural rubber, latex, buna N, buna S, hypalon, EPDM, or polyurethane. The pad can be cut from sheet material, using a steel ruler die, shearing or cutting by hand. The material can also be molded to the needed shape.
Aperture 13 can be square, rectangular, round or any convenient regular or irregular shape and can have any length and width dimensions appropriate to the described function. Examples would be in the range of 0.250″ to 1.000″.
The top and bottom plates 11 , 12 can be conductive steel or aluminum, or they can be plastic with attached metal strips to provide the desired electrical conductivity. The thickness of the plates may, for example, range from 0.015″ to 0.125″. Importantly, in the illustrated embodiment the plates must be sufficiently thin to resiliently flex and follow the pad surfaces to which they are attached under a weight load. It will be appreciated that only one of the plates is required to flex as the pad compresses and, therefore, the plates need not be identical in structure or function.
In order for electrical contact to be made between electrodes 11 and 12 by contactor 15 , pad 10 is typically required to be compressed by approximately 50%, depending on the configuration, dimensions and positioning of the contactor. This compression is effected at different applied weights, typically between 5 and 40 lbs., depending on the compression characteristics of the pad which are predetermined by blending various compounds and then testing for the compression needed.
It will be appreciated that the important feature of unit is that, as pad 10 is compressed under the load of a patient's weight applied across the pad thickness dimension, contact will ultimately be made between electrodes 11 and 12 when a predetermined load force is reached. The use of contactor 15 attached to one of the electrodes and functioning through an aperture 10 is only one way of establishing this contact. For example, an electrically conductive member may be partially embedded in pad 10 in spaced relation to one or both electrodes and positioned to make contact between the electrodes through a recess or other opening in a pad surface in response to a predetermined pad compression.
Contactor 15 can be made of a strip of spring steel, or a small spring. As an alternative to the single contactor, the top and bottom plates can be provided with a lip, each facing the other, so that lips can be used to make the electrical contact upon compression of the pad.
The lead wires can be as short as a few inches and as long as necessary to reach the control box from the sensor, depending on where the control box is to be worn. The control box can be made of metal or plastic and can have any suitable size and shape to house the indicated components.
The battery voltage may be between 1.5 volts to 9 volts. A buzzer or other alarm that is operative with the chosen voltage supplies a sound or flashing light to alert the user that that he has reached the critical weight set by the physician or therapist. That is, the unit is used to indicate to the patient that the weight being applied to the limb is at the maximum weight that the person conducting the therapy has indicated to be appropriate. Sensor units can be made to respond to a large number of different weights needed by the medical profession.
The sensor of the present invention prevents patients who are undergoing therapy for an injured limb or replaced joint from suffering damage caused by placing more weight on the limb or joint than can be safely applied at different stages of recovery. A primary advantage of the sensor of the present invention is that can be manufactured and sold for a price that is far less than other sensors currently being used for the same purpose, thereby allowing patients to purchase the unit.
As described and illustrated, the sensor can be used attached to a stocking, placed in a shoe or sandal, or attached to a form fitting appliance.
Having described preferred embodiments of new and improved weight bearing monitor system, it is believed that other modifications, variations and changes will be suggested to those skilled in the art in view of the teachings set forth herein. It is therefore to be understood that all such variations, modifications and changes are believed to fall within the scope of the present invention as defined by the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
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A weight sensor includes a pad of electrically insulative material having a through aperture and electrode plates secured to its top and bottom surfaces at least partially covering the aperture. An electrical contactor in the aperture responds to a compressive force applied across the pad thickness to electrically interconnect the electrodes and close a circuit that permits an alarm to be actuated. The sensor is disposed in footwear worn by a patient being rehabilitated from a lower limb surgery or injury. The stiffness/compressibility of the pad determines the applied patient weight or compressive force required to permit the contactor to close the circuit between the electrodes.
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DESCRIPTION
BACKGROUND OF THE INVENTION
This invention relates to improved surfactant-solvent drying compositions which include a volatile solvent that has the capability of removing water or other aqueous films from the surface of substrates. Removal of the water from the substrate to be dried is effected by displacement; drying in this manner avoids an energy consuming drying step and, in the case of metals, avoids potential corrosion attendant after the use of aqueous cleaning methods.
Volatile solvent drying compositions used in the past have often proved less than satisfactory by failing to effectively displace water from the surface to be dried. To overcome this difficulty, in accordance with the invention, certain sarcosine surfactants have been found to provide highly advantageous results in promoting water displacement from surfaces that require drying.
An additional and serious problem encountered with varying severity in the use of solvent drying solutions, depending on the specific application and substrate to be dried, is the fact that such solutions tend to emulsify and are difficult to purify or to be freed of aqueous impurities so that the drying solution can be reused. The presence of emulsions in these drying compositions interferes with the free elimination of water, such as by decantation, and ultimately interrupts the water-displacement process which is the essential objective of the substrate drying treatment.
Various surfactants have been used to solve this problem of finding a good drying solvent while dealing effectively with the emulsification problem, with little success. For example, surfactants that do not cause emulsification usually dry poorly while good water-displacing surfactants usually cause emulsification of the displaced water.
It is thus apparent that a need exists for an effective solvent/surfactant surface drying system and, particularly, a system which is readily renewable by separating the water accumulated therein during use without encountering substantial interference by the presence of an emulsion phase.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide drying solvent compositions which have improved drying capabilities and can suitably withstand severe use by their water desorption and rejection abilities. A more particular object of the invention is to provide an effective drying solvent composition that resists the formation of stable emulsion. The solvent of the invention comprises a normally liquid fluorocarbon in combination with small amounts of sarcosine surfactants and certain other surface-active materials that are compatible with the above solvent and sarcosine surfactant composition.
The combination of these surfactants with certain solvent soluble, water-insoluble demulsifiers such as (1) acetylenic diols, e.g., 2,4,7,9-tetramethyl-5-decyn-4,7-diol; and mixtures thereof with (2) aliphatic primary alcohols, e.g., those in the range of hexanol to dodecanol at relatively low concentrations; and (3) phosphate triesters having three to twelve carbon atoms in quantities approximately comparable to the total surfactant present, inhibits the formation of stable emulsion. The emulsion control effects of this combination of demulsifiers, moreover, is better than when either additive is used alone at the full total amount of the additives.
The drying composition of the invention comprises the fluorocarbon 1,1,2-trichloro-1,2,2-trifluoroethane (FC-113).
The sarcosines which may satisfactorily be used as the first category of surfactants are acylated sarcosines of the following formula:
RCON(CH.sub.3)CH.sub.2 COOH
wherein R is an alkyl or alkenyl substituent of 10-20 carbon atoms. R may also consist of a mixture of such substituents encompassing the above range of carbon atoms.
The additives of the second category employed in preventing the formation of stable emulsions in the use of the foregoing surfactant-containing solvent drying systems are selected from the group consisting of the following kinds:
1. Acetylenic diols, for example, 2,4,7,9-tetramethyl-5-decyn-4,7 diol which is available as SURFYNOL® 104 from Airco Chemical Company. Other related acetylenic diols such as; 3,6-dimethyl-4-octyne-3,6-diol (SURFYNOL-82) or 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol (SURFYNOL 124) may also be used.
2. Aliphatic primary alcohols particularly those aliphatic primary alcohols having from six to twelve carbon atoms. These may be used singly or as mixtures of alcohols in this range; and
3. Phosphate tri-esters having ester carbon atoms chains of from three to twelve carbon atoms.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the invention, solvent-drying compositions which are very effective in displacing water, particularly from metal surfaces, and which inhibit the formation of undesirable stable emulsions under even vigorous conditions of use, are provided.
In the solvent-drying solutions of the invention, the organic fluorocarbons are those compositions having a boiling point range of between about 45° C. and 50° C., such as the trichlorotrifluoroethanes, particularly preferred is the compound 1,1,2-trichloro-1,2,2-trifluoroethane.
The sarcosines employed in the compositions of the invention are used in amounts of from 0.05 weight percent to about 1.0 weight percent and preferably in the range of from about 0.1 to about 0.5 weight percent. Suitable sarcosines are the N-acylated sarcosines of the formula
RCON(CH.sub.3)CH.sub.2 COOH
wherein R is a saturated or unsaturated hydrocarbon substituent of from 10 to 18 carbon atoms.
Suitable sarcosines within this category include N-lauroyl sarcosine having a formula CH 3 (CH 2 ) 10 CON(CH 3 )CH 2 COOH, N-cocoyl sarcosine which is a mixture of C 11 H 23 CON(CH 3 )CH 2 COOH and C 13 H 27 CON(CH 3 )CH 2 COOH; N-oleoyl sarcosine having a formula which is essentially at least 80% N-oleoyl sarcosine, C 17 H 33 CON(CH 3 )CH 2 COOH, and the balance being other fatty acid moieties, and the like sarcosines, and mixtures thereof.
The demulsifier which may be employed in amounts comparable to the surfactant, i.e., in an amount of from about 0.05 weight percent to about 1 weight percent, preferably is amounts of about 0.1 to about 0.5 weight percent, is one or more of those from the following group:
1. acetylenic diols such as, 2,4,7,9-tetramethyl-5-decyn-4,7 diol, bearing a brand name SURFYNOL 104;
2. aliphatic primary alcohols having from six to twelve carbon atoms, preferably the n-octyl alcohol
3. phosphate esters having carbon atom substituents of three to twelve carbon atoms, typically, tri-n-butyl phosphate.
The relative weight of demulsifier to surfactant in the composition may vary from about a ratio of 1:8 to 8:1 but preferably is maintained within the ratio of 1:4 to 4:1, with approximately equal amounts of surfactants and demulsifiers being most advantageous in most instances.
It has been found that even more beneficial results are derived when the demulsifier materials are used in combination with each other, e.g., such as by combining the acetylenic diol type with the primary aliphatic alcohol type, or with the phosphate tri-ester type. The relative proportions of the two types of demulsifiers may vary from 1:4 to 4:1 parts by weight, usually are preferably used in a 1:1 ratio by weight. For example, a preferred composition would include a 1:1 weight ratio of (SURFYNOL-104) 2, 4, 7, 9-tetramethyl-5-decyn-4,7-diol and n-octanol as the demulsifier material.
It has been found that the compositions of the present invention possess certain variable advantages over prior art compositions in that a solvent as described may be used for relatively long periods without formation of significant amounts of stable emulsion) thereby avoiding the difficulties in recirculating the solvent and avoiding clogging of the circulating apparatus.
While the drying compositions of the present invention preferably comprise those that are stabilized against formation of emulsions, it will be understood, nevertheless, that in some cases the drying solutions, per se, without demulsifier are also advantageous. We have found that the drying compositions containing the sarcosine surfactants, where applied in processes that do not give rise to formation of substantial amounts of stable emulsion, or where such emulsion that does form may be practically removed such as by skimming from the system, may be used without demulsifier to provide a superior drying composition. This will be apparent from the examples provided hereinafter, wherein some examples illustrate compositions that are superior drying media although not necessarily substantially resistant to the formation of emulsion. Accordingly where an application requires that there be substantial absence of emulsion, such drying compositions are selected which afford this important property of being resistant to stable emulsion formulation.
In order to differentiate qualities of performance among the various compositions, for ability to displace water from wet substances and for ability to give good separations between water and solvent phases, the following test methods were used. The "Minimum Time Test" measures the efficiency of water-displacement performance and is conducted as follows:
WATER DISPLACEMENT PERFORMANCE--MINIMUM TIME TEST
(1) A stainless-steel beaker, of about 2-liter capacity is fitted with a cooling-coil of several turns of tubing that conforms closely to the inner surface of the upper part of the beaker. The coil is connected to a source of cooling fluid. This arrangement is referred to as a "boiling sump".
(2) The boiling sump is charged with 500 ml of the solution to be tested and is placed upon a thermostatted hot plate. The solution is heated to rolling boil and is refluxed off the surface of the cooling coil.
(3) Segments, i.e., "coupons" having an approximate size 18 mm×76 mm (about 3/4 inches by 3 inches) of the substrates to be tested are pre-cleaned to a condition of no-water-break cleanliness (a terminology used by those who work in the field of surface-finishing metals and other substrates to refer to a surface condition essentially free of oil film). The coupons are attached to suspension means and are wetted with water just prior to the test. The wetted coupon is completely immersed for a pre-determined time, e.g., ten seconds, in the boiling test solution. It is then raised into the vapor region above the liquid and held there for 30 sec. The coupon is then removed and examined for the presence of water on the surface. If it is dry, the process is repeated with fresh, wet coupons for shorter immersion times until "failure," i.e. a wet surface, occurs. If the coupon is wet at ten seconds, then longer immersion times are used, successively, until complete water-displacement, i.e. a dry surface, is accomplished. "Minimum time for displacement" is reported as the immersion times (seconds) between "wet" and "dry" surface conditions upon removal from the boiling sump. The shorter the time for drying, the better the water-displacement efficiency.
The "Phase-Separation Rate Test" outlined below measures the relative rates for separation of the water and solvent phases which is related to the emulsion formation and is conducted as follows:
PHASE-SEPARATION TEST
(1) This test simulates the agitation imparted to a liquid by a centrifugal circulating pump such as may be found on a vapor-phase degreasing machine that has been modified to perform an efficient water-displacement function. This test also measures the relative rates of separation for aqueous and solvent phases after the end of the agitation period. The more rapid and complete the separation of the phases, the more potentially useful is the solvent-surfactant composition in a drying machine.
(2) The test is run in a Waring® Blender (Waring Products Co.), Model 1088. The test is done at "low" speed and the built-in timer is set for ten-second running time. A one-pint jar with a tightly-fitting screw cap is used. Separation rate measurements are made in eight-ounce, tall, straight-sided wide-mouth glass jars that have screw caps.
(3) The test is conducted with a 180-ml portion of the solvent solution in the jar of the blender. To this portion is added 18 ml (10 vol%) of the aqueous phase material: water, or other aqueous process solution. The jar is closed tightly and the blender is run at "low" speed for ten seconds. The dispersion is immediately poured over into a measurement jar and the initial time is noted. Total volume height in the jar is measured along the outside of the jar with a ruler or dividers. Further readings of the depth of each phase are taken at 5, 10, 20, 30 and 60 min. of elapsed time. For each reading, the depth of each clear phase, from its top or bottom to the corresponding surface at the interface layer, is measured.
(4) These depths are than calculated as volume percents of the original total volume, or as proportions of the original phase volumes. The volume proportions may then be plotted against elapsed time for each phase and curved are obtained that show relative separation dynamics for the various mixtures. Alternatively, separation percentages for the phases at 30 and/or 60 minutes may be used for comparing relative performances of the mixtures being tested.
(5) In each case, any formation of a stable emulsion in a phase or at the interface is noted. The depth of such an emulsion is subtracted from the depth of corresponding clear phase for purposes of calculating the percent separation of that phase. For example, a stable emulsion in the aqueous phase after 60 minutes standing is zero separation of that phase, even if the solvent phase becomes completely clear.
Specific examples of the effectiveness of the compositions of the invention are summarized in the following tables. Parts and percentages are expressed by weight except as otherwise noted.
Table I shows mixtures of N-acyl sarcosine surfactants with solvent and with, or without, demulsifier additives; these were used for choosing advantageous surfactant compositions. Performance results for these mixtures when tested according to the methods described above are shown in Table II.
Table III shows compositions that were used to differentiate among the various demulsifier materials in order to choose the most advantageous ones. The qualities of phase-separations for these compositions are shown in Table IV.
Table V shows the qualities of relative water-displacement capabilities for these same compositions i.e. the composition of Examples 11-19.
Table VI shows compositions and results of performance tests, as described above, for mixtures used to evaluated the relative utilities of fluorocarbon solvents that might be used in practicing this invention.
TABLE I______________________________________COMPOSITIONS OF TEST SOLUTIONS USED FORCOMPARISONS AMONG SARKOSYL® SURFACTANTSIN WATER-DISPLACINGSOLVENT SOLUTIONSComposition SARK SARK SARK SURF. n-OCT- FCNumber O.sup.(a) L.sup.(b) LC.sup.(c) 104.sup.(d) ANOL 113.sup.5______________________________________Control 1001 0.10 -- 0.10 -- -- 99.82 0.10 -- 0.10 0.30 -- 99.53 -- -- 0.20 0.30 -- 99.54 0.10 -- 0.10 0.15 0.15 99.55 -- -- 0.20 0.15 0.15 99.56 0.10 -- 0.10 -- 0.20 99.67 -- -- 0.20 -- 0.20 99.68 -- 0.20 -- 0.15 0.15 99.59 0.10 0.10 -- 0.15 0.15 99.510 -- 0.20 -- -- -- 99.8______________________________________ .sup.(a) SARKOSYL "O" (Oleoyl Sarcosine) CibaGeigy Co. .sup.(b) SARKOSYL "L" (Lauroyl Sarcosine) CibaGeigy Co. .sup.(c) SARKOSYL "LC" (Cocoyl Sarcosine) CibaGeigy Co. .sup.(d) SURFYNOL-104 (2,4,7,9Tetramethyl-5-Decyn-4,7 Diol) Airco Chemica Co. .sup. 5 FC-113 is 1,1,2Trichloro-1,2,2-Trifluoroethane
TABLE II______________________________________COMPARISON OF PERFORMANCES OF SARKOSYL-SURFACTANT COMPOSITIONS IN FC-113 SOLVENT PHASECOMPOSITION SEPARATION MINIMUM TIME, SEC..sup.(c)NUMBER.sup.(a) VOL. %.sup.(b) Al Brass SS304.sup.(d)______________________________________Control 100 Wet Wet Wet1 ZERO 1 1 12 29 1 1 13 39 -- -- 5-104 87 1 1 1-25 39 -- -- >306 ZERO -- -- 1-27 48 -- -- 13-158 29 1 1 2-39 49 1 1-2 2-310 ZERO 1 1 1______________________________________ .sup.(a) As given in Table I .sup.(b),(c) As measured by test method given in text .sup.(d) Stainless steel, alloy No. 304.
TABLE III__________________________________________________________________________COMPOSITIONS OF SOLVENT-DRYING MIXTURESUSED IN EXAMPLES CITED BELOWINGREDIENTS, WT. %EXAMPLE SARK..sup.(a) SARK..sup.(b) SURF..sup.(c) n-OCT..sup.(d) NEO..sup.(e) F-CNUMBER O LC 104 OH 91 TNBP.sup.(f) 113__________________________________________________________________________11 0.10 0.10 NONE NONE NONE NONE 99.8 (Compara- tive).sup.(g)12.sup.(h) COMMERCIAL PRODUCT (COMPARATIVE)13 0.10 0.10 0.30 NONE NONE NONE 99.514 0.10 0.10 NONE 0.20 NONE NONE 99.615 0.10 0.10 0.15 0.15 NONE NONE 99.516 0.10 0.10 0.10 0.20 NONE NONE 99.517 0.10 0.10 0.20 0.10 NONE NONE 99.518 0.10 0.10 0.15 NONE 0.15 NONE 99.519 0.10 0.10 0.15 NONE NONE 0.15 99.5__________________________________________________________________________ .sup.(a) SARKOSYL-O, CibaGeigy Co. .sup.(b) SARKOSYL-LC, CibaGeigy Co. .sup.(c) SURFYNOL 104, Air Products and Chemicals Co. .sup.(d) n-octanol, B.P. 194-196° C. .sup.(e) NEODOL 91, Shell Chemical Co. .sup.(f) TNBP-- Tri-n-Butyl Phosphate .sup.(g) No demulsifier additive. .sup.(h) Solution of amine salt of phosphoric acid ester, in FC113, sold as a commercial drying product.
TABLE IV______________________________________QUALITY OF PHASE-SEPARATION VS. COMPOSITIONFOR MIXTURES CONTAINING 0.10 WT. % EACH OFSARKOSYL "O" AND "LC", ADDITIVES AS INDICATED,AND BALANCE OF F-C113INGREDIENTS, WT, %EX-AM-PLE- PHASE-NUM- SURF. n-OCT. NEO. SEPARA-BER 104 OH 91 TNBP TION.sup.(a), %______________________________________11 NONE NONE NONE NONE ZERO (Comparative)12 COMM'L ZERO PRODUCT (Comparative)13 0.30 NONE NONE NONE 2914 NONE 0.20 NONE NONE ZERO15 0.15 0.15 NONE NONE 8716 0.10 0.20 NONE NONE 9517 0.20 0.10 NONE NONE 3818 0.15 NONE 0.15 NONE 9519 0.15 NONE NONE 0.15 90______________________________________ .sup.(a) As measured by test method given in text.
TABLE V__________________________________________________________________________QUALITY OF WATER-DISPLACEMENT FROM TEST SUBSTRATESFOR MIXTURES CONTAINING 0.10 WT. % EACH OFSARKOSYL "O" AND- "LC", ADDITIVES AS INDICATED,AND BALANCE OF F-C 113. INGREDIENTS, WT. %EXAMPLE SURF. n-OCT. NEO. MINIMUM TIME, SEC..sup.(a)NUMBER 104 OH 91 TNBP Al Brass SS304.sup.(b)__________________________________________________________________________11 CONTROL 1 1 112 PROP. COMM'L PRODUCT 1 1 113 0.30 NONE 1 1 114 NONE 0.20 NONE NONE 1 1-2 1-215 0.15 0.15 NONE NONE 1 1 116 0.10 0.20 NONE NONE 1 3-5 5-1017 0.20 0.10 NONE NONE 1 3-5 3-518 0.15 NONE 0.15 NONE 1-2 1-2 6019 0.15 NONE NONE 0.15 1 5-8 2-3__________________________________________________________________________ .sup.(a) As measured by test method given in text. .sup.(b) Stainless steel, Alloy No. 304
TABLE VI______________________________________COMPARATIVE PERFORMANCE OF OTHERFLUOROCARBON SOLVENTS BLENDS INWATER-DISPLACEMENT COMPOSITIONS.sup.(a)WITH FC-113 PHASE-EXAMPLE F-C SEP'N, MIN. TIME, SEC.NUMBER SOLVENT % Al Brass S.S.304.sup.(d)______________________________________20 FC-113 87 1 1 121 FC-11 6 8-10 18-20 N.D.22 BLEND A.sup.(b) -- N.D. N.D. N.D.23 BLEND B.sup.(c) -- N.D. N.D. N.D.24 FC-123 100% N.D. N.D. N.D.______________________________________ N.D. = No waterdisplacement effect .sup.(a) SARKOSYL "O" AND "LC", (0.10 wt. % each) SURF--YNOL 104 (0.15 wt %) nOctanol, (0.15 wt. %); and Solvent, (99.5 wt. %) .sup.(b) BLEND A = 50.5 wt. % FC 113, and 49.5 wt. % methylene chloride BLEND B = 39.1 wt. % FC 113, and 51.6 wt. % methylene chloride and 9.3 wt % cyclopentane .sup.(d) Stainless steel, Alloy No. 304
It will be apparent to those skilled in the art that various changes may be made in the proportions and additive ingredients of the compositions described herein. Other drying applications for these surfactant demulsifier blends would readily suggest themselves to those skilled in the art.
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Surfactant-modified, 1,1,2-trichloro-1,2,2-trifluoroethane solvent compositions are provided which contain small but effective amounts, i.e., about 0.2 to about 0.5 weight percent of solvent soluble/water insoluble surfactant and/or surfactant demulsifiers and adjust to accommodate. Of particular significance are the compositions containing N-acylated sarcosine surfactants and demulsifiers of the group acetylenic diols, aliphatic primary alcohols of 6 to 12 carbon atoms, and alkyl phosphate triesters of 3 to 12 carbon atoms. The demulsifier containing compositions have the properties of effectively and essentially completely displacing water or aqueous solutions from many substrates and, even under conditions of severe agitation, separating them for removal by decantation from the solvent layer without the drawback of forming stable emulsions that prevent said decantation and interfere with sufficient processing of the solvent drying compositions through the drying apparatus.
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FIELD OF THE INVENTION
[0001] The present specification relates to a novel hetero-cyclic compound and an organic light emitting device comprising the same.
[0002] This application claims priority to and the benefits of Korean Patent Application No. 10-2013-0075662, filed with the Korean Intellectual Property Office on Jun. 28, 2013, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0003] An organic light emission phenomenon generally refers to a phenomenon that converts electric energy to light energy using an organic material. An organic light emitting device using an organic light emission phenomenon typically has a structure that includes an anode; a cathode, and an organic material layer therebetween. Herein, the organic material layer is usually formed as a multilayer structure formed with different materials in order to improve the efficiency and the stability of an organic light emitting device, and for example, may be formed with a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, holes from the anode and electrons from the cathode flow into the organic material layer when voltage is applied between the two electrodes, excitons form when the electrons and the holes injected are recombined, and light emits when these excitons fall back to the ground state.
[0004] There have been continuous demands for the development of new materials that can be used in organic light emitting devices such as above.
SUMMARY OF THE INVENTION
[0005] In view of the above, an objective of the present application is to provide a hetero-cyclic compound having a chemical structure that can perform various roles required in an organic light emitting device depending on substituents, and to provide an organic light emitting device including the hetero-cyclic compound.
[0006] In one embodiment of the present specification, a compound represented by the following Chemical Formula 1 is provided.
[0000]
[0007] In Chemical Formula 1,
[0008] X is any one of the following structural formulae,
[0000]
[0009] L1 and L2 are the same as or different from each other, each independently directly bonded; a substituted or unsubstituted arylene group; or a substituted or unsubstituted alkenylene group,
[0010] Ar1 is a substituted or unsubstituted aryl, group; or a substituted or unsubstituted heteroring group including one or more of O, N and S as a heteroatom,
[0011] L1 and L2 are different from each other, or
[0000]
[0000] and Ar1 are different from each other,
[0012] X1 to X3 are the same as or different from each other, each independently a trivalent heteroatom or CH, and at least one of X1 to X3 is a trivalent heteroatom,
[0013] Ar2 and Ar3 are the same as or different from each other, each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroring group including one or more of O, N and S as a heteroatom.
[0014] In addition, in one embodiment of the present specification, an organic light emitting device that includes a first electrode; a second electrode provided opposite to the first electrode; and one or more layers of organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the hetero-cyclic compound represented by Chemical Formula 1.
ADVANTAGEOUS EFFECTS
[0015] A novel compound according to the present specification can be used as the material of an organic material layer of an organic light emitting device, and by using the compound, an improvement of efficiency, a low driving voltage and/or an improvement of life span characteristics are possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows an example of an organic electronic device in which a substrate ( 1 ), an anode ( 2 ), a light emitting layer ( 3 ) and a cathode ( 4 ) are laminated in consecutive order by a diagram.
[0017] FIG. 2 shows an example of an organic electronic device in which a substrate ( 1 ), an anode ( 2 ), a hole injection layer ( 5 ), a hole transfer layer ( 6 ), a light emitting layer ( 3 ), an electron transfer layer ( 7 ) and a cathode ( 4 ) are laminated in consecutive order by a diagram.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0018] The present specification provides a compound represented by Chemical Formula 1.
[0019] In the present specification,
[0000]
[0000] means a site linking to other substituents.
[0020] In one embodiment of the present specification, in Chemical Formula 1, L1 and L2 are different from each other, or
[0000]
[0000] and Ar1 are different from each other.
[0021] Specifically, in one embodiment of the present specification, L1 and L2, and Ar1 and
[0000]
[0000] may be different from each other. In another embodiment, L1 and L2 different from each other, and Ar1 and
[0000]
[0000] may be the same as each other. In another embodiment, L1 and L2 the same as each other, and Ar1 and
[0000]
[0000] may be different from each other.
[0022] In one embodiment of the present specification, L1 and L2 are different from each other, each independently directly bonded; or a substituted or unsubstituted phenylene group.
[0023] In one embodiment of the present specification, L1 is directly bonded, and L2 is a substituted or unsubstituted phenylene group.
[0024] In one embodiment of the present specification, L1 is a substituted or unsubstituted phenylene group, and L2 is directly bonded.
[0025] In one embodiment of the present specification, L1 and L2 are substituted or unsubstituted phenylene groups, and each phenylene group has different substituents or has different bonding sites.
[0026] In one embodiment of the present specification, Ar1 and
[0000]
[0000] are different from each other, and Ar1 is represented by the following Chemical Formula 2.
[0000]
[0027] In Chemical Formula 2,
[0028] X4 to X6 are the same as or different from each other, each independently a trivalent heteroatom or CH, and at least one of X1 to X3 is a trivalent heteroatom,
[0029] Ar4 and Ar5 are the same as or different from each other, each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroring group including one or more of O, N and S as a heteroatom.
[0030] In one embodiment of the present specification, Ar1 and
[0000]
[0000] being different means that at least one of X1, X2, X3, Ar2 and Ar3 may be different from X4, X5, X6, Ar4 and Ar5.
[0031] In one embodiment of the present specification, Ar1 is represented by any one of the following Chemical Formula 3 to Chemical Formula 10.
[0000]
[0032] In Chemical Formulae 3 to 10,
[0033] a is an integer of 0 to 8,
[0034] b is an integer of 0 to 7,
[0035] c is an integer of 0 to 4,
[0036] d is an integer of 0 to 5,
[0037] e is an integer of 0 to 3,
[0038] X7 is S, O, NR or CRR′, and
[0039] R, R′ and R1 to R14 are the same as or different from each other, each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkylsulfoxide group; a substituted or unsubstituted arylsulfoxide group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroring group including one or more of O, N and S as a heteroatom.
[0040] In one embodiment of the present specification, positions 2 and 7 of the naphthylene of Chemical Formula 1 are substituted with L1 and L2, respectively.
[0041] In one embodiment of the present specification, positions 1 and 7 of the naphthylene of Chemical Formula 1 are substituted with L1 and L2, respectively.
[0042] In one embodiment of the present specification, positions 1 and 6 of the naphthylene of Chemical Formula 1 are substituted with L1 and L2, respectively.
[0043] In one embodiment of the present specification, positions 1 and 8 of the naphthylene of Chemical Formula 1 are substituted with L1 and L2, respectively.
[0044] In one embodiment of the present specification, the hetero-cyclic compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulae 1-1 to 1-4.
[0000]
[0045] In Chemical Formulae 1-1 to 1-4, Ar1, Ar2, Ar3, X1 to X3, and L1 and L2 are the same as those defined above.
[0046] Examples of the substituents are described below, but are not limited thereto.
[0047] In the present specification, the term “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; an imide group; an amide group; a hydroxy group; a thiol group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a silyl group; an arylalkenyl group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxide group; an arylsulfoxide group; a silyl group; a boron group; an alkylamine group; an aralkylamine group; an arylamine group; an aryl group; an arylalkyl group; an arylalkenyl group; and a heteroring group including one or more of O, N and S as a heteroatom, or means having no substituents.
[0048] In the present specification, examples of the halogen group include fluorine, chlorine, bromine and iodine.
[0049] In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, compounds having the following structures may be included, but the compound is not limited thereto.
[0000]
[0050] In the present specification, in the amide group, the nitrogen of an amide group may be once or twice substituted with hydrogen, a linear, branched or ring-chained alkyl group having 1 to 25 carbon atoms, or an aryl groups having 6 to 25 carbon atoms. Specifically, compounds having the following structures may be included, but the compound is not limited thereto.
[0000]
[0051] In the present specification, the alkyl group may be linear or branched, the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl or the like, but are not limited thereto.
[0052] In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl or the like, but are not limited thereto.
[0053] In the present specification, the alkoxy group may be linear, branched or have a ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof may include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy or the like, but are not limited thereto.
[0054] In the present specification, the alkenyl group may be linear or branched, and although not particularly limited, the number of carbon atoms is preferably 2 to 40. Specific examples thereof may include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, a stilbenyl group, a styrenyl group or the like, but are not limited thereto.
[0055] In the present specification, the aryl group may be a monocyclic aryl group or a multicyclic aryl group, and includes a case in which an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, the aryl group in the present specification may mean an aromatic ring.
[0056] When the aryl group is a monocyclic aryl group, although not particularly limited, the number of carbon atoms is preferably 6 to 25. Specifically, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group or the like may be included as the monocyclic aryl group, but the monocyclic aryl group is not limited thereto.
[0057] When the aryl group is a multicyclic aryl group, although not particularly limited, the number of carbon atoms is preferably 10 to 24. Specifically, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a crycenyl group, a fluorenyl group or the like may be included as the multicyclic aryl group, but the multicyclic aryl compound is not limited thereto.
[0058] In the present specification, the fluorenyl group has a structure in which two cyclic organic compounds are linked through one atom.
[0059] The fluorenyl group includes the structure of an open fluorenyl group, and herein, the open fluorenyl group has a structure in which the linkage of one cyclic organic compound is broken in the structure of two cyclic compounds linked through one atom.
[0060] When the fluorenyl group is substituted, it may become
[0000]
[0000] and the like. However, the examples are not limited thereto.
[0061] In the present specification, the silyl group specifically includes a trimethyl silyl group, a triethyl silyl group, a t-butyldimethyl silyl group, a vinyldimethyl silyl group, a propyldimethyl silyl group, a triphenyl silyl group, a diphenyl silyl group, a phenyl silyl group or the like, but is not limited thereto.
[0062] In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group or the like, but are not limited thereto.
[0063] In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 50. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group or the like, but are not limited thereto.
[0064] In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a multicyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a multicyclic aryl group, or a monocyclic aryl group and a multicyclic aryl group at the same time.
[0065] Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthracenylamine, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a carbazol and a triphenylamine group or the like, but are not limited thereto.
[0066] In the present specification, the heteroaryl group in the heteroarylamine group may be selected from among the examples of the heteroring group described above.
[0067] In the present specification, the heteroring group is a heteroring group including one or more of O, N and S as a heteroatom, and although not particularly limited, the number of carbon atoms is preferably 2 to 60. Examples of the heteroring group includes a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, an acridyl group, a pyridazine group, a pyrazinyl group, a qinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a dibenzofuranyl group or the like, but are not limited thereto.
[0068] In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxide group and the aralkylamine group is the same as the aryl group examples described above. Specific examples of the aryloxy group include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphonoxy, 3-biphenyloxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryloxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy or the like, and examples of the arylthioxy group include a phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group or the like, and examples of the arylsulfoxide group include a benzene sulfoxide group, p-toluene sulfoxide group or the like, but are not limited thereto.
[0069] In the present specification, the alkyl group in the alkylthioxy group and the alkylsulfoxide group is the same as the alkyl group examples described above. Specific examples of the alkylthioxy group include a methylthioxy group, an ethylthioxy group, a tert-butylthioxy group, a hexylthioxy group, an octylthioxy group or the like, and examples of the alkylsulfoxide group include a mesyl group, an ethyl sulfoxide group, a propyl sulfoxide group, a butyl sulfoxide group or the like, but are not limited thereto.
[0070] In the present specification, the arylene group and the alkenylene group mean having two binding sites in the aryl group and the alkenyl group, respectively, which mean a divalent group. Descriptions for the aryl group and the alkenyl group may be applied respectively, except that the arylene group and the alkenylene group are divalent groups.
[0071] In the present specification, the heteroatom of trivalent group includes N or P, but is not limited thereto.
[0072] In one embodiment of the present specification, the heteroatom of trivalent group is N.
[0073] In one embodiment of the present specification, X1 to X3 are the same as or different from each other, each independently N or CH, and at least one of X1 to X3 is N.
[0074] In one embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; or a substituted or unsubstituted naphthyl group.
[0075] In one embodiment of the present specification, L1 is a substituted or unsubstituted arylene group.
[0076] In one embodiment of the present specification, L1 is a substituted or unsubstituted phenylene group.
[0077] In one embodiment of the present specification, L1 is a phenylene group.
[0078] In one embodiment of the present specification, L1 is a phenylene group, and the phenylene group is
[0000]
[0079] In another embodiment, L1 is a phenylene group, and the phenylene group is
[0000]
[0080] The
[0000]
[0000] means being linked to
[0000]
[0000] or to a naphthyl group in Chemical Formula 1.
[0081] In one embodiment of the present specification, L2 is a substituted or unsubstituted arylene group.
[0082] In one embodiment of the present specification, L2 is a substituted or unsubstituted phenylene group.
[0083] In one embodiment of the present specification, L2 is a phenylene group.
[0084] In one embodiment of the present specification, L2 is a phenylene group, and the phenylene group is
[0000]
[0085] In another embodiment, L2 is a phenylene group, and the phenylene group is
[0000]
[0086] The
[0000]
[0000] means being linked to Ar1 or a naphthyl group in Chemical Formula 1.
[0087] In one embodiment, at least any one of X1 to X3 in Chemical Formula 1 may be a heteroatom of trivalent group.
[0088] Specifically, at least any one of X1 to X3 may be N or P.
[0089] In one embodiment of the present specification, all of X1 to X3 may be N.
[0090] In one embodiment of the present specification, X1 may be N, and X2 and X3 may be CH.
[0091] In one embodiment of the present specification, X2 may be N, and X1 and X3 may be CH.
[0092] In one embodiment of the present specification, X3 may be N, and X1 and X2 may be CH.
[0093] In one embodiment of the present specification, X1 and X2 may be N. In this case, X3 is CH.
[0094] In one embodiment of the present specification, X1 and X3 may be N. In this case, X2 is CH.
[0095] In one embodiment of the present specification, X2 and X3 may be N. In this case, X1 is CH.
[0096] In one embodiment of the present specification, Ar2 and Ar3 in Chemical Formula 1 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.
[0097] In one embodiment of the present specification, Ar2 is a phenyl group.
[0098] In one embodiment of the present specification, Ar2 is a naphthyl group.
[0099] In one embodiment of the present specification, Ar2 is a naphthyl group, and may be
[0000]
[0100] In another embodiment, Ar2 is a naphthyl group, and may be
[0000]
[0101] In one embodiment of the present specification, Ar2 is a biphenyl group.
[0102] In one embodiment of the present specification, Ar2 is a biphenyl group, and may be
[0000]
[0103] In one embodiment of the present specification, Ar3 is a phenyl group.
[0104] In one embodiment of the present specification, Ar3 is a naphthyl group.
[0105] In one embodiment of the present specification, Ar3 is a naphthyl group, and may be
[0000]
[0106] In another embodiment, Ar3 is a naphthyl group, and may be
[0000]
[0107] In one embodiment of the present specification, Ar3 is a biphenyl group.
[0108] In one embodiment of the present specification, Ar3 is a biphenyl group, and may be
[0000]
[0109] The
[0000]
[0000] means being linked to heterocyclic ring including X1 to X3 of Chemical Formula 1.
[0110] In one embodiment of the present specification, Ar4 and Ar5 in Chemical Formula 2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.
[0111] In one embodiment of the present specification, Ar4 and Ar5 in Chemical Formula 2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; or a substituted or unsubstituted naphthyl group.
[0112] In one embodiment of the present specification, Ar4 is a phenyl group.
[0113] In one embodiment of the present specification, Ar4 is a naphthyl group.
[0114] In one embodiment of the present specification, Ar4 is a naphthyl group, and may be
[0000]
[0115] In another embodiment, Ar4 is a naphthyl group, and may be
[0000]
[0116] In one embodiment of the present specification, Ar4 is a biphenyl group.
[0117] In one embodiment of the present specification, Ar4 is a biphenyl group, and may be
[0000]
[0118] In one embodiment of the present specification, Ar5 is a phenyl group.
[0119] In one embodiment of the present specification, Ar5 is a naphthyl group.
[0120] In one embodiment of the present specification, Ar5 is a naphthyl group, and may be
[0000]
[0121] In another embodiment, Ar5 is a naphthyl group, and may be
[0000]
[0122] In one embodiment of the present specification, Ar5 is a biphenyl group.
[0123] In one embodiment of the present specification, Ar5 is a biphenyl group, and may be
[0000]
[0124] The
[0000]
[0000] means being linked to heterocyclic ring including X4 to X6 of Chemical Formula 2.
[0125] In one embodiment of the present specification, Ar1 is Chemical Formula 2.
[0126] In one embodiment of the present specification, Ar1 is Chemical Formula 2, and X4 to X6 are N.
[0127] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X4 to X6 are N, Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.
[0128] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X4 to X6 are N, Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group.
[0129] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X4 to X6 are N, and Ar4 and Ar5 are phenyl groups.
[0130] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X4 to X6 are N, Ar4 and Ar5 are the same as or different from each other, and each independently a phenyl group or a naphthyl group.
[0131] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X4 to X6 are N, Ar4 and Ar5 are the same as or different from each other, and each independently a phenyl group or a biphenyl group.
[0132] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X5 is CH, and X4 and X6 are N.
[0133] In one embodiment of the present specification, Ar1 is Chemical Formula 2, X4 is CH, and X5 and X6 are N.
[0134] In one embodiment of the present specification, Ar1 is Chemical Formula 3.
[0135] In one embodiment of the present specification, Ar1 is Chemical Formula 3, R1 is hydrogen.
[0136] In one embodiment of the present specification, Ar1 is Chemical Formula 4.
[0137] In one embodiment of the present specification, Ar1 is Chemical Formula 4, L1 and Chemical Formula 4 are bonded at position 2 of Chemical Formula 4.
[0138] In one embodiment of the present specification, Ar1 is Chemical Formula 4, and X4 is CRR′.
[0139] In one embodiment of the present specification, Ar1 is Chemical Formula 4, X4 is CRR′, and R and R′ are each independently a substituted or unsubstituted alkyl group.
[0140] In one embodiment of the present specification, Ar1 is Chemical Formula 4, X4 is CRR′, R and R′ are methyl groups, and R2 is hydrogen.
[0141] In one embodiment of the present specification, Ar1 is Chemical Formula 5.
[0142] In one embodiment of the present specification, Ar1 is Chemical Formula 5, L1 and Chemical Formula 5 are bonded at position 3 of Chemical Formula 5.
[0143] In one embodiment of the present specification, Ar1 is Chemical Formula 5, and R3 and R4 are hydrogen.
[0144] In one embodiment of the present specification, Ar1 is Chemical Formula 6.
[0145] In one embodiment of the present specification, Ar1 is Chemical Formula 6, and R6 is hydrogen.
[0146] In one embodiment of the present specification, R5 is hydrogen.
[0147] In one embodiment of the present specification, Ar1 is Chemical Formula 7.
[0148] In one embodiment of the present specification, Ar1 is Chemical Formula 7, and R7 is a substituted or unsubstituted aryl group.
[0149] In one embodiment of the present specification, R7 is a substituted or unsubstituted phenyl group.
[0150] In one embodiment of the present specification, R7 is a phenyl group.
[0151] In one embodiment of the present, specification, R8 is hydrogen.
[0152] In another embodiment, Ar1 is Chemical Formula 8.
[0153] In one embodiment of the present specification, Ar1 is Chemical Formula 8, R9 is a substituted or unsubstituted aryl group.
[0154] In another embodiment, R9 is a substituted or unsubstituted phenyl group.
[0155] In one embodiment of the present specification, R9 is a phenyl group.
[0156] In one embodiment of the present specification, R10 is hydrogen.
[0157] In one embodiment of the present specification, R11 is hydrogen.
[0158] In one embodiment of the present specification, Ar1 is Chemical Formula 9.
[0159] In another embodiment, Ar1 is Chemical Formula 9, and R12 is hydrogen.
[0160] In one embodiment of the present specification, the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulae 1-a-1 to 1-a-14, 2-a-1 to 2-a-14, 3-a-1 to 3-a-14, and 4-a-1 to 4-a-14.
[0161] In one embodiment of the present specification, the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulae 1-b-1 to 1-b-26, 2-b-1 to 2-b-26, 3-b-1 to 3-b-26, and 4-b-1 to 4-b-26.
[0162] In one embodiment of the present specification, the compound represented by Chemical Formula 1-1 is represented by any one of the following Chemical Formulae 1-a-1 to 3-a-14, and 1-b-1 to 1-b-26.
[0000]
[0163] In one embodiment of the present specification, the compound represented by Chemical Formula 1-2 is represented by any one of the following Chemical Formulae 2-a-1 to 2-a-14, and 2-b-1 to 2-b-26.
[0000]
[0164] In one embodiment of the present specification, the compound represented by Chemical Formula 1-3 is represented by any one of the following Chemical Formulae 3-a-1 to 3-a-14, and 3-b-1 to 3-b-26.
[0000]
[0165] In one embodiment of the present specification, the compound represented by Chemical Formula 1-4 is represented by any one of the following Chemical Formulae 4-a-1 to 4-a-14, and 4-b-1 to 4-b-26.
[0000]
[0166] The compound of Chemical Formula 1 can have suitable characteristics for use as an organic material layer used in an organic light emitting device, by introducing substituents having different heterorings on both sides with a naphthalene group as the center, as shown in Chemical Formula 1.
[0167] The compound represented by Chemical Formula 1 includes a hetero-cyclic compound including at least one or more of X1 to X3. Therefore, the compound represented by Chemical Formula 1 includes a hetero-cyclic structure thereby has a suitable energy level as an electron injection and/or an electron transfer material in an organic light emitting device. In addition, a device having low driving voltage and high light efficiency can be accomplished by selecting the compounds having a suitable energy level depending on the substituents from among the compounds represented by Chemical Formula 1 in the present specification, and using them in the organic light emitting device.
[0168] In addition, by introducing various substituents to the core structure, the energy band gap can be finely adjusted, and meanwhile, characteristics at the surface between organic materials can be improved. Therefore, applications of the material can be diverse.
[0169] Meanwhile, the compound of Chemical Formula 1 has a high glass transition temperature (Tg) thereby has excellent thermal stability. Such a thermal stability improvement becomes an important factor that provides a driving stability to a device.
[0170] The compound represented by Chemical Formula 1 may be prepared based on the preparation examples described later.
[0171] The compound represented by Chemical Formula 1 may be prepared using a method in which a structure, in which a heterocyclic ring including X1 to X3 is substituted with Ar2, Ar3 and L1, is bonded to a structure, in which a naphthyl group is substituted with substituted Chemical Formula 2; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroring group including one or more of O, N and S as a heteroatom.
[0172] The hetero-cyclic compound represented by Chemical Formula 1 in addition to Chemical Formulae 1-1 to 1-4 may be prepared by modifying the number of heteroatoms in X1 to X3, Ar2, Ar3 and Lx.
[0173] In Lx, x is an integer of 1 or 2.
[0174] In addition, the present specification provides an organic light emitting device that includes the hetero-cyclic compound represented by Chemical Formula 1.
[0175] In one embodiment of the present specification, an organic light emitting device that includes a first electrode; a second electrode provided opposite to the first electrode; and one or more layers of organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the hetero-cyclic compound.
[0176] The organic material layer of the organic light emitting device in the present specification may be formed as a monolayer structure, but may also be formed as a multilayer structure in which two or more layers of the organic material layers are laminated. For example, the organic light emitting device of the present invention may have a structure that includes a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer and the like as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include less numbers of organic material layers.
[0177] In one embodiment of the present specification, the organic material layer includes a hole injection layer or a hole transfer layer, and the hole injection layer or the hole transfer layer includes the hetero-cyclic compound.
[0178] In another embodiment, the organic material layer includes a light emitting layer, and the light emitting layer includes the hetero-cyclic compound as the host of the light emitting layer.
[0179] In one embodiment of the present specification, the organic material layer includes an electron transfer layer or an electron injection layer, and the electron transfer layer or the electron injection layer includes the hetero-cyclic compound.
[0180] In one embodiment of the present specification, the electron transfer layer, the electron injection layer, or the layer simultaneously performing electron transfer and electron injection includes only the hetero-cyclic compound.
[0181] In one embodiment of the present specification, the organic material layer further includes a hole injection layer or a hole transfer layer including a compound that includes an arylamino group, a carbazole group or a benzocarbazole group, in addition to the organic material layer including the hetero-cyclic compound.
[0182] In one embodiment of the present specification, the organic material layer including the hetero-cyclic compound includes the hetero-cyclic compound as a host, and other organic compounds, metals or metal compounds as a dopant.
[0183] In another embodiment, the organic light emitting device may be an organic light emitting device having a normal type structure in which an anode, one or more layers of organic material layers and a cathode are laminated on a substrate in consecutive order.
[0184] In another embodiment, the organic light emitting device may be an organic light emitting device having an inverted type structure in which a cathode, one or more layers of organic material layers and an anode are laminated on a substrate in consecutive order.
[0185] For example, the structure of an organic light emitting device according to one embodiment of the present specification is illustrated in FIGS. 1 and 2 .
[0186] FIG. 1 illustrates the structure of an organic electronic device in which a substrate ( 1 ), an anode ( 2 ), a light emitting layer ( 3 ) and a cathode ( 4 ) are laminated in consecutive order. In the structure such as this, the hetero-cyclic compound may be included in the light emitting layer ( 3 ).
[0187] FIG. 2 illustrates the structure of an organic electronic device in which a substrate ( 1 ), an anode ( 2 ), a hole injection layer ( 5 ), a hole transfer layer ( 6 ), a light emitting layer ( 3 ), an electron transfer layer ( 7 ) and a cathode ( 4 ) are laminated in consecutive order. In the structure such as this, the hetero-cyclic compound may be included in one or more layers of the hole injection layer ( 5 ), the hole transfer layer ( 6 ), the light emitting layer ( 3 ) and the electron transfer layer ( 7 ).
[0188] In the structure such as this, the compound may be included in one or more layers of the hole injection layer, the hole transfer layer, the light emitting layer and the electron transfer layer.
[0189] The organic light emitting device of the present specification may be prepared using materials and methods known in the related art, except that one or more layers of organic material layers include the compound of the present specification, that is, the hetero-cyclic compound.
[0190] When the organic light emitting device includes multiple numbers of organic material layers, the organic material layer may be formed with identical materials or different materials.
[0191] The organic light emitting device of the present specification may be prepared using materials and methods known in the related art, except that one or more layers of organic material layers includes the hetero-cyclic compound, that is, the compound represented by Chemical Formula 1.
[0192] For example, the organic light emitting device of the present specification may be prepared by laminating a first electrode, an organic material layer and a second electrode on a substrate in consecutive order. At this time, using a physical vapor deposition (PVD) method such as a sputtering method or an e-beam evaporation method, the anode is formed by depositing a metal, a metal oxide having conductivity, or alloys thereof on the substrate, and after the organic material layer including a hole injection layer, a hole transfer layer, a light emitting layer and an electron transfer layer is formed thereon, a material that can be used as the cathode is deposited thereon, and as a result, the organic light emitting device may be prepared. In addition to this method, the organic light emitting device may be prepared by depositing a cathode material, an organic material layer and an anode material on a substrate in consecutive order.
[0193] In addition, when the organic light emitting device is prepared, the compound of Chemical Formula 1 may be formed as an organic material layer using a solution coating method as well as a vacuum deposition method. Herein, the solution coating method means spin coating, dip coating, doctor blading, ink jet printing, screen printing, a spray method, roll coating or the like, but is not limited thereto.
[0194] In addition to these methods, the organic light emitting device may also be prepared by depositing a cathode material, an organic material layer and an anode material on a substrate in consecutive order (PCT Publication No. 2003/012890). However, the preparation method is not limited thereto.
[0195] In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.
[0196] In another embodiment, the first electrode is a cathode, and the second electrode is an anode.
[0197] As the anode material, a material having large work function is normally preferable so that hole injection to the organic material layer is smooth. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc or gold, and alloys thereof; metal oxides such as zinc oxides, indium oxides, indium tin oxides (ITO) or indium zinc oxide (IZO); and mixtures of metals and oxides such as ZnO:Al or SnO 2 :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, or the like, but are not limited thereto.
[0198] As the cathode material, a material having small work function is normally preferable so that electron injection to the organic material layer is smooth. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and load, or alloys thereof; multilayer structure materials such as LiF/Al or LiO 2 /Al, or the like, but are not limited thereto.
[0199] The hole injection layer is a layer that injects holes from an electrode, and a hole injection material is preferably a compound that has an ability to transfer the holes, has a hole injection effect in an anode and has an excellent hole injection effect for a light emitting layer or a light emitting material, prevents the movement of excitons generated in the light emitting layer to an electron injection layer or an electron injection material, and in addition, has excellent thin film forming ability. The highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of an anode and the HOMO of surrounding organic material layers. Specific examples of the hole injection material include a metal porphyrin, oligothiophene, an arylamine-based organic material, a hexanitrile hexazatriphenylene-based organic material, a quinacridone-based organic material, a perylene-based organic material, anthraquinone, and a polyaniline- and polythiophene-based conductive polymer, or the like, but are not limited thereto.
[0200] The hole transfer layer is a layer that receives holes from a hole injection layer and transfers the holes to a light emitting layer, and as the hole transfer material, a material that can receive the holes from an anode or a hole injection layer, move the holes to a light emitting layer, and has high mobility for the holes is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer having conjugated parts and non-conjugated parts together, or the like, but are not limited thereto.
[0201] The light emitting material is a material that can emit light in a visible light region by receiving holes and electrons from a hole transfer layer and an electron transfer layer, respectively, and binding the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); a carbazole-based compound; a dimerized styryl compound; BAlq; a 10-hydroxybenzo quinoline-metal compound; a benzoxazole-, a benzthiazole- and a benzimidazole-based compound; a poly(p-phenylenevinylene) (PPV)-based polymer; a spiro compound; polyfluorene, rubrene or the like, but are not limited thereto.
[0202] The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative, a heteroring-containing compound, or the like. Specifically, the condensed aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound or the like, and the heteroring-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative or the like, but are not limited thereto.
[0203] The dopant material includes an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, or the like. Specifically, the aromatic amine derivative includes arylamino-including pyrene, anthracene, crycene and periflanthene as the condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and the styrylamine compound includes a compound in which a substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, and one, two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetramine or the like is included, but the styrylamine compound is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex or the like, but is not limited thereto.
[0204] The electron transfer layer is a layer that receives electrons from an electron injection layer and transfers the electrons to a light emitting layer, and as the electron transfer material, a material that can receive the electrons from a cathode, move the electrons to a light emitting layer, and has high mobility for the electrons is suitable. Specific examples thereof include an Al complex of 8-hydroxyquinoline; a complex including Alq3; an organic radical compound; a hydroxyflavone-metal complex or the like, but are not limited thereto. The electron transfer layer can be used together with any desired cathode material as is used according to technologies in the related art. Particularly, examples of the suitable cathode material are common materials that have small work function, and in which an aluminum layer or a silver layer follows. Specifically the cathode material includes cesium, barium, calcium, ytterbium and samarium, and in each case, an aluminum layer or a silver layer follows.
[0205] The electron injection layer is a layer that injects electrons from an electrode, and the electron injection material is preferably a compound that has an ability to transfer the electrons, has an electron injection effect in a cathode and has an excellent electron injection effect for a light emitting layer or a light emitting material, prevents the movement of excitons generated in the light emitting layer to the electron injection layer, and in addition, has excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone or the like, and derivatives thereof, a metal complex compound, a nitrogen-containing 5-membered ring derivative, or the like, but are not limited thereto.
[0206] The metal complex compound may include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)berylium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato) (o-cresolato)gallium, bis(2-methyl-8-quinolinato) (1-naphtholato)aluminum, bis(2-methyl-8-quinolinato) (2-naphtholato)gallium or the like, but is not limited thereto.
[0207] The organic light emitting device according to the present specification may be a top-emission type, a bottom-emission type or a dual-emission type depending on the materials used.
[0208] In one embodiment of the present specification, the hetero-cyclic compound may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.
[0209] Hereinafter, the hetero-cyclic compound represented by Chemical Formula 1 and the manufacture of an organic light emitting device including the same will be described in detail with reference to examples. However, the following examples are for the illustrative purposes only, and the scope of the present specification is not limited thereto.
EXAMPLE
[0210] Hereinafter, the present invention will be described in more detail with reference to preparation examples and experimental examples, however, the scope of the present invention is not limited to the following preparation examples and the experimental examples.
Preparation Example
Preparation Example 1
Preparation of the Following Compound 1-a-1
1) Synthesis of the Following Compound 1-A
[0211]
[0212] After the 2-chloro-4,6-diphenyl-1,3,5-triazine compound (37.1 g, 0.14 mol) and 4-chlorophenylboronic acid (23.8 g, 0.15 mol) were completely dissolved in 150 ml of tetrahydrofuran under nitrogen atmosphere, a 2M aqueous potassium carbonate solution (80 ml) was added thereto, and after tetrakis-(triphenylphosphine)palladium (3.2 g, 2.7 mmol) was added thereto, the mixture was stirred with heating for 5 hours. The temperature was lowered to room temperature, and the water layer was removed. The result was dried with anhydrous magnesium sulfate, concentrated under vacuum, then passed through a column using tetrahydrofuran:hexane=1:6, and Compound 1-A (34 g, yield: 72%) was prepared.
[0213] MS [M+H] + =344
2) Synthesis of the Following Compound 1-B
[0214]
[0215] Under nitrogen atmosphere, Compound 1-A (34 g, 98.9 mmol), bis(pinacolato)diboron (27.6 g, 108 mmol) and potassium acetate (29.1 g, 296 mmol) were mixed, added to 100 ml of dioxane, and the mixture was heated while stirring. Under reflux, bis(dibenzylideneacetone)palladium (1.7 g, 2.94 mmol) and tricyciohexylphosphine (1.6 g, 5.9 mmol) were added thereto, and the result was heated and stirred for 10 hours. After the reaction completed, the temperature was lowered to room temperature, and the result was filtered. The filtrate was poured to water, extracted with chloroform, and the organic layer was dried using anhydrous magnesium sulfate. The result was vacuum distilled, recrystallized with ethanol, and Compound 1-B (35 g, yield: 81%) was prepared.
[0216] MS [M+H] + =436
3) Synthesis of the Following Compound 1-C
[0217]
[0218] After Compound 1-B (14.5 g, 33.3 mmol) and 7-bromonaphthalen-2-ol (7.4 g, 33.3 mmol) were completely dissolved in 100 ml of tetrahydrofuran, 60 ml of a 2M aqueous potassium carbonate solution, and tetrakistriphenyl-phosphinopalladium (769 mg, 0.67 mmol) were added thereto, and then the mixture was stirred with heating for 3 hours. After the temperature was lowered to room temperature and the reaction completed, the potassium carbonate solution was removed and the yellow solid was filtered. The filtered yellow solid was washed once with tetrahydrofuran and once with ethanol, and Compound 1-C (13.2 g, yield: 88%) was prepared.
[0219] MS [M+H] + =452
4) Synthesis of the Following Compound 1-D
[0220]
[0221] After Compound 1-C (13.0 g, 28.8 mol) was dissolved THF (100 mL), triethylamine (10.0 mL, 72.0 mmol) was added thereto, and the mixture was cooled to 0° C. While maintaining the temperature, triflic anhydride (16.2 g, 57.6 mmol (was slowly added dropwise. After the temperature was raised to room temperature, the result was stirred for 2 hours. After the solvent was concentrated under reduced pressure, hexane was added thereto, and the solid produced was filtered. Compound 1-b (13.6 g, 81%) was obtained by vacuum drying the precipitate.
[0222] MS [M+H] + =584
5) Synthesis of the Following Compound 2-A
[0223]
[0224] Compound 32-A (11.8 g, 83%) was prepared using the same method as the method that prepares Compound 1-A except that 4-chloro-2,6-diphenylpyrimidine was used instead of the 2-chloro-4,6-diphenyl-1,3,5-triazine compound.
[0225] MS [M+H] + =343
6) Synthesis of the Following Compound 2-B
[0226]
[0227] Compound 2-B (21.7 g, 89%) was prepared using the same method as the method that prepares Compound 1-B except that Compound 2-A was used instead of Compound 1-A.
[0228] MS [M+H] + =435
7) Synthesis of the Following Compound 1-a-1
[0229]
[0230] After Compound 1-D (11.2 g, 19.2 mmol) and Compound 2-B (9.2 g, 21.1 mmol) were completely dissolved in 60 ml of tetrahydrofuran, 40 ml of a 2M aqueous potassium carbonate solution, and tetrakistriphenyl-phosphinopalladium (443 mg, 0.38 mmol) were added thereto, and the mixture was stirred with heating for 3 hours. After the temperature was lowered to room temperature and the reaction completed, the potassium carbonate solution was removed and the white solid was filtered. The filtered white solid was washed once with tetrahydrofuran and once with ethanol, and Compound 1-a-1 (11.3 g, yield: 80%) was prepared.
[0231] MS [M+H] + =742
Preparation Example 2
Preparation of the Following Compound 1-a-2
1) Synthesis of the Following Compound 3-A
[0232]
[0233] Compound 3-A (17.3 g, 83%) was prepared using the same method as the method that prepares Compound 1-A except that 2-chloro-4,6-diphenylpyrimidine was used instead of the 2-chloro-4,6-diphenyl-1,3,5-triazine compound.
[0234] MS [M+H] + =343
2) Synthesis of the Following Compound 3-B
[0235]
[0236] Compound 3-B (12.9 g, 82%) was prepared using the same method as the method that prepares Compound 1-B except that Compound 3-A was used instead of Compound 1-A.
[0237] MS [M+H] + =435
3) Synthesis of the Following Compound 1-a-2
[0238]
[0239] Compound 1-a-2 (11.4 g, 85%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 3-B was used instead of Compound 2-B.
[0240] MS [M+H] + =742
Preparation Example 3
Preparation of the Following Compound 1-a-5
1) Synthesis of the Following Compound 4-A
[0241]
[0242] Compound 4-A (18.8 g, 88%) was prepared using the same method as the method that prepares Compound 1-A except that 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine was used instead of the 2-chloro-4,6-diphenyl-1,3,5-triazine compound.
[0243] MS [M+H] + =420
2) Synthesis of the Following Compound 4-B
[0244]
[0245] Compound 4-B (16.5 g, 84%) was prepared using the same method as the method that prepares Compound 1-B except that Compound 4-A was used instead of Compound 1-A.
[0246] MS [M+H] + =512
3) Synthesis of the Following Compound 1-a-5
[0247]
[0248] Compound 1-a-5 (12.7 g, 88%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 4-B was used instead of Compound 2-B.
[0249] MS [M+H] + =819
Preparation Example 4
Preparation of the Following Compound 1-b-1
1) Synthesis of the Following Compound 1-b-1
[0250]
[0251] Compound 1-b-1 (13.4 g, 87%) was prepared using the same method as the method that prepares Compound 1-a-1 except that (4-(9H-carbazol-9-yl)phenyl)boronic acid was used instead of Compound 2-B.
[0252] MS [M+H] + =677
Preparation Example 5
Preparation of the Following Compound 1-b-2
1) Synthesis of the Following Compound 1-b-2
[0253]
[0254] Compound 1-b-2 (9.2 g, 89%) was prepared using the same method as the method that prepares Compound 1-a-1 except that (4-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)boronic acid was used instead of Compound 2-B.
[0255] MS [M+H] + =704
Preparation Example 6
Preparation of the Following Compound 2-a-1
1) Synthesis of the Following Compound 5-A
[0256]
[0257] Compound 5-A (22.6 g, 85%) was prepared using the same method as the method that prepares Compound 1-C except that 8-bromonaphthalen-2-ol was used instead of the 7-bromonaphthalen-2-ol compound.
[0258] MS [M+H] + =452
2) Synthesis of the Following Compound 5-B
[0259]
[0260] Compound 5-B (19.6 g, 89%) was prepared using the same method as the method that prepares Compound 1-D except that Compound 5-A was used instead of Compound 1-C.
[0261] MS [M+H] + =584
3) Synthesis of the Following Compound 2-a-1
[0262]
[0263] Compound 2-a-1 (11.3 g, 84%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 5-B was used instead of Compound 1-D.
[0264] MS [M+H] + =742
Preparation Example 7
Preparation of the Following Compound 3-a-1
1) Synthesis of the Following Compound 6-A
[0265]
[0266] Compound 6-A (23.1 q, 82%) was prepared using the same method as the method that prepares Compound 1-C except that 5-bromonaphthalen-2-ol was used instead of the 7-bromonaphthalen-2-ol compound.
[0267] MS [M+H] + =452
2) Synthesis of the Following Compound 6-B
[0268]
[0269] Compound 6-B (20.1 g, 88%) was prepared using the same method as the method that prepares Compound 1-D except that Compound 6-A was used instead of Compound 1-C.
[0270] MS [M+H] + =584
3) Synthesis of the Following Compound 3-a-1
[0271]
[0272] Compound 3-a-1 (12.9 g, 85%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 6-B was used instead of Compound 1-D.
[0273] MS [M+H] + =742
Preparation Example 8
Preparation of the Following Compound 4-a-1
1) Synthesis of the Following Compound 7-A
[0274]
[0275] Compound 7-A (25.8 g, 89%) was prepared using the same method as the method that prepares Compound 1-C except that 8-bromonaphthalen-1-ol was used instead of the 7-bromonaphthalen-2-ol compound.
[0276] MS [M+H] + =452
2) Synthesis of the Following Compound 7-B
[0277]
[0278] Compound 7-B (22.5 g, 86%) was prepared using the same method as the method that prepares Compound 1-D except that Compound 7-A was used instead of Compound 1-C.
[0279] MS [M+H] + =584
3) Synthesis of the Following Compound 4-a-1
[0280]
[0281] Compound 4-a-1 (18.1 g, 88%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 7-B was used instead of Compound 1-D.
[0282] MS [M+H] + =742
Preparation Example 9
Preparation of the Following Compound 3-b-18
[0283]
[0284] Compound 3-b-18 (19.2 g, 83%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 6-B was used instead of Compound 1-D.
[0285] MS [M+H] + =704
Preparation Example 10
Preparation of the Following Compound 4-b-18
[0286]
[0287] Compound 4-b-18 (11.6 g, 86%) was prepared using the same method as the method that prepares Compound 1-a-1 except that Compound 7-B was used instead of Compound 1-D.
[0288] MS [M+H] + =704
Experimental Example
[0289] A glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1,000 Å was placed in distilled water, in which a detergent is dissolved, and ultrasonic cleaned. At this time, a product of Fischer Corporation was used as the detergent, and as the distilled water, distilled water filtered twice with a filter manufactured by Millipore Corporation was used. After the ITO was cleaned for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes using distilled water. After the cleaning with distilled water was finished, ultrasonic cleaning was performed using an isopropyl alcohol, acetone and methanol solvent, and the substrate was dried and then transferred to a plasma washer. In addition, the substrate was washed for 5 minutes using oxygen plasma, and was transferred to a vacuum deposition apparatus.
[0290] On the transparent ITO electrode prepared as above, a hole injection layer was formed to a thickness of 500 Å by thermal vacuum depositing hexanitrile hexaazatriphenylene (HAT) of the following chemical formula.
[0000]
[0291] On the hole injection layer, a hole transfer layer was formed by vacuum depositing the following compound, 4-4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), which is a material that transfers the holes.
[0000]
[0292] Subsequently, a light emitting layer was formed on the hole transfer layer to a film thickness of 300 Å by vacuum depositing the following BH and BD in the weight ratio of 25:1.
[0000]
[0293] On the light emitting layer, an electron injection and transfer layer were formed to a thickness of 350 Å by vacuum depositing Compound 1-a-1 prepared in Preparation Example 1 and the lithium quinolate (LiQ) compound in the weight ratio of 1:1. A cathode was formed an the electron injection and transfer layer by depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 Å in consecutive order.
[0294] In the above process, the deposition rate of the organic material was maintained to be 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride of the cathode to be 0.3 Å/sec, and the deposition rate of aluminum to be 2 Å/sec, and the degree of vacuum when being deposited was maintained to be 2×10 −7 to 5×10 −6 torr, and as a result, the organic light emitting device was manufactured.
Experimental Example 2
[0295] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 1-a-2 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 3
[0296] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 1-a-5 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 4
[0297] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 1-b-1 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 5
[0298] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 1-b-2 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 6
[0299] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 2-a-1 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 7
[0300] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 3-a-1 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 8
[0301] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 4-a-1 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 9
[0302] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 3-b-18 was used instead of Compound 1-a-1 in Experimental Example 1.
Experimental Example 10
[0303] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that Compound 4-b-18 was used instead of Compound 1-a-1 in Experimental Example 1.
Comparative Example 1
[0304] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that the compound of the following ET1 was used instead of Compound 1-a-1 in Experimental Example 1.
[0000]
Comparative Example 2
[0305] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that the compound of the following ET2 was used instead of Compound 1-a-1 in Experimental Example 1.
[0000]
Comparative Example 3
[0306] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that the compound of the following ET3 was used instead of Compound 1-a-1 in Experimental Example 1.
[0000]
Comparative Example 4
[0307] The organic light emitting device was manufactured using the same method as in Experimental Example 1 except that the compound of the following ET4 was used instead of Compound 1-a-1 in Experimental Example 1.
[0000]
[0308] When current was applied to the organic light emitting device manufactured by Experimental Examples 1 to 8 and Comparative Examples 1 to 4, the results of Table 1 were obtained.
[0000]
TABLE 1
Efficiency
Color
Voltage
(cd/A@10
Coordinates
Compound
(V@10 mA/cm 2 )
mA/cm 2 )
(x, y)
Experimental
Compound
3.81
5.13
(0.136,
Example 1
1-a-1
0.127)
Experimental
Compound
3.75
4.99
(0.139,
Example 2
1-a-2
0.128)
Experimental
Compound
3.89
5.24
(0.138,
Example 3
1-a-5
0.124)
Experimental
Compound
3.88
5.31
(0.136,
Example 4
1-b-1
0.127)
Experimental
Compound
3.76
5.29
(0.133,
Example 5
1-b-2
0.121)
Experimental
Compound
3.83
5.17
(0.139,
Example 6
2-a-1
0.126)
Experimental
Compound
3.76
5.28
(0.139,
Example 7
3-a-1
0.127)
Experimental
Compound
3.59
5.31
(0.137,
Example 8
4-a-1
0.129)
Experimental
Compound
3.78
5.12
(0.136,
Example 9
3-b-18
0.125)
Experimental
Compound
3.82
5.16
(0.136,
Example 10
4-b-18
0.129)
Comparative
ET1
4.11
3.98
(0.137,
Example 1
0.126)
Comparative
ET2
4.21
4.02
(0.136,
Example 2
0.123)
Comparative
ET3
4.25
4.21
(0.139,
Example 3
0.119)
Comparative
ET4
4.32
4.04
(0.138,
Example4
0.120)
[0309] From the results of Table 1, in which Experimental Examples 1 to 8 and Comparative Examples 1 and 2 are compared, it can be verified that an organic light emitting device having excellent electron transfer and injection abilities thereby having low voltage and/or high efficiency can be provided when, with a naphthyl group as the standard, L1 and L2 are different from each other or Ar1 and Ar2 are different from each other, compared to when L1 and L2 are the same as each other and Ar1 and Ar2 are the same as each other.
[0310] In addition, as shown in Table 1, it can be verified that, when a naphthyl group is the standard, an organic light emitting device having excellent electron transfer and injection abilities thereby having low voltage and/or high efficiency can be provided compared to when other structures are the standard.
[0311] From the results of Table 1, in which Experimental Examples 1 to 8 and Comparative Example 4 are compared, it can be verified that electron transfer and injection abilities are excellent for the naphthyl group at a specific position according to one embodiment of the present specification.
REFERENCES
[0000]
1 : Substrate
2 : Anode
3 : Light Emitting Layer
4 : Cathode
5 : Hole Injection Layer
6 : Hole Transfer Layer
7 : Electron Transfer Layer
|
The present specification provides a novel compound greatly improving the life span, efficiency, electrical and chemical stability and thermal stability of an organic light emitting device, and an organic light emitting device containing the compound in an organic compound layer.
| 2 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims the benefit of prior provisional applications 61/171,702, filed on Apr. 22, 2009 and 61/186,704, filed on Jun. 12, 2009. The full disclosures of each of these prior provisional applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to medical devices, systems, and methods to treat disease. More particularly, the present invention relates to methods to treat hypertension by delivering agents to reduce hyperactive sympathetic nerve activity in the adventitia of arteries and/or veins that lead to the kidneys.
Hypertension, or high blood pressure, affects an estimated 30-40% of the world's adult population. Renal, or renovascular, hypertension can be caused by hypoperfusion of the kidneys due to a narrowing of the renal arteries. The kidneys respond by giving off hormones that signal the body to retain salt and water, causing the blood pressure to rise. The renal arteries may narrow due to arterial injury or atherosclerosis. Despite effective drug regimens to regulate the renin-angiotensin-aldosterone pathway or to remove excess fluid from the body and reduce blood pressure, some 20-30% of patients with hypertension suffer from resistant forms of the disease.
Resistant hypertension is a common clinical problem, caused when a patient is unable to control high blood pressure by systemic medication alone. Resistant hypertension is especially a problem in old and obese people. Both of these demographics are growing. While symptoms are not obvious in these patients, cardiovascular risk is greatly increased when they are unable to control their blood pressure.
Hypertension is also caused by hyperactive renal sympathetic nerves. Renal sympathetic efferent and afferent nerves run generally longitudinally along the outside of arteries leading from the aorta to the kidneys. These nerves are critically important in the initiation and maintenance of systemic hypertension. It has been shown that by severing these nerves, blood pressure can be reduced. Exemplary experiments have shown that denervation of the renal sympathetic nerves in rats with hyperinsulinemia-induced hypertension would reduce the blood pressure to normotensive levels as compared to controls [Huang W-C, et al. Hypertension 1998; 32:249-254].
Percutaneous or endoscopic interventional procedures are very common in the United States and other countries around the world. Intravascular catheter systems are used for procedures such as balloon angioplasty, stent placement, atherectomy, retrieval of blood clots, photodynamic therapy, and drug delivery. All of these procedures involve the placement of long, slender tubes known as catheters into arteries, veins, or other lumens of the body in order to provide access to the deep recesses of the body without the necessity of open surgery.
In cases where renal arterial occlusion is causing hypertension that cannot be controlled with medication, another potential therapy includes balloon angioplasty of the renal artery. In rare cases, surgical bypass grafting may be considered as a therapeutic alternative. While renal angioplasty can be effective in reducing blood pressure, angioplasty is plagued with resulting restenosis due to elastic recoil, dissection, and neointimal hyperplasia. Renal stents may improve the result, but also lead to restenosis or renarrowing of the artery due to neointimal hyperplasia.
While renal denervation had been performed with surgical methods in the past, more recently a catheter-based therapy to heat and destroy the nerves from within the renal artery using radio-frequency ablation has been studied. A human trial of the RF-ablation catheter method has also been performed, with reported reduction in blood pressure in patients enrolled in the catheter treatment arm of the study [Krum H, et al. Lancet 2009; 373(9671):1228-1230].
While the use of catheter-based radiofrequency (RF) denervation appears to have a therapeutic effect, it is unknown what long-term implications will arise from the permanent damage caused to the vessel wall and nerves by the RF procedure. Radiofrequency energy denervates the vessel by creating heat in the vessel wall. The RF probe contacts the inner lining of the artery and the RF energy is transmitted through the tissue.
Anti-hypertension therapies can be problematic in a number of respects. First, hypertension is, for the most part, an asymptomatic disease. Patients can lack compliance to medicinal regimens due to their perceived lack of symptoms. Second, even for patients that are highly compliant to drug therapy, their target blood pressure may not be reached, with little to no recourse but for intervention. Third, when intervention is taken (usually in the form of renal angioplasty and/or stenting), the long-term effects can include restenosis, progression of chronic kidney disease, and ultimately kidney failure, because angioplasty leads to activation of an injury cascade that causes fibrosis and remodeling of the target artery. Fourth, surgical techniques to bypass or denervate renal arteries are radical and can lead to a number of surgical complications. And fifth, it is unknown whether RF denervation of the artery will lead to further exacerbation of stenotic plaques, whether it is compatible with arteries in which stents have been placed, whether the energy transmission through thick plaques or fibrous intima will be enough to effect the underlying nerves procedure will work if the RF probe is in contact with a thick plaque in the majority of patients, or whether the effective deadening of not only nerves, but the smooth muscle in the arterial wall also, may lead to reactive hypervascular formation of the vasa vasorum and necrotizing plaques that, if ruptured, would result in acute kidney ischemia or chronic kidney disease. Thus, systems and protocols which are designed to produce sympathetic denervation with RF energy or surgical dissection are limited in their applicability across the breadth of hypertensive disease, or they may create new vascular complications that were not inherent to the underlying disease.
Neurotoxic agents like botulinum toxin, β-bungarotoxin (and other snake venom toxins), tetanus toxin, and α-latrotoxin, have been used or proposed for use in many surgical techniques to block nerves, reduce muscle activity or paralyze muscles. Neuromuscular blocking agents like tubocurarine, alcuronium, pipecuronium, rocuronium, pancuronium, vecuronium (and other curare-like drugs, derived originally from paralytic darts and arrows of South American tribes) have also been used to induce paralysis by competing for cholinergic receptors at the motor end-plate. The curare-like agents are short acting in comparison to the toxins. For example, botulinum toxin (which can be one of 7 different serologically distinct types, from type A to type G) have been used and is FDA approved to treat strabismus, blepharospasm, hemifacial spasm, improvement of moderate to severe frown lines (cosmetic), and for the treatment of excessive underarm sweating. Each of these uses for botulinum toxin has shown treatment effect ranging from several months to more than a year.
The lethal dose of botulinum toxin is approximately 1 ng/kg as determined by experiments in mice. Currently available forms of botulinum toxin, MYOBLOC™ and BOTOX® have specific activity of 70 to 130 U/ng and approximately 20 U/ng, respectively. One unit (1 U) is the amount of toxin found to cause death in 50% of mice tested 72 hours after intraperitoneal administration. MYOBLOC™ is available in 2500, 5000, or 10000 U vials and is prescribed for dosage totaling 2500 to 5000 U for the treatment of cervical dystonia. BOTOX® is available in 100 U per vial and is prescribed in dosages of 200-300 U for cervical dystonia, 50-75 U for axillary hyperhidrosis, or 12 U spread across 6 injections for blepharospasm. Active botulinum toxin is made up of a heavy chain and light chain with a total mass of 150 kDa; therefore, each 1 ng of active material contains approximately 4 billion active toxin molecules.
Current antihypertensive drugs typically modulate blood pressure by interrupting the renin-angiotensin-aldosterone axis or by acting as a diuretic. An earlier generation of antihypertensive agents had modes of action to directly impair the renal nervous system. Agents like guanethidine, guanacline, and bretylium tosylate would modulate hypertension by preventing release of norepinephrine (also known as noradrenaline) from sympathetic nerve terminals. With guanethidine, sympathectomy is accomplished by interfering with excitatory vesicular release and by replacing norepinephrine in synaptic vesicles. Sympathetic nerve failure has been previously demonstrated in rats and hamsters, but not humans, possibly because guanethidine was typically delivered systemically and the high local concentrations required to induce sympathetic denervation in humans would come at the risk of extremely undesirable systemic side effects. The use of guanethidine to create functional denervation in rodents is considered permanent, with no evidence of reinnervation of tissues for as long as 63 weeks after treatment in rats. In high doses, guanethidine inhibits mitochondrial respiration and leads to neuron death. Importantly for this invention, guanethidine can be used to create local denervation in a dose-dependent manner and without far-field effects. This has been seen in an experiment comparing guanethidine injection into one hindquarter of a hamster and compared to a control injection on the contralateral side, performed by Demas and Bartness, J Neurosci Methods 2001. This is an advantage for the use of the agent to localize the effect to a specific renal artery without diffusion beyond the renal sympathetic ganglion to the spinal cord or other nervous systems. Also of interest to this invention is the published observation that guanethidine selectively destroys postganglionic noradrenergic neurons (thus reducing norepinephrine) while sparing dopaminergic fibers and nonneural catecholamine-secreting cells. It is this high level of specificity for which guanethidine has been chosen as a useful therapy. Finally, guanethidine was approved by FDA for use as a systemic antihypertensive agent due to its ability to block sympathetic function, but has not been approved for local administration to cause long-term or permanent denervation.
Locally delivered guanethidine has produced localized sympathectomy in hamster hindquarters, as observed by Demas and Bartness, 2001. In a series of 10 to 20 unilateral injections of 2 microliters each containing 5 to 10 micrograms of guanethidine per microliter, into the inguinal adipose tissue of hamsters, compared to similar injections of placebo into the contralateral inguinal adipose tissue, functional sympathectomy of one side versus the other was seen with at least 200 micrograms of delivery, whether spread across 10 or 20 injections of 2 microliters each. The result was determined in this case by measuring the norepinephrine content of the tissue 2 weeks after delivery, with substantial reduction in the side that had received guanethidine versus the control (placebo) side.
Guanethidine has the chemical name Guanidine, [2-(hexahydro-1(2H)-azocinyl)ethyl]-, and is often supplied in the sulfate form, guanethidine sulfate or guanethidine monosulfate (CAS 645-43-2) with chemical name Guanidine, [2-(hexahydro-1(2H)-azocinyl)ethyl]-, sulfate (1:1). Guanethidine has been marketed under the trade name Ismelin.
Other agents have been shown to create partial or complete sympathectomy as well. These include immunosympathectomy agent anti-nerve growth factor (anti-NGF); auto-immune sympathectomy agents anti-dopamine beta-hydroxylase (anti-DβH) and anti-acetylcholinesterase (anti-AChe); chemical sympathectomy agents 6-hydroxyldopamine (6-OHDA), bretylium tosylate, guanacline, and N-(2-chloroethyl)-N-ethyl-2-bromobenzylamine (DSP4); and immunotoxin sympathectomy agents OX7-SAP, 192-SAP, anti-dopamine beta-hydroxylase saporin (DBH-SAP), and anti-dopamine beta-hydroxylase immunotoxin (DHIT). A full description of these agents is found in Picklo M J, J Autonom Nerv Sys 1997; 62:111-125. Phenol and ethanol have also been used to produce chemical sympathectomy and are also useful in the methods of this invention. Other sympatholytic agents include alpha-2-agonists such as clonidine, guanfacine, methyldopa, guanidine derivatives like betanidine, guanethidine, guanoxan, debrisoquine, guanoclor, guanazodine, guanoxabenz and the like; imadazoline receptor agonists such as moxonidine, relmenidine and the like; ganglion-blocking or nicotinic antagonists such as mecamylamine, trimethaphan and the like; MAOI inhibitors such as pargyline and the like; adrenergic uptake inhibitors such as rescinnamine, reserpine and the like; tyrosine hydroxylase inhibitors such as metirosine and the like; alpha-1 blockers such as prazosin, indoramin, trimazosin, doxazosin, urapidil and the like; non-selective alpha blockers such as phentolamine and the like; serotonin antagonists such as ketanserin and the like; and endothelin antagonists such as bosentan, ambrisentan, sitaxentan, and the like.
Additionally, agents that sclerose nerves can be used to create neurolysis or sympatholysis. Sclerosing agents that lead to the perivascular lesioning of nerves include quinacrine, chloroquine, sodium tetradecyl sulfate, ethanolamine oleate, sodium morrhuate, polidocanol, phenol, ethanol, or hypertonic solutions.
Renal sympathetic nerve activity leads to the production of norepinephrine. It has been well established that renal sympathectomy (also known as renal artery sympathectomy or renal denervation) reduces norepinephrine buildup in the kidney. This has been measured by studies that involved surgical denervation of the renal artery, published by Connors in 2004 for pigs, Mizelle in 1987 for dogs, and Katholi in 1981 for rats. In fact, it has been shown that surgical denervation of one renal artery with sham surgery on the contralateral renal artery results in reductions of approximately 90% or more in kidney norepinephrine content on the denervated side compared to the control side. This evidence of denervation is therefore used as a surrogate to test denervation methods in large animals like pigs, since these animals do not develop essential hypertension normally. Further evidence of the link between denervation and norepinephrine buildup has been presented in norepinephrine spillover from the kidney, measured in the renal vein outflow blood [as reported by Krum et al, Lancet 2009]. Further linkage has been made between the ability to reduce renal norepinephrine in large animal models (such as porcine models) indicating the ability to reduce blood pressure in hypertensive human patients.
Complete sympathectomy of the renal arteries remains problematic due to the side effects inherent with reducing blood pressure below normal levels. Over the past 30 years, an ongoing debate has taken place around the presence and impact of a “J-curve” when relating the reduction of hypertension to therapeutic benefit [Cruickshank J, Current Cardiology Reports 2003; 5:441-452]. This debate has highlighted an important point in the treatment of hypertension: that while reduction in blood pressure may reduce cardiovascular morbidity and mortality rates, too great a reduction leads to a reversal in benefit. With surgical sympathectomy, the renal efferent and afferent nerves are completely removed, so there is no ability to “titrate” the amount of sympathectomy for a given patient. An improved method is proposed here for a therapy that can be titrated to the needs of the individual patient with adventitial delivery of neurodegenerative or sympatholytic agents capable of creating dose-dependent sympathectomy. Given appropriate dose titration, therapy can be tailored to reach the bottom of the J-curve without overshooting and leading to hypotensive effects.
For all of these reasons, it would be desirable to provide additional and improved methods and kits for the adventitial/perivascular delivery of neurotoxic, sympatholytic, sympathetic nerve blocking agents or neuromuscular blocking agents (together with other agents that can modulate nerve function, neuromodulating agents) to accomplish biological and reversible denervation while not creating injury to the blood vessel or aggravating the underlying vascular disease. In particular, it would be beneficial to provide methods which specifically target therapeutic concentrations of the neuromodulating agents into the adventitia and perivascular tissue, where the sympathetic efferent and afferent nerves are located. It would be further beneficial if the methods could efficiently deliver the drugs into the targeted tissue and limit or avoid the loss of drugs into the luminal blood flow. It would be further beneficial if the methods could enhance the localization of neuromodulating agents in the adventitia and peri-adventitia, avoiding diffusion of agents to surrounding organs or nerves. It would be still further beneficial if the persistence of such therapeutic concentrations of the neuromodulating agents in the tissue were also increased, particularly in targeted tissues around the sympathetic nerves, including the adventitial tissue surrounding the blood vessel wall. Additionally, it would be beneficial to increase the uniformity of neuromodulating agent delivery over the desired treatment zone. Still further, it would be desirable if the tissue region or treatment zone into which the neuromodulating agent is delivered could be predicted and tracked with the use of visual imaging and positive feedback to an operating physician. At least some of these objectives will be met by the inventions described hereinafter.
2. Description of the Background Art
The following references are pertinent to intravascular and intraluminal drug delivery: O. Varenne and P. Sinnaeve, “Gene Therapy for Coronary Restenosis: A Promising Strategy for the New Millenium?” Current Interventional Cardiology Reports, 2000, 2: 309-315. B. J. de Smet, et. al., “Metalloproteinase Inhibition Reduces Constrictive Arterial Remodeling After Balloon Angioplasty: A Study in the Atherosclerotic Yucatan Micropig.” Circulation, 2000, 101: 2962-2967. A. W. Chan et. al., “Update on Pharmacology for Restenosis,” Current Interventional Cardiology Reports, 2001, 3: 149-155. Braun-Dullaeus R C, Mann M J, Dzau V J. Cell cycle progression: new therapeutic target for vascular proliferative disease. Circulation. 1998; 98(1):82-9. Gallo R, Padurean A, Jayaraman T, Marx S, Merce Roque M, Adelman S, Chesebro J, Fallon J, Fuster V, Marks A, Badimon J J. Inhibition of intimal thickening after balloon angioplasty in porcine coronary arteries by targeting regulators of the cell cycle. Circulation. 1999; 99:2164-2170 Herdeg C, Oberhoff M, Baumbach A, Blattner A, Axel D I, Schroder S, Heinle H, Karsch K R. Local paclitaxel delivery for the prevention of restenosis: biological effects and efficacy in vivo. J Am Coll Cardiol 2000 June; 35(7):1969-76. Ismail A, Khosravi H, Olson H. The role of infection in atherosclerosis and coronary artery disease: a new therapeutic target. Heart Dis. 1999; 1(4):233-40. Lowe H C, Oesterle S N, Khachigian L M. Coronary in-stent restenosis: Current status and future strategies. J Am Coll Cardiol. 2002 Jan. 16; 39(2):183-93. Fuchs S, Komowski R, Leon M B, Epstein S E. Anti-angiogenesis: A new potential strategy to inhibit restenosis. Intl J Cardiovasc Intervent. 2001; 4:3-6. Kol A, Bourcier T, Lichtman A H, and Libby P. Chlamydial and human heat shock protein 60 s activate human vascular endothelium, smooth muscle cells, and macrophages. J Clin Invest. 103:571-577 (1999). Farsak B, Vildirir A, Akyon Y, Pinar A, Oc M, Boke E, Kes S, and Tokgozogclu L. Detection of Chlamydia pneumoniae and Helicobacter pylori DNA in human atherosclerotic plaques by PCR. J Clin Microbiol 2000; 38(12):4408-11 Grayston J T. Antibiotic Treatment of Chlamydia pneumoniae for secondary prevention of cardiovascular events. Circulation. 1998; 97:1669-1670. Lundemose A G, Kay J E, Pearce J H. Chlamydia trachomatis Mip-like protein has peptidyl-prolyl cis/trans isomerase activity that is inhibited by FK506 and rapamycin and is implicated in initiation of chlamydial infection. Mol Microbiol. 1993; 7(5):777-83. Muhlestein J B, Anderson J L, Hammond E H, Zhao L, Trehan S, Schwobe E P, Carlquist J F. Infection with Chlamydia pneumoniae accelerates the development of atherosclerosis and treatment with azithromycin prevents it in a rabbit model. Circulation. 1998; 97:633-636. K. P. Seward, P. A. Stupar and A. P. Pisano, “Microfabricated Surgical Device,” U.S. application Ser. No. 09/877,653, filed Jun. 8, 2001. K. P. Seward and A. P. Pisano, “A Method of Interventional Surgery,” U.S. application Ser. No. 09/961,079, filed Sep. 20, 2001. K. P. Seward and A. P. Pisano, “A Microfabricated Surgical Device for Interventional Procedures,” U.S. application Ser. No. 09/961,080, filed Sep. 20, 2001. K. P. Seward and A. P. Pisano, “A Method of Interventional Surgery,” U.S. application Ser. No. 10/490,129, filed Mar. 11, 2003.
The following references are pertinent to renal denervation therapy to reduce hypertension: Calhoun D A, et al, “Resistant Hypertension: Diagnosis, Evaluation and Treatment: A scientific statement from the American Heart Association Professional Education Committee of the Council for High Blood Pressure Research,” Hypertension 2008; 51:1403-1419. Campese V M, Kogosov E, “Renal Afferent Denervation Prevents Hypertension in Rats with Chronic Renal Failure,” Hypertension 1995; 25:878-882. Ciccone C D and Zambraski E J, “Effects of acute renal denervation on kidney function in deoxycorticosterone acetate-hypertensive swine,” Hypertension 1986; 8:925-931. Connors B A, et al, “Renal nerves mediate changes in contralateral renal blood flow after extracorporeal shockwave lithotripsy,” Nephron Physiology 2003; 95:67-75. DiBona G F, “Nervous Kidney: Interaction between renal sympathetic nerves and the renin-angiotensin system in the control of renal function,” Hypertension 2000; 36:1083-1088. DiBona G F, “The Sympathetic Nervous System and Hypertension: Recent Developments,” Hypertension 2004; 43; 147-150. DiBona G F and Esler M, “Translational Medicine: The Antihypertensive Effect of Renal Denervation,” American Journal of Physiology—Regulatory, Integrative and Comparative Physiology. 2010 February; 298(2):R245-53. Grisk O, “Sympatho-renal interactions in the determination of arterial pressure: role in hypertension,” Experimental Physiology 2004; 90(2):183-187. Huang W-C, Fang T-C, Cheng J-T, “Renal denervation prevents and reverses hyperinsulinemia-induced hypertension in rats,” Hypertension 1998; 32:249-254. Krum H, et al, “Catheter-based renal sympathetic denervation for resistant hypertension: a multicentre safety and proof-of-principle cohort study,” Lancet 2009; 373(9671):1228-1230. Joles J A and Koomans H A, “Causes and Consequences of Increased Sympathetic Activity on Renal Disease,” Hypertension 2004; 43:699-706. Katholi R E, Winternitz S R, Oparil S, “Role of the renal nerves in the pathogenesis of one-kidney renal hypertension in the rat,” Hypertension 1981; 3:404-409. Mizelle H L, et al, “Role of renal nerves in compensatory adaptation to chronic reductions in sodium uptake,” Am. J. Physiol. 1987; 252(Renal Fluid Electrolyte Physiol. 21):F291-F298.
The following references are pertinent to neurotoxic or neuroblocking agents: Excerpt from Simpson L L, “Botulinum Toxin: a Deadly Poison Sheds its Negative Image,” Annals of Internal Medicine 1996; 125(7):616-617: “Botulinum toxin is being used to treat such disorders as strabismus, spasmodic torticollis, and loss of detrusor sphincter control. These disorders are all characterized by excessive efferent activity in cholinergic nerves. Botulinum toxin is injected near these nerves to block release of acetylcholine.” Clemens M W, Higgins J P, Wilgis E F, “Prevention of anastomotic thrombosis by Botulinum Toxin A in an animal model,” Plast Rectonstr Surg 2009; 123(1) 64-70. De Paiva A, et al, “Functional repair of motor endplates after botulinum neurotoxin type A poisoning: Biphasic switch of synaptic activity between nerve sprouts and their parent terminals,” Proc Natl Acad Sci 1999; 96:3200-3205. Morris J L, Jobling P, Gibbins I L, “Botulinum neurotoxin A attenuates release of norepinephrine but not NPY from vasoconstrictor neurons,” Am J Physiol Heart Circ Physiol 2002; 283:H2627-H2635. Humeau Y, Dousseau F, Grant N J, Poulain B, “How botulinum and tetanus neurotoxins block neurotransmitter release,” Biochimie 2000; 82(5):427-446. Vincenzi F F, “Effect of Botulinum Toxin on Autonomic Nerves in a Dually Innervated Tissue,” Nature 1967; 213:394-395. Carroll I, Clark J D, Mackey S, “Sympathetic block with botulinum toxin to treat complex regional pain syndrome,” Annals of Neurology 2009; 65(3):348-351. Cheng C M, Chen J S, Patel R P, “Unlabeled Uses of Botulinum Toxins: A Review, Part 1,” Am J Health-Syst Pharm 2005; 63(2):145-152. Fassio A, Sala R, Bonanno G, Marchi M, Raiteri M, “Evidence for calcium-dependent vesicular transmitter release insensitive to tetanus toxin and botulinum toxin type F,” Neuroscience 1999; 90(3):893-902. Baltazar G, Tomé A, Carvalho A P, Duarte E P, “Differential contribution of syntaxin 1 and SNAP-25 to secretion in noradrenergic and adrenergic chromaffin cells,” Eur J Cell Biol 2000; 79(12):883-91. Smyth L M, Breen L T, Mutafova-Yambolieva V N, “Nicotinamide adenine dinucleotide is released from sympathetic nerve terminals via a botulinum neurotoxin A-mediated mechanism in canine mesenteric artery,” Am J Physiol Heart Circ Physiol 2006; 290:H1818-H1825. Foran P, Lawrence G W, Shone C C, Foster K A, Dolly J O, “Botulinum neurotoxin C1 cleaves both syntaxin and SNAP-25 in intact and permeabilized chromaffin cells: correlation with its blockade of catecholamine release,” Biochemistry 1996; 35(8):2630-6. Demas G E and Bartness T J, “Novel Method for localized, functional sympathetic nervous system denervation of peripheral tissue using guanethidine,” Journal of Neuroscience Methods 2001; 112:21-28. Villanueva I, et al., “Epinephrine and dopamine colocalization with norepinephrine in various peripheral tissues: guanethidine effects,” Life Sci. 2003; 73(13)1645-53. Picklo M J, “Methods of sympathetic degeneration and alteration,” Journal of the Autonomic Nervous System 1997; 62:111-125. Nozdrachev A D, et al., “The changes in the nervous structures under the chemical sympathectomy with guanethidine,” Journal of the Autonomic Nervous System 1998; 74(2-3):82-85.
The following references are pertinent to self-assembling peptide hydrogel matrix, useful to extend pharmacokinetics as described in this invention: Koutsopoulos S, Unsworth L D, Nagai Y, Zhang S, “Controlled release of functional proteins through designer self-assembling peptide nanofiber hydrogel scaffold,” Proc Natl Acad Sci 2009; 106(12):4623-8. Nagai Y, Unsworth L D, Koutsopoulos S, Zhang S, “Slow release of molecules in self-assembling peptide nanofiber scaffold,” J Control Rel. 2006; 115:18-25. BD™ PURAMATRIX™ Peptide Hydrogel (Catalog No. 354250) Guidelines for Use, BD Biosciences, SPC-354250-G Rev 4.0. Erickson I E, Huang A H, Chung C, Li R T, Burdick J A, Mauck R L, Tissue Engineering Part A. online publication ahead of print. doi:10.1089/ten.tea.2008.0099. Henriksson H B, Svanvik T, Jonsson M, Hagman M, Horn M, Lindahl A, Brisby H, “Transplantation of human mesenchymal stems cells into intervertebral discs in a xenogeneic porcine model,” Spine 2009 Jan. 15; 34(2):141-8. Wang S, Nagrath D, Chen P C, Berthiaume F, Yarmush M L, “Three-dimensional primary hepatocyte culture in synthetic self-assembling peptide hydrogel,” Tissue Eng Part A 2008 February; 14(2):227-36. ThonhoffJR, Lou D I, Jordan P M, Zhao X, Wu P, “Compatibility of human fetal neural stem cells with hydrogel biomaterials in vitro,” Brain Res 2008 Jan. 2; 1187:42-51. Spencer N J, Cotanche D A, Klapperich C M, “Peptide- and collagen-based hydrogel substrates for in vitro culture of chick cochleae,” Biomaterials 2008 March; 29(8):1028-42. Yoshida D, Teramoto A, “The use of 3-D culture in peptide hydrogel for analysis of discoidin domain receptor 1-collagen interaction,” Cell Adh Migr 2007 April; 1(2):92-8. Kim M S, Yeon J H, Park JK, “A microfluidic platform for 3-dimensional cell culture and cell-based assays,” Biomed Microdevices 2007 February; 9(1):25-34. Misawa H, Kobayashi N, Soto-Gutierrez A, Chen Y, Yoshida A, Rivas-Carrillo J D, Navarro-Alvarez N, Tanaka K, Mild A, Takei J, Ueda T, Tanaka M, Endo H, Tanaka N, Ozaki T, “PuraMatrix facilitates bone regeneration in bone defects of calvaria in mice,” Cell Transplant 2006; 15(10):903-10. Yamaoka H, Asato H, Ogasawara T, Nishizawa S, Takahashi T, Nakatsuka T, Koshima I, Nakamura K, Kawaguchi H, Chung U I, Takato T, Hoshi K, “Cartilage tissue engineering using human auricular chondrocytes embedded in different hydrogel materials,” J Biomed Mater Res A 2006 July; 78(1):1-11. Bokhari M A, Akay G, Zhang S, Birch M A, “The enhancement of osteoblast growth and differentiation in vitro on a peptide hydrogel-polyHIPE polymer hybrid material,” Biomaterials 2005 September; 26(25):5198-208. Zhang S, Semino C, Ellis-Behnke R, Zhao X, Spirio L, “PuraMatrix: Self-assembling Peptide Nanofiber Scaffolds. Scaffolding in Tissue Engineering,” CRC Press, 2005. Davis M E, Motion J P, Narmoneva D A, Takahashi T, Hakuno D, Kamm R D, Zhang S, Lee R T, “Injectable self-assembling peptide nanofibers create intramyocardial microenvironments for endothelial cells,” Circulation 111: 442-450, 2005.
The following references are pertinent to carotid sinus syndrome (CSS) and adventitial denervation as a treatment option: Healey J, Connolly S J, Morillo C A, “The management of patients with carotid sinus syndrome: is pacing the answer,” Clin Auton Res 2004 October; 14 Suppl 1:80-6. Toorop R J, Schelting a M R, Bender M H, Charbon J A, Huige M C, “Effective surgical treatment of the carotid sinus syndrome,” J Cardiovasc Surg (Torino) 2008 Oct. 24. Toorop R J, Schelting a M R, Moll F L, “Adventitial Stripping for Carotid Sinus Syndrome,” Ann Vasc Surg 2009 Jan. 7.
BRIEF SUMMARY OF THE INVENTION
Methods and kits according to the present invention are able to achieve enhanced concentrations of neuromodulating agents in targeted tissues surrounding a blood vessel, particularly adventitial tissues, more particularly renal artery and vein adventitial tissues which surround the renal sympathetic nerves. The methods rely on vascular adventitial delivery of the neuromodulating agent using a catheter having a deployable needle. The catheter is advanced intravascularly to a target injection site (which may or may not be within a renal artery) in a blood vessel. The needle is advanced through the blood vessel wall so that an aperture on the needle is positioned in adventitial tissue typically within a perivascular region (defined below) surrounding the injection site, and the neuromodulatng agent is delivered into the perivascular region through the microneedle.
This delivery protocol has been found to have a number of advantages. First, direct injection into the perivascular region has been found to immediately provide relatively high concentrations of the neuromodulating agent in the adventitial tissue immediately surrounding the injected tissue. Second, following injection, it has been found that the injected neuromodulating agents will distribute circumferentially to substantially uniformly surround the blood vessel at the injection site as well as longitudinally to reach positions which are 1 cm, 2 cm, 5 cm, or more away from the injection site, depending upon the liquid formulation in which the drug is carried. In addition, some injected neuromodulating agents may be found to distribute transmurally throughout the endothelial and intimal layers of the blood vessel, as well as in the media, or muscular layer, of the blood vessel wall. Pathways for the distribution of the neuromodulating agent are presently believed to exist through the fatty connective tissue forming the adventitia and perivascular space and may also exist in the vasa vasorum and other capillary channels through the connective tissues. Third, the delivered and distributed neuromodulating agent(s) will persist for hours or days, again depending on their carrier, their lipophilicity, and their potential to bind to cell surface receptors and undergo endocytosis. Thus, a prolonged therapeutic effect based on the neuromodulating agent may be achieved in both the adventitia and the blood vessel wall. Fourth, after the distribution has occurred, the concentration of the neuromodulating agent throughout its distribution region will be highly uniform. While the concentration of the neuromodulating agent at the injection site will always remain the highest, concentrations at other locations in the peripheral adventitia around the injection site will usually reach at least about 10% of the concentration at the injection site, often being at least about 25%, and sometimes being at least about 50%. Similarly, concentrations in the adventitia at locations longitudinally separated from the injection site by about 5 cm will usually reach at least 5% of the concentration at the injection site, often being at least 10%, and sometimes being at least 25%. Fifth, the distribution can be traced with the use of radio-contrast agents by X-ray (or by hyperechoic or hypoechoic contrast agents by ultrasound or MRI contrast agents by magnetic resonance) in order to determine the extent of diffusion, allowing one to limit the injection based on reaching a desirable diffusion region, increase the injection based on the desire to reach a greater diffusion region, or change the injection site based on an inadequate diffusion range based on the location of the needle tip, which may be embedded in a thick plaque or located intraluminally from a thick calcification. Finally, after distribution of a neuromodulating agent such as guanethidine, the agent accumulates selectively within sympathetic neurons via the amine uptake pump, and can accumulate within neurons in vivo to concentrations of 0.5 to 1.0 millimolar (mM).
The adventitial tissue surrounding arteries and veins in the body contains sympathetic nerves that provide signal pathways for the regulation of hormones and proteins secreted by the cells and organs of the body. The efferent (conducting away from the central nervous system) and afferent (conducting toward the central nervous system) sympathetic nerves that line the renal artery are held within this adventitial connective tissue. The sympathetic nervous system is responsible for up- and down-regulation of chemicals in the body that lead to homeostasis. In the case of hypertension, the sympathetic nerves that run from the spinal cord to the kidneys signal the body to produce norepinephrine at superphysiological levels, which leads to a cascade of signals causing a rise in blood pressure. Denervation of the renal arteries (and to some extent the renal veins) removes this response and allows a return to normal blood pressure.
The benefits of the present invention are achieved by delivering neuromodulating agents, such as neurotoxic, sympatholytic, sympathetic blocking agents or neuromuscular blocking agents (together and with other agents that can modulate the transmission of nerve signals) into the adventitia or perivascular region surrounding a renal artery or vein. The perivascular region is defined as the region beyond external elastic lamina of an artery or beyond the tunica media of a vein. Usually, injection will be made directly into the region of the adventitia comprised primarily of adventitial fat cells but also comprised of fibroblasts, vasa vasorum, lymphatic channels, and nerve cells, and it has been found that the neuromodulating agent disperses through the adventitia circumferentially, longitudinally, and transmurally from injection site. Such distribution can provide for delivery of therapeutically effective concentrations of the neuromodulating drugs directly to the area where nerve cells can be affected. This is difficult or impossible to accomplish with other delivery techniques (such as parenteral hypodermic needle injection).
The adventitia is a layer of fatty tissue surrounding the arteries of the human and other vertebrate cardiovascular systems. The external elastic lamina (EEL) separates the fatty adventitial tissue from muscular tissue that forms the media of the arterial wall. Needles of the present invention pass through the muscular tissue of the blood vessel and the EEL in order to reach the adventitia and perivascular space into which the drug is injected. The renal arteries or veins that are subject of this invention usually have an internal (lumen) diameter of between 1 mm and 10 mm, more often between 3 and 6 mm, particularly after angioplasty has been used to compress any plaque that may have been impinging on the lumen. The thickness of the intima and media, which separate the lumen from the EEL, are usually in the range from 200 μm to 3 mm, more often in the range from 500 μm to 1 mm. The adventitial tissue surrounding the EEL may be several millimeters thick, but the sympathetic nerves that run to the kidneys are usually within 3 mm outside the EEL, more often within 1 mm outside the EEL.
The neuromodulating agents injected in accordance with the methods described in this invention will typically either be in fluid form themselves, or will be suspended in aqueous or fluid carriers in order to permit dispersion of the neuromodulating agents through the adventitia. Drugs may also be suspended in self-assembling hydrogel carriers in order to contain the diffusion and extend the retention of agents in the area of tissue local to the injection site.
The delivery of neuromodulating agents into the adventitia outside the EEL leads to the direct targeting and interruption of the sympathetic nerve signaling pathway. With particular relevance to botulinum toxin, after delivery to the adventitia, the toxin binds with high affinity to receptors on nerve endings, and the toxin molecules penetrate the cell membrane via receptor-mediated endocytosis. Once in the nerve cell, the toxin crosses the endosome membrane by pH-dependent translocation. The toxin then reaches the cytosol, where it cleaves polypeptides that are essential for exocytosis. Without these polypeptides, incoming nerve signals cannot trigger the release of acetylcholine, thus blocking any outgoing (or transmission of) nerve signals. Botulinum toxin has been shown to block nerve activity for more than one year in humans, though recovery of the nerve signal is seen over time.
Botulinum toxins have been used primarily for their interaction with the parasympathetic nervous system, due to the toxins' ability to inhibit release of acetylcholine at the neuromuscular junction. One aspect of the present invention is to deliver a neuromodulating agent such as botulinum toxin to the adventitia of renal arteries to affect both parasympathetic and sympathetic nerves. While preganglionic sympathetic nerves are cholinergic, post-ganglionic sympathetic nerves are adrenergic, expressing noradrenaline rather than acetylcholine. It has been shown in the literature that botulinum toxin reduces the expression of noradrenaline in addition to acetylcholine, which justifies its use as a neuromodulating agent for both parasympathetic and sympathetic nervous systems as further described in this application.
There have been rare reports of cardiovascular complications with the use of botulinum neurotoxins, including myocardial infarction or arrhythmia, some with fatal outcomes. While some of these patients had cardiovascular disease risk factors and the complication may have been unrelated to the botulinum toxin injection, the release of high levels of toxin into the bloodstream or the digestive tract is worrisome due to the possibility that a patient might contract botulism.
Botulinum toxins cleave SNARE (Soluble N-sensitive factor Attachment protein REceptor) proteins, including synaptosomal-associated protein of 25-kilodaltons (SNAP-25), syntaxin, and synaptobrevin (also known as vesicle-associated membrane protein, or VAMP). Each of these proteins are required for vesicles containing acetylcholine or noradrenaline to be released from nerve cells. In this manner, botulinum toxins prevent the exocytosis of the vesicles containing catecholamines or acetylcholine. Other pathways required for the release of acetylcholine or noradrenaline can also be modified, such as the down-regulation or abolishment of any of the SNARE proteins (which, in addition to SNAP-25, syntaxin and synaptobrevin, include synaptotagmin and Rab3a). While these effects of botulinum toxin have most often been used to stop the release of acetylcholine at the neuromuscular junction to prevent muscle movement or twitch, the toxin can also be exploited to prevent signals from transmitting through the nerves in the renal artery adventitia. The different botulinum toxin serotypes (A through G) are able to cleave different components of the SNARE complex of proteins.
While cleavage of the SNARE proteins can be accomplished with botulinum toxin, other methods may be employed to reduce or quell the hyperactive signaling in the nerves that run through the renal artery adventitia or the nerves that form other neural systems in the body. The reduction of neurotransmitters, putative neurotransmitters, or neuroactive peptides can accomplish the same goal of reducing nervous signal transmission along the renal arteries. Neurotransmitters, putative neurotransmitters, and neuroactive peptides include compounds of the amino acidergic system such as y-aminobutyrate (GABA), aspartate, glutamate, glycine, or taurine; compounds of the cholinergic system such as acetylcholine; compounds of the histaminergic system such as histamine; compounds of the monoaminergic system such as adrenaline, dopamine, noradrenaline, serotonin, or tryptamine; compounds of the peptidergic system such as angiotensin, members of the bombesin family, brakykinin, calcitonin gene related peptide (CGRP), carnosine, caerulein, members of the cholecystokinin family, corticotropin, corticotropin releasing hormone, members of the dynorphin family, eledoisin, members of the endorphin family, members of the encephalin family, members of the gastrin family, luteinizing hormone releasing hormone (LHRH), melatonin, motilin, neurokinins, members of the neuromedin family, neuropeptide K, neuropeptide Y, neurotensin, oxytocin, peptide histidine isoleucine (PHI), physalaemin, sleep inducing peptides, somatostatin, substance K, substance P, thyroid hormone releasing hormone (TRH), vasoactive intestinal peptide (VIP), or vasopressin; compounds of the purinergic system such as adenosine, ADP, AMP, or ATP; or compounds in the form of gaseous neurotransmitters such as carbon monoxide or nitric oxide.
Neural block may be accomplished with agents such as lidocaine or bupivacaine, and it has been reported that neural block may be extended with the co-injection of botulinum toxin and bupivacaine versus the toxin alone or the bupivacaine alone. The combination of agents can lead to an enhanced result because agents like bupivacaine block the influx of sodium ions into nerves, which serves to decrease action potential and nerve firing. This can also be accomplished with co-injection of toxin with calcium-channel blockers.
Sympathectomy may be accomplished with immunosympathectomy agents such as anti-nerve growth factor (anti-NGF); auto-immune sympathectomy agents such as anti-dopamine beta-hydroxylase (anti-DβH) and anti-acetylcholinesterase (anti-AChe); chemical sympathectomy agents such as 6-hydroxydopamine (6-OHDA), phenol, ethanol, bretylium tosylate, guanethidine, guanacline, and N-(2-chloroethyl)-N-ethyl-2-bromobenzylamine (DSP4); immunotoxin sympathectomy agents such as OX7-SAP, 192-SAP, anti-dopamine beta-hydroxylase saporin (DBH-SAP), and anti-dopamine beta-hydroxylase immunotoxin (DHIT); or combinations thereof. Other sympatholytic agents include alpha-2-agonists such as clonidine, guanfacine, methyldopa, guanidine derivatives like betanidine, guanethidine, guanoxan, debrisoquine, guanoclor, guanazodine, guanoxabenz, guanidine, guanadrel and the like; imadazoline receptor agonists such as moxonidine, relmenidine and the like; ganglion-blocking or nicotinic antagonists such as mecamylamine, trimethaphan and the like; MAOI inhibitors such as pargyline and the like; adrenergic uptake inhibitors such as rescinnamine, reserpine and the like; tyrosine hydroxylase inhibitors such as metirosine and the like; alpha-1 blockers such as prazosin, indoramin, trimazosin, doxazosin, urapidil and the like; non-selective alpha blockers such as phentolamine and the like; serotonin antagonists such as ketanserin and the like; endothelin antagonists such as bosentan, ambrisentan, sitaxentan, and the like; and sclerotherapeutic agents such as quinacrine, chloroquine, sodium tetradecyl sulfate, ethanolamine oleate, sodium morrhuate, polidocanol, phenol, ethanol, or hypertonic solutions.
In the case of guanethidine, systemic administration with chronic, high doses can cause functional sympathectomy, but at the expense of terrible side effects. Guanethidine causes sympathectomy by preventing the release of norepinephrine from sympathetic nerve terminals by interfering with the excitatory release of vesicles carrying norepinephrine, by replacing noradrenaline in the synaptic vesicles, by inhibiting oxidative phosphorylation in mitochondria with an effective dose in 50% of cells (ED 50 ) of 0.5 to 0.9 mM, by inhibiting retrograde transport of trophic factors such as nerve growth factor, and also by exerting cytotoxic effects by an immune-mediated mechanism.
In addition to chemical sympatholysis, additional methods of sympathectomy can be achieved such as by heating the nerves to within the range from 42° C. to 50° C.
In a first aspect of the present invention, a method for distributing a neuromodulating agent or combination of agents into the adventitial tissue and nerves surrounding a living vertebrate host's renal artery, such as a human renal artery, comprises positioning a microneedle through the wall of a renal blood vessel and delivering an amount of the neuromodulating agent or combination of agents therethrough.
The microneedle is inserted, preferably in a substantially normal direction, into the wall of a vessel (artery or vein) to eliminate as much trauma to the patient as possible. Until the microneedle is at the site of an injection, it is positioned out of the way so that it does not scrape against arterial or venous walls with its tip. Specifically, the microneedle remains enclosed in the walls of an actuator or sheath attached to a catheter so that it will not injure the patient during intervention or the physician during handling. When the injection site is reached, movement of the actuator along the vessel terminated, and the actuator is operated to cause the microneedle to be thrust outwardly, substantially perpendicular to the central axis of a vessel, for instance, in which the catheter has been inserted.
The aperture of the microneedle will be positioned so that it lies beyond the external elastic lamina (EEL) of the blood vessel wall and into the perivascular region surrounding the wall. Usually, the aperture will be positioned at a distance from the inner wall of the blood vessel which is equal to at least 10% of the mean luminal diameter of the blood vessel at the injection site. Preferably, the distance will be in the range from 10% to 75% of the mean luminal diameter.
When the aperture of the microneedle is located in the tissue outside of the EEL surrounding the blood vessel, the neuromodulating agent or combination of agents are delivered through the needle aperture, at which point the agent or combination distributes substantially completely circumferentially through adventitial tissue surrounding the blood vessel at the site of the microneedle. Usually, the agent will further distribute longitudinally along the blood vessel over a distance of at least 1 to 2 cm, and can extend to greater distances depending on dosage (volume) injected, within a time period no greater than 60 minutes, often within 5 minutes or less. While the concentration of the neuromodulating agent in the adventitia will decrease in the longitudinal direction somewhat; usually, the concentration measured at a distance of 2 cm from the injection site will usually be at least 5% of the concentration measured at the same time at the injection site, often being at least 10%, frequently being as much as 25%, and sometimes being as much as 50%. The concentration profile is greatly dependent on the size of the molecule or particle delivered into the adventitial and perivascular tissue. The concentration profile can be further tailored by the use of different carriers and excipients within the liquid or gel formulation in which the agent is carried.
In a second aspect of the present invention, the location of the aperture may be detected in advance of placing the full dose of neuromodulating agent into the adventitia by the use of, for example, X-ray, ultrasonic, or magnetic resonance imaging of a radio-contrast agent. The contrast agent may be delivered at the same time as the therapeutic agent, either in or out of solution with the therapeutic agent, or it may be delivered prior to the therapeutic agent to detect and confirm that the needle aperture is in the desirable tissue location outside the EEL. After determining the successful placement of the needle aperture, continued injection can be made through the needle under image guidance. Such methods for delivering agents provide the physician a positive visual feedback as to the location of the injection and diffusion range, and also to titrate the dose based on diffusion range and physiological response. The amounts of the agents delivered into the perivascular region may vary considerably, but imaging agents delivered before the therapeutic agent will usually be in the range of 10 to 200 μl, and often will be in the range of 50 to 100 μl. Therapeutic agent injection will then typically be in the range from 10 μl to 10 ml, more usually being from 100 μl to 5 ml, and often being from 500 μl to 3 ml.
In a third aspect of the present invention, methods for treatment of hypertension comprise positioning a microneedle through the wall of a renal artery or vein and delivering an effective dose of botulinum toxin to the adventitia surrounding vessels leading from the aorta to the kidney or from the kidney to the vena cava. A therapeutic effective dose of botulinum toxin to reduce neurotransmission and thereby reduce blood pressure can be monitored by the operating physician and titrated based on patient characteristics. This dose may be in the range from 10 pg (corresponding to approximately 0.2 U of BOTOX® or 1 U of MYOBLOC™) to 25 ng (corresponding to approximately 500 U of BOTOX® or 2500 U of MYOBLOC™), more usually being from 50 pg (corresponding to approximately 1 U of BOTOX® or 5 U of MYOBLOC™) to 10 ng (corresponding to approximately 200 U of BOTOX® or 1000 U of MYOBLOC™), and even more usually being from 100 pg (corresponding to approximately 2 U of BOTOX® or 10 U of MYOBLOC™) to 2.5 ng (corresponding to approximately 50 U of BOTOX® or 250 U of MYOBLOC™).
In a fourth aspect of the present invention, methods for treatment of hypertension comprise positioning a microneedle through the wall of a renal artery or vein and delivering an effective dose of guanethidine to the adventitia surrounding such vessels leading from the aorta to the kidney or from the kidney to the vena cava. A therapeutic effective dose of guanethidine to create sympathectomy and reduce norepinephrine release, thereby reducing blood pressure can be monitored by the operating physician and titrated based on patient characteristics. This dose may be in the range from 10 μg to 200 mg, usually 50 μg to 100 mg, more usually being from 100 μg to 50 mg, and even more usually being from 500 μg to 30 mg, and sometimes being from 500 μg to 10 mg.
In a fifth aspect of the present invention, methods for extending the activity of neuromodulating agents in target tissues comprises the use of agents that are endocytosed by nerve cells and then remain in the cells for long periods of time before becoming inactive.
In a sixth aspect of the present invention, methods for extending the activity of neuromodulating agents in target tissues comprises the delivery of such agents within a hydrogel that has a capacity for self assembly, such as a self-assembling peptide hydrogel matrix. When co-administered with the hydrogel material, molecules of the active agent are trapped in a nanofiber matrix as the hydrogel self-assembles due to contact with physiologic conditions. The hydrogel matrix may have fibers with diameter from 1 to 100 nm, for example, and pores with diameter from 1 to 300 nm, for example. Molecules trapped within the matrix may slowly diffuse through the porous structure or remain trapped within pores. The matrix may be slowly resorbed by the surrounding tissue, as peptide matrices are commonly known to do, and become simple amino acids. As the matrix is resorbed, trapped molecules of the active agent are then released into the surrounding tissues, leading to an ability to extend the pharmacokinetics of the neuromodulating agents. This is particularly useful with agents that do not remain active within cells for extended times. Desirable pharmacokinetic profiles are in the range of weeks to months or even years.
An exemplary hydrogel for use with the methods described in this invention is a self-assembling peptide hydrogel that comprises alternating hydrophilic and hydrophobic amino acids which, in the presence of physiological conditions, will spontaneously self-organize into an interwoven nanofiber matrix with fiber diameters of 10-20 nm. In the presence of proteins and small molecules, the nanofiber matrix traps the bioactive molecules within pores ranging from 5 to 200 nm. This self-assembling peptide, acetyl-(Arg-Ala-Asp-Ala) 4 -CONH 2 [Ac-(RADA) 4 -CONH 2 ] (PURAMATRIX™), has been reported as an efficient slow-delivery carrier of small molecules. The release of proteins from the nanofiber matrix has been shown to include at least two phases. The first is a “burst” of released material, wherein it has been theorized that the protein material that is loosely trapped within large pores diffuses out rapidly (over a period of several hours), then a slower release of more tightly trapped material occurs over at least several days and is governed by Brownian motion of the proteins moving through the tight matrix. A third aspect to the release kinetics is the breakdown of the peptide matrix at its boundary, thus a release of trapped protein as the peptide is resorbed by surrounding tissue. One of the advantages of the peptide hydrogel as compared to “traditional” hydrogels is that the breakdown of the peptide structure results only in amino acid byproducts, which are easily metabolized by the body. PURAMATRIX™ is available from BD Bioscience as BD™ PURAMATRIX™ Peptide Hydrogel for research use only in 1% concentration. It is used primarily as a cell culture agent, but with application for in vivo use in the delivery of cells and bioactive agents. PURAMATRIX™ has been studied for its uses as a matrix for engineering cartilage using mesenchymal cells and chondrocytes, as a carrier of mesenchymal cells for spinal disc injury, as a hepatocyte culture matrix, to support differentiation of human fetal neural stem cells in vitro, and other cell culture and regenerative medical applications. Biocompatibility studies of PURAMATRIX™ have shown that it integrates well with tissue, much like other extracellular matrix structures, and can be resorbed over a period of several weeks. It has also been shown that functional vascular structures can be seen in the nanofiber microenvironments by 28 days after injection. With specific relevance to this invention, PURAMATRIX™ has also been shown to have no deleterious effect on the proteins that it entraps or elutes over time.
In yet another aspect of the present invention, methods to treat other diseases resulting from hyperactivity of sympathetic and parasympathetic nerves comprise delivery of neuoromodulating agents for the chemical or neuromodulating denervation of arteries. While this therapy may most often be applied to renal arteries, other vascular beds can benefit from these methods. For example, denervation of the carotid artery can be used to treat patients with carotid sinus syndrome (CSS), a condition that leads to dizziness and syncope, but can be rectified by carotid adventitial denervation.
In yet another aspect of the present invention, a method for treating vascular disease comprises the delivery of neuromodulating agents to the adventitia around blood vessels. The development of atherosclerosis, vulnerable plaques, and the growth of hyperplastic neointima have each been shown to rely on parasympathetic and sympathetic nerve signaling pathways. When interrupted, these signal pathways no longer produce the agents that end up causing the vascular inflammation that results in mortality and morbidity from associated ischemic complications.
Exemplary neuromodulating agents for creating chemical or neuromodulating denervation of renal arteries or other blood vessels in the body include neurotoxins such as botulinum toxin (serotypes A through G), resinoferatoxin, alpha-bungarotoxin, beta-bungarotoxin, tetrodotoxin, tetanus toxin, alpha-latrotoxin, tetraethylammonium, and the like; neuromuscular blocking agents like tubocurarine, alcuronium, pipecuronium, rocuronium, pancuronium, vecuronium, and the like; calcium channel blockers such as amlodipine, diltiazem, felodipine, isradipine, nicardipine, nifedipine, nisoldipine, verapamil, and the like; sodium channel blockers such as moricizine, propafenone, encainide, flecainine, tocainide, mexiletine, phenytoine, lidocaine, disopyramine, quinidine, procainamide, and the like; beta-adrenergic inhibitors such as acebutolol, atenolol, betaxolol, bisoprolol, carvedilol, esmolol, labetalol, metoprolol, nadolol, nebivolol, propranolol, pindolol, sotalol, timolol, and the like; acetylcholine receptor inhibitors such as atropine and the like, immunosympathectomy agents such as anti-nerve growth factor (anti-NGF) and the like; auto-immune sympathectomy agents such as anti-dopamine beta-hydroxylase (anti-DβH), anti-acetylcholinesterase (anti-AChe) and the like; chemical sympathectomy agents such as 6-hydroxydopamine (6-OHDA), phenol, ethanol, bretylium tosylate, guanidinium compounds (e.g. guanethidine or guanacline), N-(2-chloroethyl)-N-ethyl-2-bromobenzylamine (DSP4) and the like; immunotoxin sympathectomy agents such as OX7-SAP, 192-SAP, anti-dopamine beta-hydroxylase saporin (DBH-SAP), anti-dopamine beta-hydroxylase immunotoxin (DHIT) and the like; or combinations thereof.
One particular advantage of this invention is the ability to reverse the therapy in the case that a patient responds poorly to renal denervation. For example, if toxins are used to reduce neurotransmission, anti-toxins can be delivered (either systemically or locally) to reverse the effect and improve the patient's health. Other methods for renal sympathetic denervation have relied on surgical cutting of nerves or radiofrequency energy transmission to nerves to cause damage beyond which the nerves cannot transmit signals. Each of these previous methods is irreversible (though the RF energy transmission can lead to non-permanent effects that may wear off after months to years). If patients respond poorly to either the surgical or RF denervation procedures, there is therefore little recourse.
Another particular advantage of this invention is that side effects are limited by the very low doses that lead to therapeutic effect, often in the range from 0.1 to 2.5 ng in the case of botulinum neurotoxin or often less than 5 mg of guanethidine (whereas systemic doses of 5-50 mg/kg/day do not produce reliable sympathectomy in humans), because the methods described in this invention allow precise targeting of neuromodulators into the tissue in which the sympathetic nerves are located.
Another particular advantage of this invention is that the neuromodulating agents delivered into the adventitia according to the methods described above do not lead to death of smooth muscle cells, inflammation, or restenosis, all of which can result from radiofrequency energy transmission into arterial walls from an endoluminal aspect. Rather, the agents directly target the sympathetic and parasympathetic nerves that run through the adventitia, leaving the smooth muscle and endothelium of the vessel in a functional state, healthy and able to respond to physiological signals coming from the blood or lymph traveling around and through the vessel.
Another particular advantage of this invention is that the neuromodulating agents can be tracked during their delivery by the use of contrast agents. This allows physicians to ensure that large enough doses are given to fully treat the adventitia, but small enough doses are used such that the diffusion is limited to the area of anatomical interest This limits the potential for neuromodulating agents to reach the central nervous system. The use of imaging agents in coordination with blood pressure monitoring allows physicians to actively monitor the effect of the dose while controlling the treatment range so as not to influence surrounding tissues or nervous systems.
In still further aspects of the present invention, kits for delivering neuromodulating agents to a patient suffering from hypertension comprise a catheter, instructions for use of the catheter, and instructions for delivery of the agent. The catheter has a microneedle which can be advanced from a blood vessel lumen through a wall of the blood vessel to position an aperture of the microneedle at a perivascular space surrounding the blood vessel. The instructions for use set forth any of the exemplary treatment protocols described above. The kit may also include one or more stents and one or more angioplasty balloons that can be used to open the renal arteries and improve blood flow to the kidneys.
In a further aspect of the present invention, kits for delivering neuromodulating agents to the vascular adventitia of patients suffering from disease comprise a catheter, a neuromodulating agent which may or may not be in formulation with a carrier that can extend the elution kinetics of the agent into adventitial and adjacent tissues, instructions for use of the catheter, and dosage guidelines for the agent. The catheter has a microneedle which can be advanced from a blood vessel lumen through the wall of the blood vessel to position an aperture of the microneedle at a location outside the EEL of the blood vessel in the perivascular tissue or adventitia. The agent will usually be able to distribute circumferentially and longitudinally in the perivascular space and adventitia surrounding the blood vessel over a distance of at least 1 cm within a time of no greater than 5 minutes, usually within 1 minute or less. The instructions for use set forth any of the exemplary treatment protocols described above. The kit may also include one or more stents and one or more angioplasty balloons that can be used to open the renal arteries and improve blood flow to the kidneys.
The present invention provides methods that are enhanced by catheters that place a needle aperture outside the EEL of a blood vessel by deploying the needle from the inside of the vessel. These catheters may take on various forms. In one exemplary embodiment, a balloon or inflatable actuator is inflated to unfurl a balloon from around a microneedle that his inserted roughly perpendicularly through the vessel wall, as further described in commonly owned U.S. Pat. Nos. 6,547,803; 7,547,294; and 7,666,163. Another such exemplary embodiment employs a balloon that inflates and translates a needle and extrudes the needle tip along a path into the vessel wall. Such an exemplary embodiment has been shown with commonly owned U.S. Pat. No. 7,141,041. In each of these exemplary embodiments, multiple components may be combined into the same balloon or pressure component, such that one part of the wall is non-distensible and another part of the wall is compliant or elastomeric, such that a single inflation step, whether it involves volume or pressure, may be useful to activate both the non-distensible and compliant structures simultaneously or in series. Such enhanced embodiments for delivery catheters are described in U.S. Pat. No. 7,691,080. Exemplary methods which can be used for delivering neuromodulating agents into the adventitia are described in copending commonly owned application Ser. No. 10/691,119. The full disclosure of each of these commonly owned patents and applications are incorporated herein by reference.
It is recognized that the use of these devices and techniques to deliver to the adventitia around renal arteries is useful in the treatment of hypertension, it is also evident that the use of these devices and techniques can be applied to other arteries, such as the carotid artery, to accomplish similar goals.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a schematic, perspective view of an intraluminal injection catheter suitable for use in the methods and systems of the present invention.
FIG. 1B is a cross-sectional view along line 1 B- 1 B of FIG. 1A .
FIG. 1C is a cross-sectional view along line 1 C- 1 C of FIG. 1A .
FIG. 2A is a schematic, perspective view of the catheter of FIGS. 1A-1C shown with the injection needle deployed.
FIG. 2B is a cross-sectional view along line 2 B- 2 B of FIG. 2A .
FIG. 3 is a schematic, perspective view of the intraluminal catheter of FIGS. 1A-1C injecting therapeutic agents into an adventitial space surrounding a body lumen in accordance with the methods of the present invention.
FIGS. 4A-4D are cross-sectional views of the inflation process of an intraluminal injection catheter useful in the methods of the present invention.
FIGS. 5A-5C are cross-sectional views of the inflated intraluminal injection catheter useful in the methods of the present invention, illustrating the ability to treat multiple lumen diameters.
FIG. 6 is a perspective view of a needle injection catheter useful in the methods and systems of the present invention.
FIG. 7 is a cross-sectional view of the catheter FIG. 6 shown with the injection needle in a retracted configuration.
FIG. 8 is a cross-sectional view similar to FIG. 7 , shown with the injection needle laterally advanced into luminal tissue for the delivery of therapeutic or diagnostic agents according to the present invention.
FIG. 9 is a schematic illustration of an artery together with surrounding tissue illustrating the relationship between the perivascular tissue, the adventitia, and the blood vessel wall components.
FIG. 10A is a schematic illustration of the kidney and arterial structure that brings blood to the kidney.
FIG. 10B is a schematic illustration of FIG. 10A with sympathetic nerves shown leading from the aorta around the renal artery to the kidney.
FIG. 10C is a cross-sectional view along line 10 C- 10 C of FIG. 10B .
FIGS. 11A-11C are cross-sectional views similar to FIGS. 4A and 4D , shown with the injection needle advanced into the adventitia for progressive delivery of agents to sympathetic nerves according to the present invention.
FIG. 11D is a cross-sectional view along line 11 D- 11 D of FIG. 11A .
FIG. 11E is a cross-sectional view along line 11 E- 11 E of FIG. 11B .
FIG. 11F is a cross-sectional view along line 11 F- 11 F of FIG. 11C .
FIG. 12 is an illustration showing how botulinum toxin interacts with nerve cells to prevent the exocytosis of acetylcholine.
FIG. 13 is a graphical presentation of experimental data described herein.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will preferably utilize microfabricated catheters for intravascular injection. The following description and FIGS. 1-8 provide three representative embodiments of catheters having microneedles suitable for the delivery of a neuromodulating agent into a perivascular space or adventitial tissue. A more complete description of the catheters and methods for their fabrication is provided in U.S. Pat. Nos. 7,141,041; 6,547,803; 7,547,294; 7,666,163 and 7,691,080, the full disclosures of which have been incorporated herein by reference.
The present invention describes methods and kits useful for the delivery of neuromodulating agents into the adventitia around renal arteries in order to reduce blood pressure in the treatment of hypertension. In each kit, a delivery catheter may be combined with instructions for use and a therapeutically effective amount of a neuromodulating agent as defined above.
As shown in FIGS. 1A-2B , a microfabricated intraluminal catheter 10 includes an actuator 12 having an actuator body 12 a and central longitudinal axis 12 b . The actuator body more or less forms a U-shaped or C-shaped outline having an opening or slit 12 d extending substantially along its length. A microneedle 14 is located within the actuator body, as discussed in more detail below, when the actuator is in its unactuated condition (furled state) ( FIG. 1B ). The microneedle is moved outside the actuator body when the actuator is operated to be in its actuated condition (unfurled state) ( FIG. 2B ).
The actuator may be capped at its proximal end 12 e and distal end 12 f by a lead end 16 and a tip end 18 , respectively, of a therapeutic catheter 20 . The catheter tip end serves as a means of locating the actuator inside a body lumen by use of a radio opaque coatings or markers. The catheter tip also forms a seal at the distal end 12 f of the actuator. The lead end of the catheter provides the necessary interconnects (fluidic, mechanical, electrical or optical) at the proximal end 12 e of the actuator.
Retaining rings 22 a and 22 b are located at the distal and proximal ends, respectively, of the actuator. The catheter tip is joined to the retaining ring 22 a , while the catheter lead is joined to retaining ring 22 b . The retaining rings are made of a thin, on the order of 10 to 100 microns (μm), substantially flexible but relatively non-distensible material, such as Parylene (types C, D or N), or a metal, for example, aluminum, stainless steel, gold, titanium or tungsten. The retaining rings form a flexible but relatively non-distensible substantially “U”-shaped or “C”-shaped structure at each end of the actuator. The catheter may be joined to the retaining rings by, for example, a butt-weld, an ultra sonic weld, integral polymer encapsulation or an adhesive such as an epoxy or cyanoacrylate.
The actuator body further comprises a central, expandable section 24 located between retaining rings 22 a and 22 b . The expandable section 24 includes an interior open area 26 for rapid expansion when an activating fluid is supplied to that area. The central section 24 is made of a thin, semi-flexible but relatively non-distensible or flexible but relatively non-distensible, expandable material, such as a polymer, for instance, Parylene (types C, D or N), silicone, polyurethane or polyimide. The central section 24 , upon actuation, is expandable somewhat like a balloon-device.
The central section is capable of withstanding pressures of up to about 200 psi upon application of the activating fluid to the open area 26 . The material from which the central section is made of is flexible but relatively non-distensible or semi-flexible but relatively non-distensible in that the central section returns substantially to its original configuration and orientation (the unactuated condition) when the activating fluid is removed from the open area 26 . Thus, in this sense, the central section is very much unlike a balloon which has no inherently stable structure.
The open area 26 of the actuator is connected to a delivery conduit, tube or fluid pathway 28 that extends from the catheter's lead end to the actuator's proximal end. The activating fluid is supplied to the open area via the delivery tube. The delivery tube may be constructed of Teflon© or other inert plastics. The activating fluid may be a saline solution or a radio-opaque dye.
The microneedle 14 may be located approximately in the middle of the central section 24 . However, as discussed below, this is not necessary, especially when multiple microneedles are used. The microneedle is affixed to an exterior surface 24 a of the central section. The microneedle is affixed to the surface 24 a by an adhesive, such as cyanoacrylate. Alternatively, the microneedle maybe joined to the surface 24 a by a metallic or polymer mesh-like structure 30 (See FIG. 2A ), which is itself affixed to the surface 24 a by an adhesive. The mesh-like structure may be-made of, for instance, steel or nylon.
The microneedle includes a sharp tip 14 a and a shaft 14 b . The microneedle tip can provide an insertion edge or point. The shaft 14 b can be hollow and the tip can have an outlet port 14 c , permitting the injection of a neuromodulating or drug into a patient. The microneedle, however, does not need to be hollow, as it may be configured like a neural probe to accomplish other tasks. As shown, the microneedle extends approximately perpendicularly from surface 24 a . Thus, as described, the microneedle will move substantially perpendicularly to an axis of a lumen into which has been inserted, to allow direct puncture or breach of body lumen walls.
The microneedle further includes a neuromodulating or drug supply conduit, tube or fluid pathway 14 d which places the microneedle in fluid communication with the appropriate fluid interconnect at the catheter lead end. This supply tube may be formed integrally with the shaft 14 b , or it may be formed as a separate piece that is later joined to the shaft by, for example, an adhesive such as an epoxy. The microneedle 14 may be bonded to the supply tube with, for example, an adhesive such as cyanoacrylate.
The needle 14 may be a 30-gauge, or smaller, steel needle. Alternatively, the microneedle may be microfabricated from polymers, other metals, metal alloys or semiconductor materials. The needle, for example, may be made of Parylene, silicon or glass. Microneedles and methods of fabrication are described in U.S. application Ser. No. 09/877,653, filed Jun. 8, 2001, entitled “Microfabricated Surgical Device”, the entire disclosure of which is incorporated herein by reference.
The catheter 20 , in use, is inserted through an opening in the body (e.g. for bronchial or sinus treatment) or through a percutaneous puncture site (e.g. for artery or venous treatment) and moved within a patient's body passageways 32 , until a specific, targeted region 34 is reached (see FIG. 3 ). The targeted region 34 may be the site of tissue damage or more usually will be adjacent the sites typically being within 100 mm or less to allow migration of the therapeutic or diagnostic agent. As is well known in catheter-based interventional procedures, the catheter 20 may follow a guide wire 36 that has previously been inserted into the patient. Optionally, the catheter 20 may also follow the path of a previously-inserted guide catheter (not shown) that encompasses the guide wire.
During maneuvering of the catheter 20 , well-known methods of X-ray fluoroscopy or magnetic resonance imaging (MRI) can be used to image the catheter and assist in positioning the actuator 12 and the microneedle 14 at the target region. As the catheter is guided inside the patient's body, the microneedle remains furled or held inside the actuator body so that no trauma is caused to the body lumen walls.
After being positioned at the target region 34 , movement of the catheter is terminated and the activating fluid is supplied to the open area 26 of the actuator, causing the expandable section 24 to rapidly unfurl, moving the microneedle 14 in a substantially perpendicular direction, relative to the longitudinal central axis 12 b of the actuator body 12 a , to puncture a body lumen wall 32 a . It may take only between approximately 100 milliseconds and five seconds for the microneedle to move from its furled state to its unfurled state.
The microneedle aperture, may be designed to enter body lumen tissue 32 b as well as the adventitia, media, or intima surrounding body lumens. Additionally, since the actuator is “parked” or stopped prior to actuation, more precise placement and control over penetration of the body lumen wall are obtained.
After actuation of the microneedle and delivery of the agents to the target region via the microneedle, the activating fluid is exhausted from the open area 26 of the actuator, causing the expandable section 24 to return to its original, furled state. This also causes the microneedle to be withdrawn from the body lumen wall. The microneedle, being withdrawn, is once again sheathed by the actuator.
Various microfabricated devices can be integrated into the needle, actuator and catheter for metering flows, capturing samples of biological tissue, and measuring pH. The device 10 , for instance, could include electrical sensors for measuring the flow through the microneedle as well as the pH of the neuromodulating being deployed. The device 10 could also include an intravascular ultrasonic sensor (IVUS) for locating vessel walls, and fiber optics, as is well known in the art, for viewing the target region. For such complete systems, high integrity electrical, mechanical and fluid connections are provided to transfer power, energy, and neuromodulatings or biological agents with reliability.
By way of example, the microneedle may have an overall length of between about 200 and 3,000 microns (μm). The interior cross-sectional dimension of the shaft 14 b and supply tube 14 d may be on the order of 20 to 250 um, while the tube's and shaft's exterior cross-sectional dimension may be between about 100 and 500 μm. The overall length of the actuator body may be between about 5 and 50 millimeters (mm), while the exterior and interior cross-sectional dimensions of the actuator body can be between about 0.4 and 4 mm, and 0.5 and 5 mm, respectively. The gap or slit through which the central section of the actuator unfurls may have a length of about 4-40 mm, and a cross-sectional dimension of about 50 μm to 4 mm. The diameter of the delivery tube for the activating fluid may be between 100 and 500 μm. The catheter size may be between 1.5 and 15 French (Fr).
Referring to FIGS. 4A-4D , an elastomeric component is integrated into the wall of the intraluminal catheter of FIG. 1-3 . In FIG. 4A-D , the progressive pressurization of such a structure is displayed in order of increasing pressure. In FIG. 4A , the balloon is placed within a body lumen L. The lumen wall W divides the lumen from periluminal tissue T, or adventitia A*, depending on the anatomy of the particular lumen. The pressure is neutral, and the non-distensible structure forms a U-shaped involuted balloon 12 similar to that in FIG. 1 in which a needle 14 is sheathed. While a needle is displayed in this diagram, other working elements including cutting blades, laser or fiber optic tips, radiofrequency transmitters, or other structures could be substituted for the needle. For all such structures, however, the elastomeric patch 400 will usually be disposed on the opposite side of the involuted balloon 12 from the needle 14 .
Actuation of the balloon 12 occurs with positive pressurization. In FIG. 4B , pressure (+ΔP 1 ) is added, which begins to deform the flexible but relatively non-distensible structure, causing the balloon involution to begin its reversal toward the lower energy state of a round pressure vessel. At higher pressure +ΔP 2 in FIG. 4C , the flexible but relatively non-distensible balloon material has reached its rounded shape and the elastomeric patch has begun to stretch. Finally, in FIG. 4D at still higher pressure +ΔP 3 , the elastomeric patch has stretched out to accommodate the full lumen diameter, providing an opposing force to the needle tip and sliding the needle through the lumen wall and into the adventitia A. Typical dimensions for the body lumens contemplated in this figure are between 0.1 mm and 50 mm, more often between 0.5 mm and 20 mm, and most often between 1 mm and 10 mm. The thickness of the tissue between the lumen and adventitia is typically between 0.001 mm and 5 mm, more often between 0.01 mm and 2 mm and most often between 0.05 mm and 1 mm. The pressure +ΔP useful to cause actuation of the balloon is typically in the range from 0.1 atmospheres to 20 atmospheres, more typically in the range from 0.5 to 20 atmospheres, and often in the range from 1 to 10 atmospheres.
As illustrated in FIGS. 5A-5C , the dual modulus structure shown in FIGS. 4A-4D provides for low-pressure (i.e., below pressures that may damage body tissues) actuation of an intraluminal medical device to place working elements such as needles in contact with or through lumen walls. By inflation of a constant pressure, and the elastomeric material will conform to the lumen diameter to provide full apposition. Dual modulus balloon 12 is inflated to a pressure +ΔP 3 in three different lumen diameters in FIGS. 5A , 5 B, and 5 C for the progressively larger inflation of patch 400 provides optimal apposition of the needle through the vessel wall regardless of diameter. Thus, a variable diameter system is created in which the same catheter may be employed in lumens throughout the body that are within a range of diameters. This is useful because most medical products are limited to very tight constraints (typically within 0.5 mm) in which lumens they may be used. A system as described in this invention may accommodate several millimeters of variability in the luminal diameters for which they are useful.
The above catheter designs and variations thereon, are described in published U.S. Pat. Nos. 6,547,803; 6,860,867; 7,547,294; 7,666,163 and 7,691,080, the full disclosures of which are incorporated herein by reference. Co-pending application Ser. No. 10/691,119, assigned to the assignee of the present application, describes the ability of substances delivered by direct injection into the adventitial and pericardial tissues of the heart to rapidly and evenly distribute within the heart tissues, even to locations remote from the site of injection. The full disclosure of that co-pending application is also incorporated herein by reference. An alternative needle catheter design suitable for delivering the therapeutic or diagnostic agents of the present invention will be described below. That particular catheter design is described and claimed in U.S. Pat. No. 7,141,041, the full disclosure of which is incorporated herein by reference.
Referring now to FIG. 6 , a needle injection catheter 310 constructed in accordance with the principles of the present invention comprises a catheter body 312 having a distal end 314 and a proximal 316 . Usually, a guide wire lumen 313 will be provided in a distal nose 352 of the catheter, although over-the-wire and embodiments which do not require guide wire placement will also be within the scope of the present invention. A two-port hub 320 is attached to the proximal end 316 of the catheter body 312 and includes a first port 322 for delivery of a hydraulic fluid, e.g., using a syringe 324 , and a second port 326 for delivering the neuromodulating agent, e.g., using a syringe 328 . A reciprocatable, deflectable needle 330 is mounted near the distal end of the catheter body 312 and is shown in its laterally advanced configuration in FIG. 6 .
Referring now to FIG. 7 , the proximal end 314 of the catheter body 312 has a main lumen 336 which holds the needle 330 , a reciprocatable piston 338 , and a hydraulic fluid delivery tube 340 . The piston 338 is mounted to slide over a rail 342 and is fixedly attached to the needle 330 . Thus, by delivering a pressurized hydraulic fluid through a lumen 341 tube 340 into a bellows structure 344 , the piston 338 may be advanced axially toward the distal tip in order to cause the needle to pass through a deflection path 350 formed in a catheter nose 352 .
As can be seen in FIG. 8 , the catheter 310 may be positioned in a blood vessel BV, over a guide wire GW in a conventional manner. Distal advancement of the piston 338 causes the needle 330 to advance into tissue T surrounding the lumen adjacent to the catheter when it is present in the blood vessel. The therapeutic or diagnostic agents may then be introduced through the port 326 using syringe 328 in order to introduce a plume P of agent in the cardiac tissue, as illustrated in FIG. 8 . The plume P will be within or adjacent to the region of tissue damage as described above.
The needle 330 may extend the entire length of the catheter body 312 or, more usually, will extend only partially into the therapeutic or diagnostic agents delivery lumen 337 in the tube 340 . A proximal end of the needle can form a sliding seal with the lumen 337 to permit pressurized delivery of the agent through the needle.
The needle 330 will be composed of an elastic material, typically an elastic or super elastic metal, typically being nitinol or other super elastic metal. Alternatively, the needle 330 could be formed from a non-elastically deformable or malleable metal which is shaped as it passes through a deflection path. The use of non-elastically deformable metals, however, is less preferred since such metals will generally not retain their straightened configuration after they pass through the deflection path.
The bellows structure 344 may be made by depositing by parylene or another conformal polymer layer onto a mandrel and then dissolving the mandrel from within the polymer shell structure. Alternatively, the bellows 344 could be made from an elastomeric material to form a balloon structure. In a still further alternative, a spring structure can be utilized in, on, or over the bellows in order to drive the bellows to a closed position in the absence of pressurized hydraulic fluid therein.
After the therapeutic material is delivered through the needle 330 , as shown in FIG. 8 , the needle is retracted and the catheter either repositioned for further agent delivery or withdrawn. In some embodiments, the needle will be retracted simply by aspirating the hydraulic fluid from the bellows 344 . In other embodiments, needle retraction may be assisted by a return spring, e.g., locked between a distal face of the piston 338 and a proximal wall of the distal tip 352 (not shown) and/or by a pull wire attached to the piston and running through lumen 341 .
The perivascular space is the potential space over the outer surface of a “vascular wall” of either an artery or vein. Referring to FIG. 9 , a typical arterial wall is shown in cross-section where the endothelium E is the layer of the wall which is exposed to the blood vessel lumen L. Underlying the endothelium is the basement membrane BM which in turn is surrounded by the intima I. The intima, in turn, is surrounded by the internal elastic lamina IEL over which is located the media M. In turn, the media is covered by the external elastic lamina (EEL) which acts as the outer barrier separating the arterial wall, shown collectively as W, from the adventitial layer A. Usually, the perivascular space will be considered anything lying beyond the external elastic lamina EEL, including regions within the adventitia and beyond.
Turning now to FIG. 10A-C , the renal arterial location and structure are shown. In FIG. 10A , the aorta (Ao) is shown as the central artery of the body, with the right renal artery (RRA) and left renal artery (LRA) branching from the aorta to lead blood into the kidneys. For example, the right renal artery leads oxygenated blood into the right kidney (RK). In FIG. 10B , the nerves (N) that lead from the aorta to the kidney are displayed. The nerves are shown to surround the renal artery, running roughly parallel but along a somewhat tortuous and branching route from the aorta to the kidney. The cross-section along line 10 C- 10 C of FIG. 10B is then shown in FIG. 10C . As seen in this cross-sectional representation of a renal artery, the nerves (N) that lead from aorta to kidney run through the arterial adventitia (A) and in close proximity but outside the external elastic lamina (EEL). The entire arterial cross section is shown in this FIG. 10C , with the lumen (L) surrounded by, from inside to outside, the endothelium (E), the intima (I), the internal elastic lamina (IEL), the media (M), the external elastic lamina (EEL), and finally the adventitia (A).
As illustrated in FIG. 11A-F , the methods of the present invention may be used to place an injection or infusion catheter similar to those illustrated by FIGS. 1-5 into a vessel as illustrated in FIG. 10C and to inject a plume (P) of neuromodulating agent into the adventitia (A) such that the agent comes in contact with the nerves (N) that innervate the adventitia of the renal artery. As can be seen in FIG. 11A , a catheter in the same state as FIG. 4A , wherein an actuator is shielding a needle so that the actuator can be navigated through the vessels of the body without scraping the needle against the vessel walls and causing injury, is inserted into an artery that has a media (M), an adventitia (A), and nerves (N) within the adventitia and just outside the media. A cross-section along line 11 D- 11 D from FIG. 11A is shown in FIG. 11D . It can be seen from this cross section that a therapeutic instrument comprised similarly to those in FIGS. 1-3 , with an actuator ( 12 ) attached to a catheter ( 20 ) and a needle ( 14 ) disposed within the actuator.
Turning to FIGS. 11B and 11E , we see the same system as that in FIGS. 11A and 11D , again where FIG. 11E is a view of the cross-section along line 11 E- 11 E from FIG. 11B . In FIGS. 11B and 11E , however, the actuator that has been filled with a fluid, causing the actuator to unfurl and expand, and the needle aperture to penetrate the media and into the adventitia where nerves are located. After the needle penetrates to the adventitia, a plume (P) that consists of either diagnostic agent such as radio-opaque contrast medium or neuromodulating agent such as botulinum toxin or guanethidine or a combination of the diagnostic and therapeutic agents is delivered beyond the EEL and into the adventitia. The plume (P) begins to migrate circumferentially and longitudinally within the adventitia and begins to come into contact with the nerve fibers that run through the adventitia. At this point, the physician may begin to notice the therapeutic effects. Usually, the plume P that is used to diagnose the presence of the injection and the location of the injection is in the range from 10 to 100 μl, more often around 50 μl. The plume will usually indicate one of four outcomes: (1) that the needle has penetrated into the adventitia and the plume begins to diffuse in a smooth pattern around and along the outside of the vessel, (2) that the plume follows the track of a sidebranch artery, in which case the needle aperture has been located into the sidebranch rather than in the adventitia, (3) that the plume follows the track of the artery in which the catheter is located, indicating that the needle has not penetrated the vessel wall and fluid is escaping back into the main vessel lumen, or (4) that a tightly constricted plume is forming and not diffusing longitudinally or cyndrically around the vessel, indicating that the needle aperture is located inward from the EEL and inside the media or intima. The plume is therefore useful to the operating physician to determine the appropriateness of continued injection versus deflation and repositioning of the actuator at a new treatment site.
In FIGS. 11C and 11F , where FIG. 11F is a cross-sectional view across the line 11 F- 11 F from FIG. 11C , one can see that after the plume is used to diagnose the appropriate tissue location of injection, further injection can be performed to surround the vessel with the neuromodulating agent. The extent of the final plume P* is usually fully circumferential around the artery and usually travels longitudinally by at least 1 cm when the injection volume is between 300 μl and 1 ml. In many cases, less than these volumes may be required in order to observe a therapeutic benefit to the patient's hypertension. At this point, the neuromodulating agent has penetrated the nerves around the entire artery, blocking the transmission of nerve signals and thereby creating chemical, neuromodulating, or biological denervation.
FIG. 12 illustrates the process by which botulinum toxin interrupts the transmission of nerve signals. In FIG. 12 , it is seen that the toxin, here labeled “botulinum neurotoxin”, is comprised of a “light chain” and a “heavy chain”. The heavy chain is critical to bind the botulinum neurotoxin receptors and allow the botulinum neurotoxin to enter the cell by endocytosis. Once in the cell, the light chain of botulinum neurotoxin separates from the heavy chain in this illustration and cleaves SNARE proteins “syntaxin”, “synaptobrefin”, and “SNAP 25”. When these SNARE proteins are cleaved, vesicles containing acetylcholine cannot be released from the nerve into the synaptic cleft. While this is shown in FIG. 12 for the neuromuscular junction, this is merely illustrative of the mechanism by which botulinum neurotoxin interacts with nerve cells, as it has also been shown that botulinum neurotoxins prohibit the release of acetylcholine and noradrenaline from other nerve junctions.
The following Experiments are offered by way of illustration, not by way of limitation.
EXPERIMENTAL
Studies were performed in a normal porcine model to determine if adventitial delivery of guanethidine could reduce kidney norepinephrine (NE), a marker for successful denervation. Successful denervation is well known to reduce blood pressure in hypertensive patients.
Renal denervation evidenced by NE reduction: Guanethidine monosulfate was diluted in 0.9% NaCl to a concentration of 12.5 mg/ml, then further diluted in iodinated contrast medium to a final concentration of 10 mg/ml. This solution was injected using a Mercator MedSystems Bullfrog Micro-Infusion Catheter (further described in this application and detailed in FIG. 11A-F ) into the adventitia of both renal arteries, approximately halfway between the aorta and the hilum of the kidney. The injection was monitored with X-ray visualization of contrast medium to confirm adventitial distribution, which was confirmed to carry the injectate longitudinally and circumferentially around the artery, as well as transversely into the perivascular tissue. No injection was made into control animals, and historical controls from Connors 2004 were used as comparators.
Twenty-eight days after injection, kidneys and renal arteries were harvested. Kidney samples were taken using the method established by Connors 2004. Briefly, cortex tissue samples from the poles of the kidneys were removed and sectioned into approximately 100 mg segments. From each kidney, samples from each pole were pooled for analysis. Renal arteries were perfusion fixed in 10% neutral buffered formalin an submitted for histopathology.
Histology: Arteries appeared normal at 28 days, with no signs of vascular toxicity. Perivascular indications of denervation were apparent from lymphocyte, macrophage and plasma cell infiltration into adventitial nerve bodies, with nerve degeneration characterized by hypervacuolization and eosinophilia.
Radio-immunoassay: NE levels in renal cortex tissue revealed average levels of 64 nanograms (ng) NE per gram (g) of renal cortex. When compared to normal controls of 450 ng/g, this represents a reduction in renal cortex NE of 86%. These data are shown in FIG. 13 .
Additional comparison can be made to the reduction in renal cortex NE from surgical denervation, which Connors 2004 reported as 97% and Krum 2008 reported as 94%. Furthermore, the reduction in kidney NE reported with the use of radiofrequency catheter ablation of the renal nerves has been reported as 86%. The radiofrequency method has since been used in clinical trials and evidence has been shown that the ablation of the nerves, resulting in reduced NE by 86%, directly translates to reduced hypertension in patients, with reports of systolic pressure reduction of 27 mmHg and diastolic reduction of 17 mmHg, twelve months after treatment.
While the above is a complete description of the preferred embodiments of the invention, various alternatives, modifications, and equivalents may be used. Therefore, the above description should not be taken as limiting the scope of the invention which is defined by the appended claims.
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Sympathetic nerves run through the adventitia surrounding renal arteries and are critical in the modulation of systemic hypertension. Hyperactivity of these nerves can cause renal hypertension, a disease prevalent in 30-40% of the adult population. Hypertension can be treated with neuromodulating agents (such as angiotensin converting enzyme inhibitors, angiotensin II inhibitors, or aldosterone receptor blockers), but requires adherence to strict medication regimens and often does not reach target blood pressure threshold to reduce risk of major cardiovascular events. A minimally invasive solution is presented here to reduce the activity of the sympathetic nerves surrounding the renal artery by locally delivering neurotoxic or nerve-blocking agents into the adventitia. Extended elution of these agents may also be accomplished in order to tailor the therapy to the patient.
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CROSS REFERENCE TO RELATED APPLICATION
Reference is made to and priority claimed from U.S. Provisional Application Ser. No. 60/532,288, filed Dec. 23, 2003, entitled A METHOD FOR TESTING A PLASTIC SLEEVE FOR AN IMAGE CYLINDER OR A BLANKET CYLINDER.
FIELD OF THE INVENTION
The present invention is directed to electronic digital printing devices. More particularly, the present invention is directed to an electronic printhead having a variable exposure width.
BACKGROUND OF THE INVENTION
Many electronic digital printers apply print characters to paper via multiple exposure elements of an exposure device. In some printers, such as the NexPress 2100 from NexPress Solutions LLC, the exposure elements are light emitting diodes (“LEDs”) and the exposure device is an LED printhead.
The LEDs are typically controlled by a printhead driver integrated circuit (“IC”). Each driver IC may control many LEDs, and a printer may include multiple driver ICs.
Known LED printhead assemblies and other types of printheads typically having a “fixed width” architecture, meaning that a unique substrate assembly is designed to match the product exposure width requirements. With the known printheads, for every line of exposure, all of the LED driver ICs populated on the substrate must be reloaded for every line of exposure. Specifically, the data register for each LED element must be resent data for each and every line of exposure. Intended “off” LEDs must be loaded with a zero data value for each line. In many applications, certain LEDs at the ends of an LED printhead are not used and must be continually loaded with zero data. This redundant operation to load unused LEDs with zero data wastes a significant amount of data loading bandwidth and therefore limits the speed of the printing device.
Since known LED printheads are a fixed width they tend to be used for specific products. It is not practical to use a wider LED printhead for narrower product applications due to-unnecessary data loading and bandwidth loss.
Fixed width does not allow for running a reduced image area at a higher speed without increasing the data rate of flow. Known LED image path driving systems can easily be adapted to a change in the amount of data sent, but cannot easily increase the speed at which the data is sent.
FIG. 1 is a block diagram of a prior art fixed width printhead. Printhead 10 is formed from a string of LEDs 18 . Printhead 10 has a fixed width 12 based on the entire string of LEDs 18 . For an image area requirement 14 , some of the LEDs form unused areas 16 and 17 . However, unused areas 16 , 17 still must be loaded with zero data for each and every line of exposure. As discussed, this reduces the speed of the printing device.
Based on the foregoing, there is a need for a flexible printhead in which unused portions can be turned off or disabled.
SUMMARY OF THE INVENTION
The present invention is a driver IC for an electronic printhead with variable exposure width. The driver IC includes a plurality of registers corresponding to exposure elements and a token input. The driver IC further includes circuitry coupled to the registers. The circuitry is adapted to bypass received data from the registers in response to a token received from the token input.
By bypassing sections of unused areas, the overall speed of the printhead can be increased. This improves data bandwidth and also data robustness since less data needs to be sent.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a prior art fixed width printhead;
FIG. 2 is a block diagram of a portion of an LED printhead board illustrating one embodiment of the present invention; and
FIG. 3 is a circuit diagram of circuitry that performs the token bypass function in each driver IC in accordance with one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the present invention is a flexible width LED printhead that allows for a variable printhead imaging width by disabling unused LEDs.
FIG. 2 is a block diagram of a portion of an LED printhead board 20 illustrating one embodiment of the present invention. Printhead board 20 includes a substrate 30 and a string of driver ICs 21 - 25 mounted on substrate 30 . Each driver IC 21 - 25 is coupled to LEDs (not shown) or other types of exposure elements. In other embodiments, printhead board 20 will include more than five driver ICs, depending on the desired width of the printhead. In one embodiment, each driver IC on board 20 is coupled to 96 LEDs, and each driver IC is approximately ⅓ inch long.
In one embodiment, each driver IC 21 - 25 includes a token input 31 , a token output 32 , a clock input (“SCLK”) 34 , and a data input/output bus 33 . Data bus 33 maybe at the “front” of the driver ICs, as shown in FIG. 2 , or it may be on the side of the driver ICs. In one embodiment, a token is one or more digital bits or any type of signal that can toggle between multiple values.
Data is initially received by a driver IC at an end of the string of driver ICs 21 - 25 , and is passed to the other driver ICs in a serial fashion using token control. Token control is a direction control of data loading inside the driver ICs. Data for multiple exposure elements is passed from right to left or from left to right in a serial fashion along the string of driver ICs 21 - 25 so that multiple exposure element registers can be loaded by one external data bus (e.g., data bus 33 ). The token shifts by one element on every clock transition.
One embodiment of the present invention bypasses selective driver ICs on the string of driver ICs 21 - 25 from receiving data to reduce the exposure width of the printhead. For example, in FIG. 2 driver ICs 21 - 23 are bypassed in one embodiment. In one embodiment, a “token bypass” function, which involves transmitting a bypass token among the driver ICs, is used to bypass selective driver ICs.
When no driver ICs are bypassed, as in the prior art and embodiments of the present invention when the entire exposure width of the printhead is used, data is presented to the input data bus and serially loaded into the multiple LED registers of each driver IC using the token and clock signals. When the input token is activated at a particular driver IC, each clock edge latches the LED data to the input data register and passes token control to the next register. When the last LED clock or token advancement is received and data is latched, the token is passed out of the driver IC token output signal to the next driver IC token input signal.
In contrast, the token bypass function in accordance with one embodiment of the present invention bypasses the whole driver IC token/input data register-loading portion. When token bypass is activated the input token signal is passed through a single flip-flop to the token output pad. The token passing latency through the driver IC is only one clock period. When token bypass is activated, no input LED registers are loaded.
FIG. 2 illustrates the token bypass operation in which driver ICs 21 - 23 are desired to be bypassed because, for example, the LEDs associated with those driver ICs are part of an unused exposure area of the printhead. The token bypass bit is enabled for those three driver ICs. When the driver ICs are bypassed it is not necessary to supply multiple clocks and multiple zero data into driver IC 21 , then driver IC 22 then driver IC 23 before loading the first desired driver IC, driver IC 24 (assuming a left to right loading of data). Instead, only one clock period per bypassed driver IC is required and data begins loading into driver IC 24 on the fourth clock period. Since some LED driver ICs typically include of up to 100 or more LED elements and driving circuits, this produces significant time reduction of data loading in order to arrive at a desired starting printing point. Further, the starting point is easily changeable by software making active operating exposure width changes easy to perform.
In one embodiment, each driver IC 21 - 25 includes circuitry for performing the token bypass function. FIG. 3 is a circuit diagram of circuitry 100 that performs the token bypass function in each driver IC in accordance with one embodiment of the present invention. Circuitry 100 includes Joint Test Action Group (“JTAG”) Tap controller 102 and a JTAG control register 103 . JTAG TAP controller 102 can be a standard JTAG compliant controller used for accessing JTAG control register 103 in accordance with the JTAG IEEE 1149.1 boundary scan standard. Control register 103 may be a standard JTAG register and its purpose is to enable or disable the token bypass function.
In one embodiment, bit- 0 of control register 103 activates the token bypass feature. When set to zero the token bypass is not enabled, the loading data flows into the driver IC within LED registers 105 (i.e., one register per each exposure element) until all LED registers are filled on clock edges (SCLK), then the token signal is passed out to the token output through a selector 106 and a token delay flip-flop 107 for use by the next connected driver IC connected. When bit- 0 of control register 103 is set to one the token bypass function is enabled, the data and token signal bypasses LED registers 105 and the token signal exits the driver IC at delay flip-flop 107 one clock edge later.
In other embodiments, the circuitry of FIG. 3 can be duplicated in multiple sections within a driver IC to allow finer resolution of the bypass areas. For example, a portion of the LEDs on a single driver IC can be bypassed.
As disclosed, embodiments of the present invention allow driver ICs in a string of driver ICs to be bypassed from the data loading process. This allows software adjustment of the active exposure area and allows flexibility of active exposure width, making one printhead device compatible for multiple width situations (e.g., multiple end products).
By bypassing sections of unused areas, the overall speed of a printhead can be increased. This improves data bandwidth and also data robustness since less data needs to be sent.
In addition, embodiments of the present invention allow widths smaller than the total width to be operated at higher speed since less data is required. Higher speed modes can be achieved by shrinking the active area. For example, paper one-half in size to the overall printhead maximum width can be run at twice the speed by bypassing one-half the driver ICs.
Further, production scanning and testing times can be lowered. Driver ICs that are not being scanned or tested can be bypassed. By only enabling the desired driver ICs under test, significantly lower amounts of data need to be sent during the data-loading phase.
Several embodiments of the present invention are specifically illustrated and/or described herein. However, it will be appreciated that modifications and variations of the present invention are covered by the above teachings and within the purview of the appended claims without departing from the spirit and intended scope of the invention.
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A printhead with a variable exposure width having a plurality of exposure elements defining a given exposure width. A plurality of driver ICs are coupled to the exposure elements, each driver IC including a plurality of registers. A data bus is coupled to the plurality of driver ICs. Circuitry is provided in a first driver IC of the plurality of driver ICs for having data received from the data bus bypass the plurality of registers in the first driver IC to disable unused exposure elements of the plurality of exposure elements, whereby the exposure width can be varied from the given width, and data loading bandwidth is minimized.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a biocompatible, implantable electrode for electrically active medical devices. The electrode has an optimized surface topography for improved electrical performance. Such a electrode is suitable for devices which may be permanently implanted in the human body as stimulation electrodes, such as pacemakers, or as sensors of medical conditions. Such is achieved by the application of ultrafast high energy pulses to the surface of a solid, monolithic electrode material for the purpose of increasing the surface area and thereby decreasing its after-potential polarization.
[0003] 2. Description of the Related Art
[0004] There is great commercial interest in producing active implantable devices which are typically electrodes used for the stimulation of tissue or the sensing of electrical bio-rhythms. The electrical performance of implantable electrodes can be enhanced by increasing the external surface area which is in contact with tissues inside the body. It is known that increasing the surface area of an implantable electrode increases the double layer capacitance of the electrode and reduces the after-potential polarization, thereby increasing device battery life, or allowing for lower capture thresholds, and improved sensing of certain electrical signals, such as R and P waves. It is known in the art to apply a coating to increase the surface area of the electrode thereby reducing the after-potential polarization. A reduction in after-potential polarization results in an increase in charge transfer efficiency by allowing increased charge transfer at lower voltages. This is of particular interest in neurological stimulation. Double layer capacitance is typically measured by means of electrochemical impedance spectroscopy. In this method an electrode is submerged in a electrolytic bath and a small cyclic wave is imposed on the electrode. The current and voltage response of the electrode/electrolyte system is measured to determine the double layer capacitance. The capacitance is the predominant factor in the impedance at low frequencies (<10 Hz) and thus the capacitance is typically measured at frequencies of 0.001 Hz-1 Hz.
[0005] The current state of the art for increasing the surface area of an implantable electrode is to apply a suitable coating to the surface of electrode substrates. A principal concern in any coating application is the joining of the substrate and coating material and the adhesion between them. In this regard, U.S. Pat. No. 5,571,158 shows a stimulation electrode having a porous surface coating whose active surface area is essentially larger than the surface area defined by the geometrical basic shape of the electrode. U.S. Pat. No. 6,799,076 discloses an electrode having a substrate with a first layer covering at least a portion of the substrate, and a second layer covering at least a portion of the first layer. The first layer consists of a carbide, nitride or carbonitride of titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. The second layer includes iridium. U.S. Pat. No. 5,318,572 teaches a high efficiency tissue stimulating and signal sensing electrode. A lead has a porous electrode of platinum-iridium with recessed areas or grooves formed into the surface. The grooves allow for acute electrode stabilization as a result of clot formation and endocardial tissue capture. At least one layer of a porous coating of 20-200 micron diameter spherical particles are deposited on the surface of the base electrode to obtain a porous macrostructure for promoting chronic tissue ingrowth. A microstructure surface coating is applied to increase the active surface area and enhance electrical efficiency by lowering electrochemical polarization and increasing electrical capacitance.
[0006] A particular concern for these techniques is that a section of coating might become dislodged in use and become an irritant. Current techniques for testing the adhesion of a coating to a substrate results in the destruction of the test piece which is costly and requires statistical evidence to validate the test method and sampling. A better alternative to a coating would be the modification of the electrode substrate material itself, thereby eliminating the issue of poor adhesion and the potential of coating particles becoming dislodged during use. Prior attempts to produce a suitable modified surface which does not include a coating have failed due to mechanical limitations. An example is found in U.S. patent publication 2011/0160821 where the surface is laser etched, thus producing ridges with features 25,000 nm to 250,000 nm. For a suitable electrode, the surface features need to be sub-millimeter, for example, from about 1 nm to about 1000 nm. Others have taught laser ablation of electrode surfaces, however, such techniques cannot achieve the nanometer scale feature size of this invention.
[0007] The present invention solves these issues by the application of ultra-fast energy pulses supplied to the surface. It has now been found that energy pulses delivered by means of an ultrafast laser produces surface structures on the order of 50 nm to 500 nm which is ideal for tissue stimulation. This process is produced not by laser etching and removal of material but by a restructuring of the surface. In the laser etching process of U.S. patent publication 2011/0160821 the surface is modified through the impingement of the laser, and the smallest feature that can be made equates to the size of the focused laser beam, which is limited by the wavelength of the laser, typically 200-1600 nm.
SUMMARY OF THE INVENTION
[0008] The invention provides an electrode comprising a solid, monolithic substrate having an outer peripheral surface; the outer peripheral surface having a topography defined by a plurality of voids distributed about the outer peripheral surface and extending a depth through the substrate; said voids having a depth through the substrate of from about 50 nm to about 500 nm; and said voids having a width of from about 50 nm to about 500 nm; said voids being spaced from adjacent voids a distance of from about 50 nm to about 250 nm.
[0009] The invention also provides a method for producing an electrode comprising a solid, monolithic substrate having an outer peripheral surface; the outer peripheral surface having a topography defined by a plurality of voids distributed about the outer peripheral surface and extending a depth through the substrate; said voids having a depth through the substrate of from about 50 nm to about 500 nm; and said voids having a width of from about 50 nm to about 500 nm; each void being spaced from adjacent voids a distance of from about 50 nm to about 250 nm, the method comprising exposing a solid, monolithic substrate to from about 10 to about 500 pulses of laser irradiation having a wavelength of from about 200 nm to about 1600 nm, at a pulse width of from about 1 femtosecond to about 5 picoseconds, and at a irradiance of from about 200 watts/cm 2 to about 5000 watts/cm 2 .
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 illustrates the surface topography of an inventive electrode produced according to the conditions of Example 1.
[0011] FIG. 2 shows a illustrates the surface topography of an inventive electrode produced according to the conditions of Example 2.
[0012] FIG. 3 shows a illustrates the surface topography of an comparative electrode produced according to the conditions of Comparative Example 3.
[0013] FIG. 4 shows a illustrates the surface topography of an inventive electrode produced according to the conditions of Example 4.
[0014] FIG. 5 shows a illustrates the surface topography of an comparative electrode produced according to the conditions of Comparative Example 5.
DESCRIPTION OF THE INVENTION
[0015] Surface morphologies of implanted biomedical electrodes are designed to improve interaction with surrounding tissues. The invention provides biological benefits which exploit nanometer-scale features such as a reduced likelihood of infection, and functional benefits such as improved electrical transfer. The invention produces nanometer-scale features on biocompatible metals such as platinum by exposure to a femtosecond laser operating at various wavelengths. Laser induced surface structures produce an array of voids with length and depth ranging from about 50 nm to about 500 nm, depending on the laser parameters employed.
[0016] The invention realizes a performance advantage over typical prior art surface modifications by achieving an optimal surface geometry, which maximizes the effective surface area of the electrode while minimizing the after-potential polarization effect, thereby increasing charge transfer efficiency. After-potential polarization is the voltage remaining on an electrode after a stimulation pulse on the electrode from a device such as a pacemaker. It is a measure of how efficiently the charge is injected into the tissue.
[0017] It is known that the method for charge transfer in a medical electrode is by the charging and discharging of the electrical double layer capacitance formed on the surface of the electrode. This layer can be thought of as a simple parallel plate model in which the tissue to be stimulated is separated from the electrode surface by a barrier primarily of water, Na, K and Cl. The thickness of this layer is dictated by the concentration of the electrolyte in the body and is therefore uniform over the working life of the electrode. The thickness of an electrical double layer formed by an electrical conductor in 0.9% saline, i.e., body fluid is on the order of 1 nm and the expected thickness of the double layer capacitance formed in normal body electrolyte would be from about 0.5 nm to about 10 nm, more typically from about 5 to about 6 nm.
[0018] A typical human cell is on the order of from about 5,000 nm to about 10,000 nm in size. Because the cells are much larger than the layer and much smaller than the electrode surface, the cells can be thought of as being parallel to the surface of the electrode. As the non-polarized electrolyte (the electrolyte present but not participating in the electrical double layer) increases, the impedance of the tissue-electrode system increases. This is known as the solution resistance. The increased impedance results in a less effective charge transfer due to a dissipation of voltage along the solution resistance path. To minimize this impedance, the tissue to be stimulated should be as close to the electrode surface as possible. It would therefore be preferred, for these purposes, to have the electrode surface flat and placed parallel to the tissue.
[0019] The invention thus provides an electrode comprising a solid, monolithic substrate having an outer peripheral surface. The substrate comprises a biocompatible metal suitable for implanting within the tissues of a mammal. Examples non-exclusively include platinum, steel, alloys of platinum and iridium, alloys of nickel and cobalt, and combinations thereof. In one embodiment, the outer peripheral surface of an electrode has an area of from about 1 mm 2 to about 20 mm 2 , preferably from about 3 mm 2 to about 12 mm 2 . The electrode may have any suitable configuration or shape such as a tubular, flat, mushroom or corkscrew shape. The outer peripheral surface has a topography defined by a plurality of voids distributed about the outer peripheral surface and extending a depth through the substrate. The voids have a depth through the substrate of from about 50 nm to about 500 nm, preferably from about 100 nm to about 250 nm. The voids have a width of from about 50 nm to about 500 nm, preferably of from about 100 nm to about 250 nm. The voids are spaced from adjacent voids a distance of from about 50 nm to about 250 nm.
[0020] An electrode according to the invention, is produced by exposing an outer peripheral surface of a solid, monolithic substrate of such a biocompatible metal to pulses of laser irradiation. In one embodiment, a laser beam which produces a spot size of 100,000-800,000 nm is used to produce the structures. In one embodiment, the number of pulses of laser irradiation per spot ranges from about 10 to about 500 pulses, preferably from about 50 to about 400, and more preferably from about 100 to about 300. In one embodiment, the pulse wavelength is of from about 200 nm to about 1600 nm, preferably from about 400 to about 1,000, and more preferably from about 400 to about 800. In one embodiment, the pulse width ranges from about 1 femtosecond to about 5 picoseconds, preferably from about 100 femtoseconds to about 3 picoseconds, and at a irradiance of from about 200 watts/cm 2 to about 5000 watts/cm 2 . Typically the laser irradiation produces a spot diameter of from about 10 μm to about 10,000 μm, preferably from about 25 μm to about 2,500 μm, and more preferably from about 50 μm to about 1,000 μm. Examples of suitable lasers non-exclusively include a Coherent Libra-F Ti:Sapphire amplifier laser system, and a Coherent AVIA laser. According to the invention, the resulting electrode has a polarization of about 1,000 mV or less, preferably about 500 mV or less, and more preferably about 200 mV or less. It has been determined that the lower the polarization of the electrode, the more optimized is the surface topography for improved electrical performance. The desirable characteristics of the surface, those being high double layer capacitance of the electrode and a low after-potential polarization effect, are enhanced when the surface area of the electrode is increased. A reduction in after-potential polarization results in an increase in charge transfer efficiency by allowing increased charge transfer at lower voltages. Thus a reduction of after-potential polarization increases device battery life, and improves sensing of certain electrical signals.
[0021] In use, the inventive electrode has at least one electrical connector electrically attached at an end thereof to the substrate. Typically, this may be a wire of a suitable material such as a biocompatible, conductive material such as platinum, silver, copper, a superalloy such as MP35N, or a superplastic such as Nitrol. In one embodiment, the other end of the wire is connected to an electrical pulse generator such as a cardiac pacemaker. In another embodiment, the other end of the wire is connected to an electrical measurement device such as a sensor of biological conditions, or a voltage recording device.
[0022] The following non-limiting examples serve to illustrate the invention.
EXAMPLES
[0023] A series of cylindrical platinum electrodes having a diameter of 2.2 mm and an active length of 0.75 mm was processed via ultrafast laser texturing. Each of the cylinders was rotated on its axis while the laser impinged the surface at a nearly oblique angle and the wavelength, number of pulses and laser irradiance were varied. Variations in operating parameters give the indicated potential polarization results. A Coherent Libra-F Ti:Sapphire amplifier laser system was used for the exposure.
Example 1
[0024] In this example, the laser exposure had a wavelength of 800 nm, an irradiance of 400 W/cm 2 and 100 pulses per spot. The resulting polarization was 600 mV. An example of a small surface feature size is approximately 4 nm and an example of a large surface feature size is approximately 107 nm.
Example 2
[0025] In this example, the laser exposure had a wavelength of 800 nm, an irradiance of 400 W/cm 2 and 10 pulses per spot. The resulting polarization was 829 mV. The surface topography is shown in FIG. 2 . The structure appears to be similar to that of Example 1, but the depth of the features is not as pronounced.
Example 3
Comparative
[0026] In this example, the laser exposure had a wavelength of 800 nm, an irradiance of 100 W/cm 2 and 50 pulses per spot. The resulting polarization was 1100 mV, which is similar to that of an un-processed sample. FIG. 3 shows the desired inventive structure does not appear to be present.
Example 4
[0027] In this example, the laser exposure had a wavelength of 400 nm, an irradiance of 1000 W/cm 2 and 100 pulses per spot. The resulting polarization was 700 mV. FIG. 4 shows the structure appears to be similar to FIG. 1 but with less definition in the features.
Example 5
Comparative
[0028] In this example, the laser exposure had a wavelength of 400 nm, an irradiance of 64 W/cm 2 and 10 pulses per spot. The resulting polarization was 996 mV. The surface does not present any features of the invention. The only features present are due to the process used to form the material into bar stock.
[0029] While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily appreciated by those of ordinary skill in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives which have been discussed above and all equivalents thereto.
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A biocompatible, implantable electrode for electrically active medical devices. The implantable medical electrode has a surface geometry which optimizes the electrical performance of the electrode, while mitigating the undesirable effects associated with prior art porous surfaces. The electrode has an optimized surface topography for improved electrical performance. Such a electrode is suitable for devices which may be permanently implanted in the human body as stimulation electrodes, such as pacemakers, or as sensors of medical conditions. Such is achieved by the application of ultrafast high energy pulses to the surface of a solid, monolithic electrode material for the purpose of increasing the surface area and thereby decreasing its after-potential polarization.
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BACKGROUND OF THE INVENTION
The present methods and apparatuses relate in general to dropping a hockey puck. More specifically, the present methods and apparatuses relate to dropping a hockey puck to facilitate, simulate, or practice a hockey face-off.
A “face-off” is a significant part of the sport of hockey. In competition, a referee releases a hockey puck (also referred to as the “puck”) toward a playing surface between two opposing hockey players. Preferably, the puck is released such that it is relatively flat when it contacts the playing surface so that one player does not gain an advantage due to a peculiar bounce of an undesirably oriented puck. Once the puck is released, the players quickly vie for control of the puck. Accordingly, hockey players of all ages and skill levels earnestly seek to improve their face-off skills in order to “win” more face-offs.
A number of devices have been constructed to help hockey players practice face-offs without the need for an additional person to release the puck. However, these conventional devices do not provide robust convenience, portability, stability, or consistency. For example, some conventional devices must be connected to an external power source by a power cord. Such devices are not convenient for practicing at a typical ice rink where the nearest power source may be a significant distance away from a typical face-off position. Consequently, it is not uncommon for a lengthy power cord to be cumbersomely positioned across the playing surface. Further, at some practice locations, an external power source may not be readily available.
Other conventional devices are designed to be fixedly mounted to a support structure such as a wall. Such mounted devices have several shortcomings. For example, significant effort is often required to move a mounted device. Further, an owner of a typical ice rink facility, e.g., a governmental entity, may not allow a practice device to be mounted to the walls of the facility, even temporarily. Further still, a face-off next to a wall does not accurately simulate actual face-off situations that typically occur some distance from the wall of an ice rink. For example, if a device is mounted to a wall, the wall can obstruct the players' face-off options.
Some conventional devices are not stable. For example, some devices provide bases that are not large or sturdy enough to remain stable during a face-off. When players scramble to control a released puck, such devices may be easily tipped over, thereby interfering with the face-off. Further, lack of stability can cause the pucks to be dropped in an inconsistent manner, which inconsistencies can cause undesirable results. For example, a puck may be released at a non-flat angle, thereby causing the angled puck to take a peculiar bounce off of the playing surface. The peculiar bounce may unfairly bias the face-off in favor of one player.
Other conventional hockey practice devices are not designed to simulate a face-off. For example, many conventional devices are designed to propel pucks in a horizontal or generally non-vertical direction. Such devices do not simulate face-off situations, but instead provide practice for receiving or contacting pucks that are moving laterally over a playing or practice surface. In short, conventional hockey face-off practice devices do not provide robust convenience, portability, stability, or consistency.
The existing art does not teach or even suggest a solution to the challenges identified above. There is no motivation in the art to solve the problems identified above. Furthermore, the approaches of the existing art affirmatively teach away from a comprehensive solution to such obstacles.
SUMMARY OF THE INVENTION
The present methods and apparatuses relate in general to dropping a hockey puck. More specifically, the present methods and apparatuses relate to dropping a hockey puck to facilitate, simulate, or practice a hockey face-off. Various embodiments of the methods and apparatuses can be configured to provide convenience, portability, stability, and/or consistency for dropping a hockey puck to facilitate a hockey face-off.
In some embodiments, a frame can support a puck housing component (“puck housing”) and a feed mechanism. The feed mechanism may be configured to feed the hockey puck from the puck housing to a feed chute. A release mechanism can receive the hockey puck from the feed chute. The release mechanism may be configured to release the hockey puck according to a release rate. In some embodiments, the release rate is predefined by the operator of the device. A power source can be carried by the frame and be configured to power the feed and the release of the hockey puck.
In some embodiments, a hockey puck can be fed from a puck housing to a release mechanism. The hockey puck can be received and leveled at the release mechanism, including extending a stopper to receive the hockey puck. The hockey puck can be secured, including extending a gripper to secure the hockey puck. The stoppers can retract. The hockey puck may be released at a predetermined interval after the stoppers retract.
BRIEF DESCRIPTION OF THE DRAWINGS
Certain embodiments of the present apparatuses and methods will now be described, by way of examples, with reference to the accompanying drawings, in which:
FIG. 1 is a perspective view diagram illustrating an example of a hockey face-off apparatus.
FIG. 2 is a rear-view diagram illustrating an example of a hockey face-off apparatus.
FIG. 3 is a side-view diagram illustrating an example of a hockey face-off apparatus.
FIG. 4 is a top-view diagram illustrating an example of a hockey face-off apparatus.
FIG. 5 is a side-view diagram illustrating an example of a release assembly for a hockey face-off apparatus with grippers in a generally open position.
FIG. 6 is a side-view diagram illustrating an example of a release assembly for a hockey face-off apparatus with the grippers in a generally closed position.
FIG. 7 is a circuit diagram illustrating an example of a control system and connected actuators.
FIG. 8 is a circuit diagram illustrating an example of a control system and connected actuators, including a puck dropper.
FIG. 9 is a flow chart diagram illustrating an example of a process for dropping a puck for facilitating a hockey face-off.
FIG. 10 is a flow diagram illustrating an example of a process for dropping a puck for facilitating a hockey face-off.
DETAILED DESCRIPTION
I. INTRODUCTION OF ELEMENTS AND DEFINITIONS
The present methods and apparatuses relate in general to dropping a hockey puck. More specifically, the present methods and apparatuses relate to dropping a hockey puck to facilitate a hockey face-off.
Referring now to the drawings, FIG. 1 is a perspective view of a hockey face-off apparatus (the “apparatus”) 100 . The apparatus 100 can include a wide variety of different components and configurations. The apparatus 100 in FIG. 1 includes: a frame 110 ; a feed mechanism 120 coupled to or otherwise in contact with said frame 110 , a puck housing component (“puck housing”) 130 coupled to or otherwise in contact with said frame 110 ; a feed chute 140 coupled to or otherwise in contact with said frame 110 ; and a release assembly 150 coupled to or otherwise in contact with said feed chute 140 . The apparatus 100 further includes: wheels 155 configured to support the frame 110 ; a compressor 160 , a power source 165 , and a control unit 170 supported by the frame 110 ; and a stow assembly 175 coupled to the frame 110 . As shown in FIG. 1 , the release assembly 150 can include a stopper 180 , a gripper 185 , and a puck dropper 190 . Each of these elements is discussed in more detail below.
A. FRAME
The frame 110 can be configured for positioning on a support surface. Preferably, the frame 110 may be positioned on a generally horizontal surface such as a playing surface comprising ice. The frame 110 can be configured to stand alone without tipping during operation. As shown in FIG. 1 , the frame 110 may comprise beams arranged to help prevent the apparatus 100 from tipping. The beams should comprise a structurally strong material, such as aluminum, steel, and the like.
The frame 110 can be arranged in a wide variety of configurations by operators of the apparatus that are capable of supporting certain elements of the apparatus 100 . In other words, the apparatus 100 may be self-contained. As shown in FIG. 1 , the frame 110 can support the feed mechanism 120 , the puck housing 130 , the feed chute 140 , the release assembly 150 , the air compressor 160 (also referred to as the “compressor 160 ”), the power source 165 , the control unit 170 , and the stow assembly 175 . In FIG. 1 , the frame 110 comprises beams are arranged to form a generally three-dimensional shape capable of supporting elements of the apparatus 100 . A wide variety of different support structures can perform the functionality of the frame 110 .
By being configured to support the various components mentioned above, the frame 110 is portable. Accordingly, the apparatus 100 can be configured to be self-contained to enhance its portability. In addition, as shown in FIG. 1 , the frame 110 may be supported by the wheels 155 or other components to further enhance its portability.
The frame 110 may form generally horizontal surfaces capable of supporting certain elements of the apparatus. As shown in FIG. 1 , the frame 110 defines a generally horizontal area that is used to support the compressor 160 and the power source 165 . The frame 110 of FIG. 1 also forms a generally horizontal surface for receiving a puck from the puck housing 130 . The feed mechanism 120 may be positioned proximate to this position for feeding the puck toward the feed chute 140 .
B. POWER SOURCE
The power source 165 can be supported and/or housed by the frame 110 . As shown if FIG. 1 , the power source 165 may rest on and/or be fixed to a horizontal surface of the frame 110 . Accordingly, in some embodiments, the power source 165 is onboard the apparatus 100 , eliminating the need for an external power supply. The power source 165 may comprise any device capable of supplying sufficient power to the apparatus 100 , such as a battery.
C. COMPRESSOR
The compressor 160 can be supported and/or housed by the frame 110 . As shown in FIG. 1 , the power source 165 may rest on and/or be fixed to a horizontal surface of the frame 110 . Accordingly, in some embodiments, the compressor 160 is on-board the apparatus, eliminating the need for an external air compressor.
The compressor 160 can comprise any device capable of generating sufficient air pressure for operation of the apparatus 100 . The compressor 160 will be further discussed below in relation to the control unit 170 .
D. STOW ASSEMBLY
The stow assembly 175 can be coupled to the frame 110 and configured to stow the removable feed chute 140 and the release assembly 150 . The feed chute 140 and the release assembly 150 will be discussed in detail below. As shown in FIG. 1 , the stow assembly 175 may comprise a number of beams extending from the frame 110 and configured to support the feed chute 140 . The beams can support the feed chute 140 in a stow position.
E. FEED MECHANISM
The feed mechanism 120 can include any mechanism capable of causing a puck to enter the feed chute 140 . For example, the feed mechanism 120 may comprise an actuator, e.g., a pneumatic actuator or solenoid, capable of feeding the puck to the feed chute 140 . In a preferred embodiment, the feed mechanism 120 comprises an actuator configured to extend to push the puck toward the feed chute 140 .
As shown in FIG. 1 , the feed mechanism 120 may be coupled to the frame 110 at a position proximate to the bottom end of the puck housing 130 . Preferably, the feed mechanism 120 and puck housing 130 are configured such that only one puck at a time can be fed to the feed chute. For example, the feed mechanism 120 can be configured to push the bottom-most puck out from under the puck housing 130 and toward the feed chute 140 . Accordingly, the puck housing 130 should be positioned at an appropriate height above a generally horizontal surface such that the feed mechanism 120 feeds one puck at a time to the feed chute 140 .
The feed mechanism 120 can be configured to accelerate pucks at a specific feed rate. Accordingly, the feed mechanism 120 may be controlled by the control unit 170 , and the control unit 170 may determine the feed rate. The control unit 170 and the feed rate are discussed below.
F. PUCK HOUSING
The puck housing 130 can be configured to house a number of pucks. As shown in FIG. 1 , the puck housing 130 may include a generally tube-shaped cylinder of appropriate size to house the pucks. The puck housing 130 should include open ends such that pucks may be inserted into the puck housing 130 at one end and exit, in turn, at the other end. Preferably, the puck housing 130 is shaped to help orient the pucks in generally transverse positions. Accordingly, the pucks can be arranged in the puck housing 130 as a stack of transversely-oriented pucks.
The puck housing 130 can include any structure capable of guiding the pucks toward the feed mechanism 120 and/or the feed chute 140 . As shown in FIG. 1 , the puck housing 130 can be coupled to or otherwise in contact with the frame 110 at a generally vertical orientation. Such an orientation utilizes gravity to help guide the pucks generally downward toward the feed mechanism 120 . Other mechanisms, e.g., a spring, can also be used to bias the pucks toward the feed mechanism 120 .
As mentioned above, the exit end of the puck housing 130 shown in FIG. 1 can preferably be positioned a certain distance above a horizontal surface of the frame 110 . Accordingly, the bottom-most puck of the puck housing 130 may descend toward the feed mechanism 120 , exit the puck housing, and rest upon the horizontal surface at a position proximate to the feed mechanism 120 . Preferably, the puck housing 130 is positioned at a certain distance from the horizontal surface such that the bottom-most puck has completely exited the puck housing 130 as it rests on the horizontal surface, while the puck just above the bottom-most puck has not completely exited the puck housing 130 as the bottom-most puck rests on the horizontal surface. This allows the feed mechanism 120 to push only the bottom-most puck out from under the puck housing 130 . The feed mechanism 120 then retracts and the next puck in the puck housing 130 descends until it rests on the horizontal surface and becomes the new bottom-most puck of the stack. The feed mechanism 120 can then repeat the process by accelerating the new bottom-most puck toward the feed chute 140 .
G. FEED CHUTE
The feed chute 140 can comprise any mechanism configured to facilitate delivery of a puck from the puck housing 130 area to the release assembly 150 . As shown in FIG. 1 , the feed chute 140 can comprise a first end coupled to the frame 110 and a second end extending generally laterally away from the frame 110 . The second end can be coupled to the release assembly 150 . The first end should be coupled to the frame 110 such that when the feed mechanism 120 actuates, the first end can receive the puck being fed to the feed chute 140 .
Upon receiving the puck, the feed chute 140 should help deliver the puck to the release assembly 150 . In FIG. 1 , the feed chute 140 is sloped generally downward as it extends away from the frame 110 . The generally downward slope utilizes gravity to cause the puck to travel toward the release assembly 150 . Alternatively, other forces may be used to cause the puck to move, such as a conveyor or spring mechanism.
As shown in FIG. 1 , the feed chute 140 may comprise beams spanned by a surface capable of carrying and guiding the puck as it travels toward the release assembly 150 . The surface should be conducive to movement of the puck toward the release assembly 150 . The beams may be elevated in relation to the surface to prevent the puck from prematurely exiting the feed chute 140 .
Further, the feed chute 140 may be removable. In other words, the feed chute 140 can be decoupled from the frame 110 . This allows the apparatus 100 to be configured for convenient travel or stowage. As discussed above, the feed chute 140 can be configured for stowage at the stow assembly 175 .
By being configured to extend away from the frame 110 , the feed chute 140 can position the release assembly 150 so that the release assembly 150 is no closer to the frame 110 than a predetermined distance. In preferred embodiments, the operator of the apparatus 100 can select the predetermined distance from a range of available distances. The distance between the release assembly 150 and the frame 110 allows the puck to be released over a playing surface at some distance away from the frame 110 , thereby providing an open drop zone for simulating a hockey face-off. FIGS. 2-4 show a rear-view, a side-view, and a top-view of the apparatus 100 of FIG. 1 .
H. RELEASE ASSEMBLY
FIG. 5 shows a side-view diagram illustrating an example of the release mechanism 150 for the apparatus 100 . As shown in FIG. 5 , the release assembly 150 may be positioned to receive the puck from the feed chute 140 . Once the puck has been received, the release assembly 150 can release the puck at approximately a predetermined interval. As shown in FIG. 5 , the release assembly 150 may include a frame structure configured to support the stopper mechanism 180 (also referred to as the “stoppers 180 ”) and the gripper mechanism 185 (also referred to as the “grippers 185 ”). The stoppers 180 and the grippers 185 should be configured to work together to receive and release the puck. In some embodiments, the gripper mechanism 185 and the stopper mechanism 180 comprise pneumatic actuators or solenoids. The apparatus can incorporate grippers 185 and stoppers 180 made up of a wide variety of different materials and subcomponents.
The stopper mechanism 180 can be configured to receive the puck. The stopper mechanism 180 may comprise a number of stopper actuators 510 configured to cause support plates 520 to extend and retract. As shown in FIG. 4 , the release assembly 150 can comprise two stoppers 180 positioned for receiving the puck. Before the puck enters the release assembly 150 from the feed chute 140 , the support plates 520 of the stoppers 180 should extend to positions for catching the puck. The support plates 520 may be positioned at a height that allows the puck to come to rest on the extended support plates 520 .
In some embodiments, a mechanism may be provided to help catch the puck by stopping the lateral momentum of the puck as it enters the release assembly 150 from the feed chute 140 . For example, the gripper mechanism 185 can be configured to function as a backstop to help stop the lateral momentum of the puck. When a backstop is provided, the puck should still come to rest on the extended support plates 520 of the stopper mechanism 180 .
Preferably, the support plates 520 help level the puck with respect to a surface that is either generally horizontal or in a preferred embodiment, substantially horizontal. Accordingly, the support plates 520 may form generally horizontal surfaces upon which the puck can rest at a generally horizontal orientation, which is desirable for simulating a hockey face-off environment.
Once the puck is at rest on the support plates 520 of the stopper mechanism 180 , the gripper mechanism 185 can extend to secure the puck. As shown in FIG. 5 , the gripper mechanism 185 may comprise two oppositely positioned grippers 185 that can be extended and retracted by actuators. FIG. 5 shows the grippers 185 in a generally “open” position. When the puck is at rest on the support plates 520 , the grippers 185 may extend to a generally “closed” position as shown in FIG. 6 . By so extending, the grippers 185 secure the puck by the sides of the puck.
The grippers 185 can be configured to center the puck. Preferably, when the grippers 185 extend to secure the puck, the grippers 185 position the puck to be generally centered with respect to the puck dropper 190 . This enables the puck dropper 190 to apply a force to the puck in such a way that the puck can maintain a generally level orientation as it falls toward a playing surface. Preferably, the grippers 185 consistently place each puck in substantially the same position with respect to the puck dropper 190 .
The grippers 185 can be shaped to facilitate the centering of the puck. As shown in FIGS. 1 and 4 , the grippers 185 may comprise oppositely positioned sloped surfaces. For example, the sloped surfaces may form a general V-shape, U-shape, or other shape capable of centering the puck as the grippers 185 extend. When the grippers 185 extend to secure the puck, the sloped surfaces cause the puck to move toward a predetermined position. Accordingly, each puck can be positioned at approximately the predetermined position.
After the grippers 185 have secured the puck, the stoppers 180 can retract out from underneath the puck. The stoppers 180 should allow the grippers 185 a sufficient time to secure the puck before retracting. By the retracting process, the stoppers 180 clear an area beneath the puck to allow the puck to fall toward a playing surface upon being released.
The grippers 185 can retract to release the puck. In some embodiments, the puck is dropped toward the playing surface when the grippers 185 retract. In other embodiments, another mechanism, such as the puck dropper 190 , is configured to drop the puck towards the playing surface after the grippers 185 have retracted.
Preferably, the grippers 185 retract after a predetermined interval of time that corresponds with a selected or predetermined release rate. The release rate can be variable such that the pucks can be released after different predetermined intervals. The predetermined interval can be a certain amount of time measured from some event. For example, the predetermined interval can comprise an amount of time after the stoppers 180 retract or after the grippers 185 extend. The timing of the extension and retraction of the stoppers 180 and the grippers 185 are controlled by the control unit 170 , which is discussed in further detail below.
I. PUCK DROPPER
The puck dropper 190 can be configured to drop the puck toward the playing surface. Accordingly, the puck dropper 190 can comprise any mechanism capable of releasing the puck toward the playing surface. For example, the puck dropper 190 may include but is in no way limited to a pneumatic actuator, a solenoid, a vacuum generator, a quick exhaust mechanism, and an air blaster. Preferably, the puck dropper 190 accelerates the puck toward the playing surface while also helping to maintain the generally horizontal orientation of the puck.
In some embodiments, the puck dropper 190 is configured to form a vacuum to secure the puck, and then destroy the vacuum to release the puck. For example, FIG. 5 shows the puck dropper 190 having a suction member 530 . Once the grippers 185 have secured the puck, the suction member 530 may extend to contact the upper surface of the puck. A vacuum can then be formed between the suction member 530 and the puck. Once the vacuum is formed, the grippers 185 may retract such that the puck is suspended from the suction member 530 . The suction member 530 may retract to raise the puck. At this position, the puck is ready to be dropped toward the playing surface. The dropping of the puck can include the puck dropper 190 accelerating the puck toward the playing surface.
The puck dropper 190 can release the puck by destroying the vacuum. In particular, the puck dropper 190 may blast a gas, such as air, through the suction member 530 toward the puck to destroy the vacuum, thereby releasing the puck. Further, the blast of air can apply a force on the puck to accelerate the puck toward the playing surface. In addition, the suction member 530 may extend to push the puck toward the playing surface. The timing of the first extension, vacuum formation, retraction, vacuum destruction, and second extension can be controlled by the control unit 170 , which is discussed in further detail below.
Preferably, the puck dropper 190 applies a force to the puck such that the puck can maintain a generally level orientation as it descends toward the playing surface. As discussed above, the grippers 185 can center the puck in relation to the puck dropper 190 . This allows the force applied by the puck dropper 190 to be centralized with respect to the puck so that the force does not cause the puck to rotate as it descends.
While the puck dropper 190 is helpful for accelerating a puck toward the playing surface to facilitate a hockey face-off, some embodiments of the apparatus 100 do not include the puck dropper 190 . In such embodiments, the puck can be caused to free fall toward the playing surface when the grippers 185 retract to release the puck.
J. CONTROL UNIT
As shown in FIG. 1 , the control unit 170 may be coupled to the frame 110 . The control unit 170 can comprise a housing configured to house a control system. Further, the control unit 170 may include an interface configured to allow a user (e.g. operator) of the apparatus 100 to access and adjust the control system. The control system of the control unit 170 can be powered by the power source 165 .
FIG. 7 shows a control system 700 according to one embodiment of the apparatus 100 . As shown in FIG. 7 , the compressor 160 may be coupled to a dump valve 702 and a check valve 705 . The compressor 160 , the check valve 705 , and an air reservoir 710 may be coupled together to form a volume chamber 712 . Accordingly, the compressor 160 can build and maintain air pressure within the volume chamber 712 and the air reservoir 710 . The volume chamber 712 can hold air such that air pressure can be built up within the volume chamber 712 . The volume chamber 712 couples a number of components of the control system 700 together such that air pressure can be provided to the components, which components will be described below.
The check valve 705 can affect the air pressure within the volume chamber 712 and the air reservoir 710 . For example, the check valve 705 may be configured to maintain residual pressure in the volume chamber 712 by preventing backflow of air when the apparatus 100 is not operating. Further, the check valve 705 may help maintain an appropriate range of air pressure in the volume chamber 712 when the apparatus 100 is operating. For example, if the air pressure exceeds a predetermined threshold, the check valve 705 may open to reduce the air pressure.
The dump valve 702 can affect the air pressure between the compressor 160 and the check valve 705 . When the apparatus 100 is not operating, the dump valve 702 is normally open. Consequently, the compressor 160 can start up without a pressure load against it. Once the compressor 160 has begun to operate, the dump valve 702 should close to allow air pressure to be increased or maintained in the volume chamber 712 . Further, the dump valve 702 may open during operation of the apparatus 100 to lower the air pressure or to stop the air pressure in the volume chamber 712 from being increased. For example, if the air pressure of the volume chamber 712 exceeds a predetermined threshold, the dump valve 702 may open to help lower the air pressure.
A pressure switch 715 and a pressure sensor 718 can be connected to the volume chamber 712 or the air reservoir 710 to help control air pressure by controlling the operation of the dump valve 702 and the compressor 160 . As shown in FIG. 7 , the pressure switch 715 and the pressure sensor 718 may be coupled to volume chamber 712 . The pressure sensor 718 can then measure the air pressure of the volume chamber 712 . The pressure switch 715 is configured to switch according to the measured air pressure. Specifically, the pressure switch 715 can turn off the compressor 160 and/or open the dump valve 702 when air pressure reaches a maximum predetermined threshold. Conversely, the pressure switch 715 can turn on the compressor 160 and/or close the dump valve 702 when the air pressure falls below a minimum predetermined threshold. Thus, the pressure switch 715 and the pressure sensor 718 can help maintain the air pressure of the volume chamber 712 and the air reservoir 710 within predetermined boundaries while the apparatus 100 is operating, thereby maintaining an optimum operating air pressure. In a preferred embodiment, the predetermined range of operating air pressure is approximately 50 pounds per square inch (PSI) to 80 PSI (3,447–5,516 millibars).
The air reservoir 710 can be coupled to an emergency switch 720 and an emergency valve 725 . The emergency valve 725 should normally be open to allow air to flow from the air reservoir 710 to a regulator 730 . This allows air to flow from the air reservoir 710 to help increase or maintain air pressure at the regulator 730 .
The emergency switch 720 can be actuated by the user of the apparatus 100 . If the emergency switch 720 is actuated during operation of the apparatus 100 , the emergency valve 725 closes so that air cannot flow from the air reservoir 710 to the regulator 730 . Accordingly, the forward components of the system 700 should exhaust air up to the emergency valve 725 and stop cycling when the air pressure becomes less than some threshold.
The regulator 730 can control the air pressure available to the forward components of the system 700 . As shown in FIG. 7 , the regulator 730 may be coupled to a gauge 735 that can determine the air pressure of the volume chamber 712 at or near the regulator 730 . The gauge 735 provides data representative of the air pressure to the regulator 730 . The regulator 730 can be configured to adjust the air pressure to help maintain a predetermined optimum air pressure available to the forward components of the control system 700 . For example, the regulator 730 may be configured to maintain the air pressure measured by the gauge 735 at approximately 40 PSI (2,758 millibars). If the measured air pressure is greater than approximately the optimum air pressure, the regulator 730 can increase a rate of release of the air from the system 700 . Conversely, if the measured air pressure is less than approximately the optimum air pressure, the regulator 730 may decrease the rate of release and/or allow more air to flow to the forward components to help increase air pressure. Preferably, the regulator 730 helps prevent a backflow of air from the forward components of the system 100 toward the air reservoir 710 .
The regulator 730 can be coupled to a feed switch 740 . The feed switch should be accessible to the user. When the feed switch 740 is in an “on” position, the control system 700 cycles. When the feed switch 740 is in the “on” position, air can flow from the regulator 730 to the forward components of the system 700 , including a pulse generator 745 that may be coupled to the feed switch 740 . When the feed switch 740 is in an “off” position, air should not easily flow from the regulator 730 to the pulse generator 745 . For example, if the system 700 is operating and the feed switch 740 is placed in the “off” position, air will substantially stop flowing from the regulator 730 to the pulse generator 745 . The pulse generator 745 should then complete its last cycle with the remaining available air. Once the air pressure becomes less than approximately some threshold, the system 700 should stop cycling.
When the power source 165 is providing power and the feed switch 740 is actuated to the “on” position, the compressor 160 charges the control system 700 to approximately an optimum operating pressure. Once the optimum pressure has been reached, the pressure switch 715 turns “off” the compressor 160 to generally stop the buildup of air pressure caused by the compressor 160 . The pulse generator 745 begins operating when the feed switch 740 is switched to the “on” position.
As the pulse generator 745 operates, it sends a pulse signal to other components of the control system 700 . The pulse signal is sent at a specific frequency representative of a feed rate. The feed rate defines a rate at which the pucks are fed to the feed chute 140 as discussed above. The feed rate may be variable, allowing the user to determine the feed rate. In some embodiments, the feed rate is approximately ten seconds.
As shown in FIG. 7 , the pulse generator 745 can be coupled to a feed valve 750 . The feed valve 750 should be configured to toggle according to a characteristic of the pulse signal. Accordingly, the feed valve 750 should toggle based on the feed rate represented by the pulse signal. As the feed valve 750 toggles, it controls connections of the volume chamber 712 to certain forward components. For example, the feed valve 750 may connect a subset of forward components of the control system 700 to the volume chamber 712 , while disconnecting other forward components of the system 700 from the volume chamber 712 .
When the feed valve 750 toggles responsive to the pulse signal, the feed mechanism 120 can be actuated. As shown in FIG. 7 , the feed valve 750 may be coupled to a feed extension chamber 752 and a feed retraction chamber 754 of the feed mechanism 120 . When the pulse signal indicates an extend signal, the feed valve 750 should connect the feed extension chamber 752 to the volume chamber 712 . In response, the feed mechanism 120 should actuate to cause a proximate puck to be fed to the feed chute 140 as discussed above.
The feed valve 750 should cause the feed mechanism 120 to retract in response to a changed characteristic of the pulse signal. For example, when the pulse signal changes to indicate a retract signal, the feed valve 750 can toggle to connect the feed retraction chamber 754 to the volume chamber 712 , while also disconnecting the extension chamber 752 from the volume chamber 712 . This should cause the feed mechanism 120 to retract. The feed valve 750 should be configured to cause the feed mechanism 120 to extend according to the feed rate defined by the pulse signal.
The feed valve 750 can be coupled to a stop valve 755 . Similar to the feed valve 750 , the stop valve 755 can control connections of the volume chamber 712 to forward components of the system 700 . As shown in FIG. 7 , the stop valve 755 can be coupled to stop extension chambers 760 and stop retraction chambers 765 of the stoppers 180 . Accordingly, the stop valve 755 can toggle to cause the stoppers 180 to extend and retract by controlling air pressure in the chambers 760 , 765 in the same way discussed above in relation to the feed mechanism 120 .
Upon receiving the extend signal, the stop valve 755 can cause the stopper plates 520 to extend to positions for catching the puck as the puck exits the feed chute 140 . Specifically, when the extend signal is sent to stop valve 755 , the stop valve 755 should toggle to connect the stop extension chambers 760 to the volume chamber 712 . The air pressure then builds up at the stop extension chambers 760 and causes the stopper plates 520 of the stoppers 180 to extend into position for catching and leveling the puck as discussed above.
The stop valve 755 can also be coupled to a timer 770 that is coupled to a grip valve 775 . As shown in FIG. 7 , the stop valve 755 is coupled to the timer 770 such that the extend signal sent from the stop valve 755 to the stoppers 180 is also sent to the timer 770 . Upon receipt of the extend signal, the timer 770 delays the extend signal approximately a predetermined interval before sending a maintained extend signal to the grip valve 775 . By delaying the transmission of the maintained extend signal to the grip valve 775 , the timer 770 provides sufficient time for the puck to be caught and leveled by the stoppers 180 before the grippers 185 extend to secure the puck. In some embodiments, the predetermined interval is approximately two to three seconds.
The grip valve 775 can be configured to cause the grippers 185 to actuate after the predetermined interval. As shown in FIG. 7 , the grip valve 775 may be coupled to grip extension chambers 780 and grip retraction chambers 782 of the grippers 185 . Accordingly, the grip valve 775 can toggle to cause the gripper 180 to extend and retract by controlling air pressure in the chambers 780 , 785 in the same way discussed above in relation to the feed mechanism 120 . This allows the grip valve 775 to cause the grippers 185 to extend to secure the puck while the puck is supported by the stopper plates 520 . For example, when the maintained extend signal is sent to grip valve 775 , the grip valve 775 should toggle to connect the grip extension chambers 780 to the volume chamber 712 . Air pressure then builds up and causes the grippers 185 to extend to secure the puck.
Once the grippers 185 have secured the puck, the stoppers 180 can then retract. Accordingly, the control system 700 should be configured to cause the stoppers 180 to retract after the grippers 185 have had sufficient time to secure the puck. As shown in FIG. 7 , the timer 770 can also be coupled to a flow controller 785 that is coupled to the stop valve 755 . The timer 770 sends the maintained extend signal to the flow controller 785 . The flow controller 785 may be configured to delay the maintained extend signal by an interval that provides the grippers 780 sufficient time to secure the puck. After this delay, the flow controller 785 sends the delayed extend signal to the stop valve 755 .
The stop valve 755 should be configured to cause the stoppers 180 to retract in response to receiving the delayed extend signal from the flow controller 785 . For example, the stop valve 755 can toggle to connect the stop retraction chambers 765 of the stoppers 180 to the volume chamber 712 . A retract signal is then sent to the stoppers, causing air pressure to build up in the stop retraction chambers 765 such that the stopper plates 520 retract. When the stop valve 755 connects the stop retraction chambers 765 to the volume chamber 712 , the stop extension chambers 760 should be disconnected from the volume chamber 712 such that air pressure is decreased in the stop extension chambers 760 . This allows the stopper plates 520 to retract without being resisted by the air pressure of the volume chamber 712 . Preferably, when the stop extension chambers 760 are disconnected from the volume chamber 712 , the stop extension chambers 760 are connected to atmospheric pressure to sufficiently decrease the associated air pressure.
After the stopper plates 520 have retracted, the control system 700 can be configured to cause the grippers 185 to retract to release the puck. As shown in FIG. 7 , the stop valve 755 can be coupled to a release timer 790 such that the retract signal sent from the stop valve 755 to the stoppers 180 is also received by the release timer 790 . Similar to the timer 770 , the release timer 790 can delay the retract signal approximately a predetermined interval before sending a delayed retract signal to the grip valve 775 .
Upon receipt of the delayed retract signal, the grip valve 775 should cause the grippers 185 retract to release the puck as discussed above. In particular, the grip valve 775 should connect the grip retract chambers 782 to the volume chamber 712 , causing air pressure to build up at the grip retract chambers 782 such that the grippers 185 retract. When the grip valve 775 connects the grip retraction chambers 782 to the volume chamber 712 , the grip extension chambers 780 should be disconnected from the volume chamber 712 such that air pressure is decreased in the grip extension chambers 780 . This allows the grippers 185 to retract without being resisted by the air pressure of the volume chamber 712 . Preferably, when the grip extension chambers 780 are disconnected from the volume chamber 712 , the grip extension chambers 780 are connected to atmospheric pressure to sufficiently decrease the air pressure in the grip extension chambers 780 .
As discussed above, the puck is released when the grippers 185 retract. Preferably, the rate at which the pucks are released is variable. The release rate can be defined at least in part by the predetermined interval of delay provided by the release timer 790 . Accordingly, the delay provided by the release timer 790 can be variable. For example, the release timer 790 may be accessible by the user for adjusting the predetermined interval. In some embodiments, the predetermined interval of delay is within a range of approximately one to five seconds.
In short, the control system 700 should be configured to cause the feed mechanism 120 , the stoppers 180 , and the grippers 185 to extend and retract at appropriate times to facilitate a feeding, a receiving, a securing, and a dropping of the puck. While the components shown in FIG. 7 illustrate one configuration of the control system 700 , those skilled in the art will readily recognize that other configurations of the control system 700 can be implemented to cause the feed mechanism 120 , the stoppers 180 , and the grippers 185 to extend and retract at appropriate times.
FIG. 8 shows another control system 800 configured to control operation of the apparatus 100 . In addition to providing many of the features of the control system 700 , the control system 800 can control operation of the puck dropper 190 . As shown in FIG. 8 , many of the components of the control system 800 may be configured as described above in relation to the control system 700 . For example, the components of the control system 800 from the compressor 160 to the feed mechanism 120 can be configured as discussed in relation to the control system 700 of FIG. 7 .
As shown in FIG. 8 , the pulse generator 745 may be configured to send the pulse signal to the stop valve 755 . The stop valve 755 then toggles such that the stoppers 180 are caused to extend as discussed above. As in the control system 700 , the stop valve 755 can also be configured to send the extend signal to the timer 770 . The timer 770 can delay and send the maintained extend signal to the grip valve 775 as discussed above. Upon receipt of the maintained extend signal, the grip valve 775 causes the grippers 185 to extend to secure the puck as discussed above.
The control system 800 can include components for controlling the puck dropper 190 . As shown in FIG. 8 , the stop valve 755 and the grip valve 775 can be coupled to a vacuum valve 820 and a drop valve 830 . The vacuum valve 820 may be coupled to a vacuum generator 840 that is coupled to the puck dropper 190 . The drop valve 830 can also be coupled to the puck dropper 190 . In particular, the drop valve 830 may be coupled to a drop extension chamber 845 and a drop retraction chamber 850 of the puck dropper 190 .
The vacuum valve 820 and the drop valve 830 should be configured to cause the puck dropper 190 to timely secure and release the puck as discussed above. Accordingly, the vacuum valve 820 can receive the maintained extend signal from the grip valve 775 . Upon receipt of the maintained extend signal, the vacuum valve 820 should toggle to cause the vacuum generator 840 to begin operating to form a vacuum. Specifically, when operating, the vacuum generator 840 works to form a vacuum at the suction member 530 of the puck dropper 190 . When the suction member 530 contacts the puck, a vacuum is formed between the puck and the suction member 530 . The vacuum should be of sufficient strength to secure the puck to the suction member 530 .
The suction member 530 should be caused to timely extend to contact the puck such that the vacuum can be formed. As shown in FIG. 8 , the drop valve 830 can receive the maintained extend signal. Upon receipt of this signal, the drop valve 830 should toggle to cause the suction member 530 to extend. In particular, the drop valve 830 can be coupled to the drop extension chamber 845 . When the drop valve 830 toggles, the drop extension chamber 845 becomes connected to the volume chamber 712 such that air pressure causes the suction member 530 to extend to contact the puck. When the suction member 530 contacts the puck, a vacuum forms to secure the puck as discussed above.
Preferably, the puck is secured by the suction member 530 when the puck is being held by the grippers 185 . This allows the puck to be consistently centered when secured by the suction member 530 . By being consistently centered with relation to the suction member 530 , the pucks can be released at a substantially level orientation as discussed above. Further, by centering the puck, an acceleration force applied to the puck is centered such that the force does not cause the puck to rotate away from its substantially level orientation as it descends.
The control circuit 800 can be configured such that the stoppers 180 and the grippers 185 retract after the puck has been secured by the suction member 530 . As shown in FIG. 8 , the grip valve 775 is coupled to the release timer 790 such that the release timer 790 may receive the maintained extend signal. Upon receiving the maintained extend signal, the release timer 790 delays the signal as discussed above in relation to FIG. 7 . The delay should be sufficient to allow the puck dropper 190 to secure the puck as discussed above.
After delaying the maintained extend signal, the release timer 790 sends the delayed signal to the stop valve 755 . Upon receipt of the delayed signal, the stop valve 755 should toggle to connect the stop retraction chambers 765 of the stoppers 180 and the grip retraction chambers 782 of the grippers 185 to the volume chamber 712 . The stop extension chambers 760 of the stoppers 180 and the grip extension chambers 780 of the grippers 185 should correspondingly be disconnected from the volume chamber 712 . This causes the stoppers 180 and grippers 185 to retract, leaving the puck secured to the puck dropper 190 .
After the stoppers 180 and the grippers 185 have retracted, the control system 800 may cause the suction member 530 to retract to raise the puck. For example, when the grip valve toggles to retract the grippers 185 , the maintained extend signal is terminated, and the drop valve 830 toggles to connect the drop retraction chamber 850 to the volume chamber 712 . The drop valve 830 should also disconnect the drop extension chamber 845 from the volume chamber 712 . In response, air pressure builds up in the drop retraction chamber 850 such that the suction member 530 retracts, raising the secured puck.
The control system 800 can be configured to cause the puck dropper 190 to drop the puck after a predetermined interval. For example, a drop timer 870 can be configured to receive the retract signal from the stop valve 755 . As shown in FIG. 8 , the drop timer 870 is coupled to the stop valve 755 . Upon receipt of the retract signal, the drop timer 870 delays the retract signal approximately the predetermined interval before sending the delayed retract signal forward. Similar to the release timer 790 , the drop timer 870 can be variable. For example, the drop timer 870 may be accessible to and adjustable by the user of the apparatus 100 . In some embodiments, the predetermined interval can be varied within an approximate range of one to five seconds.
The vacuum valve 820 and the drop valve 830 can be configured to cause the puck dropper 190 to drop the puck upon receiving the delayed retract signal. As shown in FIG. 8 , the drop timer 870 may be coupled to the vacuum valve 820 and the drop valve 830 . The drop valve 830 is coupled to the drop timer 870 via an exhaust control 880 . The exhaust control 880 is configured to generally stop air from flowing backwards through volume chamber 712 . This allows the delayed retract signal to form sufficient air pressure to cause the drop valve 830 to toggle.
When the drop valve 830 toggles responsive to the delayed retract signal, the drop extension chamber 845 is connected to the volume chamber 712 . In response, air pressure quickly builds up in the drop extension chamber 845 such that the suction member 530 extends, pushing the puck generally downward. The drop valve 830 should also disconnect the drop retraction chamber 850 from the volume chamber 712 to release resistive air pressure from the drop retraction chamber 850 .
Further, the suction member 530 should be configured to extend quickly. For example, the drop valve 830 can be coupled to the drop retraction chamber 850 via a quick exhaust 890 . The quick exhaust 890 should be configured to facilitate a quick escape of air from the drop retraction chamber 850 to help minimize any resistance to the extension of the suction member 530 . Accordingly, the suction member 530 can extend to help accelerate the puck generally downward.
When the vacuum valve 820 toggles responsive to the delayed retract signal, the vacuum generator is turned off. Accordingly, the vacuum at the suction member 530 is terminated. This allows the puck to be accelerated by the suction member 530 quickly extending downward as discussed above.
Further, an air blast can be applied to the puck to help accelerate the puck downward. When the vacuum valve 820 toggles responsive to the delayed retract signal, the puck dropper 190 can be connected to the volume chamber 712 . This allows the air pressure of the volume chamber 712 to apply a force to the puck to accelerate the puck downward.
Thus, the vacuum valve 820 and the drop valve 830 should be configured to work together to control the puck dropper 190 . Further, by using the puck dropper 190 in combination with the grippers 185 , the apparatus 100 can repeatedly and consistently drop a puck toward a playing surface at a substantially horizontal orientation. As discussed above, such a substantially flat orientation is preferred when dropping the puck for a hockey face-off.
The control systems 700 , 800 can be configured to continue to cycle to drop one puck at a time toward the playing surface. The control systems 700 , 800 may be configured to stop cycling after losing sufficient air pressure from the volume chamber 712 . The control systems 700 , 800 can also be configured stop cycling after the feed switch 740 is turned “off,” the emergency switch 720 is turned “off,” or the supply of pucks in the puck housing 130 is exhausted.
II. PROCESS FLOW VIEWS
FIG. 9 is a flow chart diagram illustrating an example of a process for dropping a puck for facilitating a hockey face-off. At step 910 , a puck is fed to the release mechanism 150 . The puck can be fed to the release mechanism 150 in any of the ways discussed above, including the feed mechanism 120 feeding the puck to the feed chute 140 . At step 920 , the stoppers 180 are extended to receive the puck from the feed chute 140 as discussed above. At step 930 , the puck can be leveled as discussed above. At step 940 , the puck is secured in any of the ways discussed above. For example, the grippers 185 can extend to grip the puck, and/or the suction member 530 may extend to form a vacuum at the puck. At step 950 , the stoppers 180 are retracted as discussed above. At step 960 , the puck can be released in any of the ways discussed above, including by retracting the grippers 185 and/or destroying the vacuum at the suction member 530 . The steps 910 – 960 shown in FIG. 9 can be repeated until the puck housing 130 is emptied of all pucks. The operator can configure the apparatus to deploy a predetermined number of pucks over a predetermined period of time, with a predetermined interval of time between deployments.
FIG. 10 is a flow diagram of another example of a process for dropping a puck for facilitating a hockey face-off. The puck can be fed to the release mechanism 150 (step 1010 ), received by an extended stopper 180 (step 1020 ), leveled (step 1030 ), and secured (step 1040 ) in any of the ways discussed above in relation to steps 910 – 940 . At step 1050 , the puck can be centered, preferably with respect to the puck dropper 190 as discussed above. At step 1060 , a vacuum may be formed at the suction member 530 . The suction member 530 can be extended to contact and secure the puck as discussed above. At step 1070 , the stopper 180 can be retracted as discussed above. At step 1080 , the puck can be released by retracting the grippers 185 as discussed above. At step 1090 , the vacuum can be destroyed as discussed above, thereby dropping the puck toward a playing surface. At step 1095 , the puck can be accelerated toward the playing surface in any of the ways discussed above, including an air blast and/or a quick extension of the suction member 530 toward the playing surface. Steps 1010 – 1095 may repeat until the puck housing 130 is exhausted of pucks.
III. ALTERNATIVE EMBODIMENTS
The foregoing embodiments were chosen and described in order to illustrate principles of the methods and apparatuses as well as some practical applications. The preceding description enables others skilled in the art to utilize the methods and apparatuses in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the methods and apparatuses be defined by the following claims, including the full scope of equivalents to which such claims are entitled. In accordance with the provisions of the patent statutes, the principles and modes of operation of the present methods and apparatuses have been explained and illustrated in exemplary embodiments. However, it must be understood that the present methods and apparatuses may be practiced otherwise than is specifically explained and illustrated without departing from their spirit or scope.
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Methods and apparatuses for dropping a hockey puck (collectively the “system”). The system can facilitate or simulate hockey face-offs. Various embodiments of the system can be configured to provide convenience, portability, stability, and/or consistency for dropping a hockey puck to facilitate a hockey face-off. A frame can support a puck housing and a feed mechanism. The feed mechanism may be configured to feed the hockey puck from the puck housing to a feed chute. A release mechanism can receive the hockey puck from the feed chute. The release mechanism may be configured to release the hockey puck according to a predefined release rate. A power source can be carried by the frame and be configured to power the feed and the release of the hockey puck.
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BACKGROUND OF THE INVENTION
This invention relates generally to an apparatus for pitching a ball whereby the ball is delivered in free fall by the force of gravity, and more particularly to an economical ball hit game designed for children as well as adults. The ball pitcher of the present invention when attached to an ordinary garden hose provides a water-powered apparatus which automatically pitches balls on a continuous basis. Due to the method of ball delivery, there is no fear of being hurt by a speeding pitch. It also allows a player to play alone, as well as with any number of other players.
Many ball servers or pitchers are known in the prior art. However, these devices are typically expensive, complex and are too sophisticated for use by a child. Further, delivery is usually accomplished by means of compressed air or spring action which hurls the ball at significant velocities which could easily injure a young player. For example, U.S. Pat. No. 4,207,857 of Balka, Jr. issued June 17, 1980 discloses an automatic ball serving device whereby balls are delivered by a firing panel powered by compressed air. U.S. Pat. No. 3,236,521 of Knott issued Feb. 22, 1966 discloses a baseball bat which incorporates either spring loaded or fluid pressure delivery means. The operation of such a device is fairly complicated in that ball delivery is effectuated by acts of the batter and requires a certain amount of coordination which most children do not posses. U.S. Pat. No. 2,955,823 of Chanko issued Oct. 11, 1960 discloses a batting practice device whereby, similar to U.S. Pat. No. 3,236,521, ball delivery is effectuated by acts of the batter which require a certain amount of coordination, detracting from the batter's hitting concentration.
Accordingly, it is an object of the present invention to provide an apparatus for a ball hitting game whereby a ball is delivered in free fall by the force of gravity.
Another object of the present invention is to provide an economical ball hitting game which is safe and easy to use by small children.
Still another object is to provide a simple water powered apparatus that pitches balls commensurate with the height of a player.
SUMMARY OF THE INVENTION
In accomplishing these and other objects in accordance with the present invention an automatic ball pitcher may include an elongated cylindrical member having a top end and support means for maintaining said top end at a variable height and position. A first ball or spherical object is inserted into the elongated member and a second ball is also inserted adjacent the first ball in order to displace the first ball when a volume of water is introduced into said elongated member. Inlet means are employed for regulating the introduction of the wafer into the elongated member and outlet means are further employed to release the fluid from the elongated member when the first and second balls are displaced. Once a ball is displaced from the top end of the elongated member by the introduction of water, it free falls by the force of gravity, falling in the direction of the ground until it is hit by the swing of a bat, raquet or other device.
Further objects, features and advantages of the present invention will be more fully appreciated by reference to the following detailed description when taken in conjunction with the accompanying drawings. It is to be understood that the drawings are designed for the purposes of illustration only and are not intended as a definition of the limits of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, wherein similar referenced characters denote similar elements throughout the several figures:
FIG. 1 is a perspective view of the pitching apparatus of the present invention while in use;
FIG. 2 is a sectional view of FIG. 1 taken along lines 2--2 of FIG. 1;
FIG. 2a is a sectional view illustrating an alternative embodiment of the present invention
FIG. 3 is a sectional view of FIG. 1 taken along lines 3--3 of FIG. 1; and
FIG. 4 is a sectional view of FIG. 1 taken along the lines 4--4 of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Generally referring to FIGS. 1, 3 and 4, an automatic pitching apparatus incorporating one embodiment of the present invention is identified generally by the reference numeral 10. Pitching apparatus 10 includes a hollow elongated member 12, a support means 14, a water supply apparatus 16 and a spherical object or ball 18 that has been dispensed from the top end of elongated member 12 by the introduction of water into elongated member 12 by water supply apparatus 16. The water supply apparatus must be connected to a source of water by, for example, a typical garden hose. Once ball 18 has been dispensed, a player 20 will attempt to hit ball 18 by swinging a bat 22, racquet, or other device typically used to a hit a ball.
Ball 18 must be of a size to fit within elongated member 12 and in the perferred embodiment it should be manufactured from a buoyant material, i.e., a material that allows it to float or rise when submerged in water. Typically ball 18 is manufactured of plastic, such as a Wiffle Ball, and measures three inches in diameter even though other types of balls employing other diameters wll certainly fall within the scope of the present invention (such as a tennis ball, hand ball, stick ball, etc.). Of course, member 12 shall have interior dimensions sufficient to accommodate the size of the ball or balls used.
Ball 18 is dispensed from elongated member 12 when water is introduced into the elongated member. As the volume of water in member 12 is increased, ball 18 (being manufactured of buoyant material), will float to the top of elongated member 12 until it is forced out of the top end. Once it is forced out, gravity will force it to fall in the direction of the ground, providing player 20 with a chance to hit it. Any number of balls can be loaded into elongated member 12 and the frequency of displacement can be varied by adjusting the water flow rate into elongated member 12.
In the preferred embodiment elongated member 12 is of a cylindrical configuration and approximately six feet in length which allows it to be loaded with approximately twenty-five balls (not shown) prior to commencing play. Typically, elongated member 12 is formed of polyvinyl chloride (PVC) pipe although it could be manufactured of any other known material from which pipes are currently manufactured, such as copper or any other rigid material that would be in accordance with the present invention. Further, elongated member 12 does not have to be cylindrical in shape. It could have, for example, a rectangular or triangular cross-section limited only by its interior dimensions such as to freely permit passage of the balls used throughout its length.
FIG. 2 shows ball 18 being dispensed from the top end of elongated member 12. Water 24 is shown to be in contact with balls 26 and 28. Since balls 26 and 28 are buoyant, they float and displace balls 30, 32 and 34 throughout the length of elongated member 12 and dispense ball 18 out the top end of elongated member 12 when the volume of water 24 in elongated member 12 is increased.
Ball 26 is shown to be completely submerged in water 24 and ball 28 is shown to be partially submerged. Since these balls are buoyant, it is important to realize that they are submerged under water 24 due to the weight of the other balls contained in elongated member 12. The number of balls submerged in water 24, therefore, would be dependent on the size, weight and number of other balls loaded into elongated member 12. Further, all of the balls loaded in member 12 do not have to be buoyant. The only balls that need to be buoyant are those located at the bottom end of elongated member 12. It will be appreciated by one skilled in the art that the number of buoyant balls required would be dictated by the total number of non-buoyant balls and by their size and weight. Thus one would need to include a sufficient number of buoyant balls to displace the remaining balls throughout the length of elongated member 12 and dispensing them out the top end of elongated member 12 when water is introduced and its volume increased.
Balls 26, 28 and 30 have a surface ornamentation sufficient to differentiate their appearance from the other balls in member 12. Typically this is accomplished by painting them a bright color, such as red. These balls function to warn the user that the supply of balls is used up, or that there are only a limited number of balls left, depending on whether or not the player desires to hit balls 26, 28 and 30. It should be noted that any number of balls can be differentiated and other means could be employed to notify the player that the supply of balls is used up or about to be used up, such as a counter or any other means known to one skilled in the art.
With reference to FIG. 2a, if the ball 26 and 28 deteriorate when placed in direct contact with water like, for example a tennis ball, it would be within the scope of the present invention to employ a gasket means 35 between water 24 and the first ball, i.e., ball 26. The gasket mean 35 functions to prevent water from coming in contact with the balls, and displaces the balls throughout the length of elongated member 12 and out its top end. FIG. 2a shows gasket means 35 in a piston-type configuration. However, it will be appreciated by those skilled in the art that gasket means 35 can be designed in alternative configurations.
With reference now to FIGS. 1 and 4, water supply apparatus 16 functions to regulate the flow of water into and out of elongated member 12. Water supply apparatus 16 includes a T joint 36, an inlet value 38 and an outlet valve 40. The bottom end of member 12 is supported by and engaged to a T joint 36. The base of T joint 36 may be weighed down to stabilize water supply apparatus 16 by filling it with a dense composition such as conncrete. T joint 36 is connected to inlet valve 38 and outlet valve 40. Inlet valve 38 is connected to a main water supply by hose 42. Inlet valve 38 can be a restriction type valve that is capable of controlling the water flow rate into member 12 and hence the frequency upon which the balls are dispensed out of member 12. It is in accordance with the present invention that hose 42 is to be a regular garden hose although other types of hoses may be used.
When use of the present invention is desired, outlet valve 40 is in a closed position and inlet valve 38 is in an open position. The main water supply is turned on and water is carried by hose 42 through inlet valve 38 and T-joint 36 and into elongated member 12. Elongated member 12 begins to fill with water which then causes balls (which have been loaded into elongated member 12) to be dispensed out of elongated member 12 at a frequency commensurate with the water flow rate. Typically the water flow rate is controlled by adjusting inlet valve 38. Once all of the balls have been dispensed, inlet valve 38 is closed and outlet valve 40 is opened in order to release the volume of water presently contained within elongated member 12. Once the volume of water is released, outlet valve 40 is closed, elongated member 12 is again loaded with balls and the game is once again ready to be played.
Referring now to FIGS. 1 and 3, pitching apparatus 10 can accommodate the height of player 20 by adjusting the top end of elongated member 12 to a desired height and position. This is accomplished by support means 14 which includes a triangular support 44 and a clamp 46 including half-members 46a and 46b. Half members 46a and 46b are hingeably connected to triangular support 38 by a screw and wingnut assembly 48. Elongated member 12 is positioned within the inside diameter of half-members 46a and 46b until elongated member 12 is desirably supported. Half-members 46a and 46b secure elongated member 12 by frictionally engaging elongated member 12 when screw and wingnut assembly 50 is tightened. The top end of elongated member 12 can be further adjusted by loosening screw and wingnut assembly 48 and positioning triangular support 44 to a desired location and then tightening wingnut assembly 48. The phantom position of FIG. 1 shows one alternative position of apparatus 10, obtained by adjusting support means 14. Typically, the height of the top end of elongated member 12 should be able to be adjusted through a range of 3 to 5 feet. Of course, such range is exemplary of the preferred embodiment only and would depend on the size of player 20, the size of support means 14 and the length of elongated member 12.
As will be readily apparent to those skilled in the art, the invention may be used in other specific forms or for other purposes without departing from its scope or central characteristics. The present embodiment is therefore to be considered as illustrative and not restrictive, the scope of the invention being indicated by the claims rather than by the foregoing description, and all embodiments which come within the range of equivalence of the claims are intended to be embodied.
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An automatic ball pitcher includes an elongated cylindrical member having a top end and a support means for maintaining said top end at a desired height and position. A ball or spherical object is inserted into the elongated member and dispensed out the top end of said elongated member when a volume of water is introduced into said elongated member. Inlet means are employed for regulating the introduction of the water into said elongated member and outlet means are further employed to release the water from said elongated member once said ball has been dispensed. After the ball is dispensed, it free falls by the force of gravity until it is hit by the swing of a bat, racquet or other device.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application No. 60/494,533 filed Aug. 12, 2003, entitled “Robotic Platform” and U.S. Provisional Patent Application No. 60/520,548, filed Nov. 14, 2003, entitled “Robotic Platform With Removable Drive And Accessory Cage” the contents of both of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to a hobby robot and, more specifically, to a support structure for use with the hobby robot.
2. Description of Related Art
Building a robot from scratch is an excellent way to learn a lot about robotics, but is not the only way to get started. A robot kit that includes a pre-fabricated platform or support structure, motor, wheels, etc. can assist a builder through the initial learning curve and save a builder time, frustration and money, so that the builder can more quickly enter the programming or customizing aspects of robotics.
Currently, manufactured robotic platforms are extremely crude, garage-built, proprietary units, as currently no build standards exist in the field of robotic platforms. In terms of existing commercial robotic platforms, a fixed-shelf approach is utilized for mounting hardware and related peripherals to the robot. Although the fixed-shelf approach is appropriate for containing the hardware and related peripherals on the actual robot during actual use of the robot, the fixed-shelf approach is not conducive to continued upgrades or modifications that a builder may perform on the robot. Namely, replacing or modifying a specific piece of hardware may require the temporary removal of other hardware in order to provide manageable access to that specific piece of hardware. In the robotics field, especially during the initial build and testing process, hardware and peripherals may need to be constantly replaced or modified until an intended function of the robot operates satisfactorily. With each such replacement or modification attempt, it is usually the case that the temporarily removed hardware is thereafter reattached and/or reconnected so that the robot can be tested to determine the degree of success of the replacement or modification attempt. The aforementioned process may occur repeatedly during the course of an initial build or at a later time when only modifications are made to an existing hardware and peripheral configuration of the robot. The removal of hardware only for the purposes of accessing other hardware adds unproductive time to the build or modification process. This may result in added frustration on the part of the builder, as he or she may already be frustrated due to the fact that a certain intended aspect of building or modification is not proceeding or performing as intended.
It is, therefore, desirable to overcome the above problems and others by providing a robotic platform or support structure that allows a builder to efficiently build and modify a robot.
SUMMARY OF THE INVENTION
Accordingly, I have invented a hobby robot having an encasement shell surrounding a support structure. The structure includes a cavity defined within the support structure, wherein the cavity includes fasteners or functional equivalents positioned within the cavity for removably coupling at least one mounting element to an interior portion of the cavity. The support structure also includes fasteners for securing an encasement shell to the support structure. The mounting element may be a tray or hardware that performs a desired function in connection with the operation of the robot. The support structure is adapted to receive a self-contained power source and wheels or treads for imparting motive force to the support structure.
The support structure is modeled after current industry standard personal computing cases. Utilizing a familiar existing standard allows various standard-sized hardware and peripherals to be quickly and easily associated with and secured to the support structure. The flexibility of building and modifying hardware that is inherent in standard personal computing cases is now available to hobbyists and researchers to easily mount and remove almost any hardware and peripheral to the support structure in a similar manner. Specifically, the support structure allows for removable, adaptable, and relocatable mounting elements, such as trays or shelves, to be installed on the support structure.
In conjunction with encasement shells, the robot appears as a highly finished, professionally engineered, and an aesthetically appealing robotic platform, as opposed to a make-shift home made platform of significantly lesser engineering quality and cosmetic appeal. Furthermore, the present invention solves the problem of hobbyists, researchers, etc., having to build their own robotic platform. The inventive robotic platform also avoids the need for the builder to secure outside assistance from, for example, engineers and metal fabricators, and the costs associated therewith. The inventive robotic platform is a simple out-of-the-box solution that provides an inexpensive and accurate alternative to building a home made robotic platform.
Still other desirable features of the invention will become apparent to those of ordinary skill in the art upon reading and understanding the following detailed description, taken with the accompanying drawings, wherein like reference numerals represent like elements throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front perspective view of a robot having an encasement shell with mounting elements protruding therefrom, in accordance with the present invention.
FIG. 2 is a perspective exploded view showing a support structure within the encasement shell supporting the mounting elements shown in FIG. 1 ;
FIG. 3 is a side view of the robot of FIG. 1 showing the mounting elements partially in phantom in relation to the support structure;
FIG. 4 is a front view of a first alternative embodiment robot having circuit boards shown in phantom attached to the support structure;
FIG. 5 is an exploded view of the first alternative embodiment robot of FIG. 4 , showing the support structure within the encasement shell supporting the circuit boards; and
FIG. 6 is a front perspective view of a second alternative embodiment robot having the mounting elements of FIG. 1 oriented vertically.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
For purposes of the description hereinafter, spatial or directional terms shall relate to the invention as it is oriented in the drawing figures. However, it is to be understood that the invention may assume various alternative variations, except where expressly specified to the contrary. It is also to be understood that the specific apparatus illustrated in the attached drawings, and described in the following specification, is simply an exemplary embodiment of the invention. Hence, specific dimensions and other physical characteristics related to the embodiments disclosed herein are not to be considered as limiting.
FIGS. 1-3 depicts an exemplary embodiment of the present invention. Specifically, FIG. 1 depicts an exterior of a robot 10 , such as a hobby robot, having an encasement shell 12 . As shown in FIG. 2 , the encasement shell 12 encloses a support structure 14 , which in turn supports various mounting elements 16 a - c . FIG. 3 depicts an exemplary embodiment of imparting motive force to the support structure 14 , namely, a drive wheel 18 in communication with a motor 20 . Additionally, support wheels 22 may be integrated into the support structure 14 to provide balancing functions. The robot 10 in FIGS. 1 & 2 is shown from a front perspective view, although it should be understood that the hidden rear view may be similar to the front view, depending on the configuration of the robot 10 . Therefore, the designations “front” and “rear” for the robot 10 , are used only in relation to how the robot 10 appears oriented in the drawings. It is to be understood that in operation, the robot 10 the front and rear of the robot may be reversed depending on the movement of the robot in relation to the builder or user.
With specific reference to FIGS. 1 & 2 , the encasement shell 12 may serve as a protective encasement for the robot 10 . Thus, any sensitive hardware or peripherals within the robot 10 are protected from unauthorized access and environmental elements or contamination. Additionally, the encasement shell 12 provides an aesthetic appeal to outside observers, as the hardware or peripherals and associated wiring and electrical components are concealed behind the encasement shell 12 . Desirably, the encasement shell 12 is formed from plastic or fiberglass. However, it is to be understood that any suitable material may be utilized. The encasement shell 12 may be customized to allow for additional functionality of the robot 10 . For example, a portion of the encasement shell 12 may be constructed of a non-opaque substance, such as clear glass, to allow a camera 24 to view the operating environment of the robot 10 while protected within the encasement shell 12 . Furthermore, the encasement shell 12 may be configured to allow sensors and other hardware to be mounted thereon. Other hardware may include, but is not limited to light(s), vent(s), LCD panel(s), audio speaker(s), microphone(s), etc. Additionally, the encasement shell 12 may include cut-outs or punch-outs that may be optionally utilized to house and access components during the building of the robot 10 . Alternatively, the encasement shell 12 may be fully enclosed, thereby requiring the builder to remove the encasement shell from the support structure 14 to access the internal components of the robot 10 . Desirably, the encasement shell 12 is constructed of two or more panels that may be separated from either one another to form the support structure 12 , thereby allowing access to the hardware and peripherals inside the robot 10 . It is to be understood that the encasement shell 12 may alternatively be of a unitary design. It is envisioned that such a unitary design would provide a hinge mechanism for allowing access to the support structure 12 . The encasement shell 12 may be secured to the support structure in various ways including, but not limited to a snap fit, friction fit, screwing, bolting, fastening, etc. For example, a plurality of hooks 25 arranged on the support structure 14 may engage interior portions of the encasement shell 12 . Desirably, the encasement shell 12 is constructed to provide a compatible fit with the support structure 14 and any other components of the robot 10 . For example, as shown in FIG. 1 , the encasement shell 12 is molded to provide a sufficient opening for free movement of the support wheels 22 . Furthermore, although not explicitly shown in the figures, a bottom portion of the encasement shell 12 is adapted to allow the drive wheel 18 to extend therethrough. Sufficient ground clearance is provided by the encasement shell 12 to allow uninhibited moment of the assembled robot 10 .
The support structure 14 is adapted to receive various mounting elements 16 a - c and other hardware or peripherals that may be associated with the operation of the robot 10 . Desirably, the support structure 14 is modeled after current industry standard personal computing cases, as such cases include configurations conducive to receiving hardware and peripherals utilized in robot construction. For example, current personal computing cases are basically a framed metallic structure that includes predrilled screw holes, and vertical and horizontal cross-members for supporting computer related components. However, although existing personal computing cases may be used, it is to be understood that support structure 14 may be fabricated and implemented to provide a desired degree of configurability in the design of the robot 10 . Desirably, the support structure 14 is formed from sheet aluminum and stamped steel, however, it is to be understood that any suitable material may be utilized. It is also desirable that the support structure 14 be sufficiently rigid to support the intended hardware and peripherals, yet not be too heavy to negatively impact the overall weight considerations in the design of the robot. The support structure 14 may be manufactured using the same processes that are utilized in the manufacture of personal computing cases. Desirably, the support structure 14 is constructed of various substantially horizontal and vertical members, such as members 26 a , 26 b and 27 a , 27 b , respectively, joined in a frame-like configuration. It is to be understood that the frame or frame-like configuration of the support structure 14 depicted in the figures is only an exemplary embodiment and may be substituted with other frame configurations depending on the needs of the builder and/or the specific application of the robot 10 .
Desirably, builders in the field of robotics may utilize current off-the-shelf computer hardware and peripherals in the design of robots. Such hardware and peripherals include, but are not limited to mother/daughter boards (with associated computer components such as memory, processors, riser cards, etc.), data storage (hard disk drives, optical drives, media reader, non-volatile/volatile memory, etc), and miscellaneous optional components intended for increasing the functionality or aesthetic nature (slide rails, speaker system, I/O interface, rack mounts, riser cards, face plates, etc.)
The support structure 14 may be configured to receive one or more of the aforementioned hardware or peripherals. Specifically, the support structure 14 includes various cavities or bays, such as bays 28 a and 28 b , for supporting various mounting elements. Desirably, each cavity or bay is substantially rectilinear in shape, however it is to be understood that each cavity or bay may be shaped to suitably accommodate the corresponding shape of the mounting elements to be supported therein. The bays 28 a and 28 b are bounded by various horizontal and vertical members of the support structure 14 . For example, bay 28 a is bounded by the horizontal members 26 a , 26 b , and the vertical members 27 a and 27 b . Desirably, the bays 28 a and 28 b are sized to accommodate various off-the-shelf computer hardware and software. For example, bay 28 a may have an industry-standard width of 5¼″ to accommodate an optical drive, whereas bay 28 b may be have an industry-standard width of 3½″ to accommodate a floppy disk or a hard drive. With specific reference to FIGS. 1 & 2 , the builder may utilize a tray, an optical drive, and a face plate, depicted as mounting elements 16 a , 16 b , and 16 c , respectively, to be received within the bay 28 a . It is to be understood that the arrangement of the mounting elements 16 a - c shown in FIGS. 1-3 is for exemplary purposes only. Thus, the arrangement of the mounting elements 16 a - c is dictated by the builder and/or needs of the robot 10 . It is also to be understood that for the purpose of clarity, the necessary cables and specific electrical connections to and from the hardware and peripherals are not depicted in the figures.
As shown in FIGS. 1-3 , the mounting elements 16 a - c may be removably attached to the support structure 14 . Specifically, lateral ends of each of the mounting elements 16 a - c are attached to the substantially parallel vertical members 27 a , 27 b so that the mounting elements 16 a - c span the width of the bay 28 a . The tray 16 a and the optical drive 16 b may be attached directly to the vertical members 27 a , 27 b via screws or other suitable fasteners threaded into pre-drilled holes 30 . The tray 16 a may be adapted to receive a circuit board, such as a daughterboard 32 , or other component to which constant modifications may be made during the course of building and testing the robot 10 . Alternatively, the daughterboard 32 may be directly secured within the bay 28 a if the daughterboard 32 is configured as a rack mount. Desirably, the face plate 16 c is utilized to cover an area of the bay 28 a which is not utilized by any component, and therefore provide a cosmetic covering for the empty area. Specifically, the face place 16 c may be attached to the vertical members 27 a , 27 b by a snap-fit, friction fit, or other attachment mechanism. In this particular embodiment, the builder has already selected a suitable removable media storage device (i.e., CD-ROM), and therefore, a floppy disk may not be necessary. Hence, a hard drive (not shown) may be installed in the bay 28 b . The present invention may include slide rail attachments having corresponding connectors 29 a , 29 b attached to the bay 28 a and one or more of the mounting elements 16 a - c, respectively. The slide rail attachments allow the mounting elements 16 a - c to easily slide in and out of the bay 28 a . The installation and operation of slide rail attachments and functional equivalents are known in the art and will not be specifically discussed herein. Even though the robot 10 has the encasement shell 12 installed, the mounting elements 16 a - c may be partially removed to protrude beyond the encasement shell 12 , as shown in FIG. 1 or may be completely removed. As shown in FIG. 3 , the support structure 14 may support mounting elements in addition to mounting elements 16 a - c . For example, mounting elements 16 d - f may be mounted in the rear of the robot 10 . Due to the highly configurable aspect of the support structure 14 , the mounting elements 16 a - f may be positioned in any suitable arrangement. For example, the mounting element 16 f may be interchanged with the face plate 16 c.
With reference to FIGS. 4 & 5 , and with continuing reference to FIGS. 1-3 , a first alternative embodiment robot 34 is shown. The first alternative embodiment robot 34 is of similar construction as robot 10 except for the configuration of a support structure 36 . Namely, the support structure 36 is constructed of cut-out portions 38 for supporting circuit boards, such as motherboards 40 , therein. Thus, the motherboards 40 can easily be accessed, removed, and replaced, simply by sliding them in and out of the cut-out portions 38 of the support structure. The cut-out portions 38 may also include cable management holes 42 for routing cables and wiring therethrough. It is to be understood that the cut-out portions 38 may also be integrated into robot 10 to provide even greater configurability and building efficiency in the robot 10 . Furthermore, slide rail attachments having corresponding connectors 29 a , 29 b may also be utilized in connection with the first alternative embodiment robot 34 .
With reference to FIG. 6 , and with continuing reference to FIG. 4 , a second alternative embodiment robot 44 is shown. The second alternative embodiment robot 44 is of similar construction as the robot 10 except for the arrangement of the mounting elements 16 a - c. Specifically, the mounting elements 16 a - c are mounted in a vertical orientation, as opposed to a horizontal orientation. Thus, the mounting elements 16 a - c may be attached to the substantially parallel horizontal members 26 a , 26 b so that the mounting elements 16 a - c span the height of the bay 28 a . It is to be understood that the cut-out portions 38 shown in FIGS. 4 & 5 may also be integrated into robot 44 to provide even greater configurability and building efficiency in the robot 44 . Furthermore, slide rail attachments having corresponding connectors 29 a , 29 b may also be utilized in connection with the second alternative embodiment robot 44 .
It is intended that the robot 10 , the first alternative embodiment robot 34 , and the second alternative embodiment robot 44 each have a mechanism for imparting motive force to the support structure 14 . With specific reference to the robot 10 in FIG. 3 , the support structure is configured to support the drive wheel 18 and the support wheels 22 . In this exemplary embodiment, the support wheels 22 provide stability and balance to the robot 10 . The drive wheel 18 may be either directly or indirectly powered by the motor 20 . For example, FIG. 3 depicts a drive belt 46 that transfers energy from the motor 20 to the drive wheel 18 . This embodiment provides an accurate differential drive system with optical wheel encoders and motor driver circuitry. It is to be understood that the support structure 14 may be configured to support any suitable mechanism for imparting motive force. Furthermore, it is to be understood that the robot 10 may include, in addition or substitution to the wheels, treads that would allow the robot 10 to navigate terrain that may ordinarily be accessible to wheeled-only robots. The support structure 14 may be configured to receive a battery 48 for providing power to various components of the robot 10 , including but not limited to the motor, the mounting elements, and the hardware and peripherals.
The present invention allows a builder to replace or modify a specific piece of hardware without requiring the builder to temporarily remove obstructive hardware that prevents effective access to the specific hardware that needs to be replaced or modified. For example, if the builder wishes to replace the optical drive 16 b with a different component, the builder simply slides out the optical drive 16 b from the bay 28 a without having to remove any adjacent hardware. In this case, no adjacent hardware is required to be removed because no adjacent hardware is obstructing the removal of the optical drive 16 b . In another example, if the builder wishes to access the daughterboard 32 and make changes thereto, the builder simply slides out the tray 16 a without having to disturb other hardware. It is to be understood that if the encasement shell 12 does not include an opening from which the mounting elements 16 a - c may be removed, that the mounting elements 16 a - c may still be removed from the bay 28 a after the encasement shell is removed from the robot 10 . This embodiment may be desirable if a builder wants to prevent unauthorized access to and/or removal of the mounting elements 16 a - c , which would otherwise be accessible through the opening of the encasement shell 12 . In addition to providing efficient access to various hardware and peripherals, the support structure is conducive to cable management. Uncluttered cable arrangements not only allow the builder more room in which to work, but also aid in the efficient air flow critical to proper functioning of electrical components.
The invention has been described with reference to the desirable embodiments. Obvious modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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A hobby robot having a support structure includes a cavity defined within the support structure, wherein the cavity includes means positioned within the cavity for removably coupling at least one mounting element to an interior portion of the cavity. The support structure also includes means for securing an encasement shell to the support structure. The mounting element may be a tray or hardware that performs a desired function in connection with the operation of the robot. The support structure is adapted to receive a self-contained power source and means for imparting motive force to the support structure.
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BACKGROUND OF THE INVENTION
The invention proceeds from an endoscopic instrument according to the preamble of patent claim 1.
DESCRIPTION OF THE PRIOR ART
An endoscopic instrument of this type in the form of a ligaturing instrument is described in DE-A-3504202. This instrument comprises a hollow shank, to the distal end of which is releasably arranged an arcuate needle type threading piece for a ligature thread, and at the proximal end of this hollow shank there is provided a handle. The hollow shank comprises a continuous longitudinal slit which is distally formed with a broadened opening. A locking body for the ligature thread may be applied through this opening. Whilst the ligament thread at the distal side is inserted into the threading piece, in the proximal direction the ligature thread is inserted through the slit of the hollow shank into this shank. With the help of a trocar the ligature instrument together with the ligature thread inserted therein is guided towards the location in the body of the patient to be treated. Although the ligature thread with this instrument is located protected in the hollow shaft during the introduction of the instrument into the body cavity of the patient, there is however the danger that the ligature thread becomes dislocated out of the slit of the hollow shank, which with the practical use of the ligature thread may lead to the entangling of the thread in the body region concerned and thus to unnecessary stress for the patient and complications.
In DE-C-2300840 another ligature instrument is disclosed. This instrument comprises a hollow inner shank with a handle at right angles to this shank at its proximal end, an operating element in the form of a tube surrounding the inner shank and a tube pair running through the inner shank. This tube pair extends distally from the inner shank with a straight section and ends in a distal roughly annular formation. The tube surrounding the inner shank of this known ligature instrument extends in the tube's initial position from the handle up to roughly the annular formation which it maintains closed, this being due to the expanding spring force of the handle. The ends of the tube pair embodying the annular formation expand radially outwards on account of their immanent pretensioning when the operating element is pulled back. The tube pair itself forms a continuous forward and rearward running guiding lumen for the ligature thread. This ligature instrument has proven to be awkward in practical handling, i.e. on introducing the ligature thread into this instrument, since in particular the ligature thread must be threaded into the one tube part of the tube pair with the help of an additional assisting instrument and then pulled back through the other tube part, in order to provide threading material in the annular fomation.
Furthermore, binding and ligature needles are generally known which are comprised of a handle and a needle part in one piece. Distally, the needle part has a desired arch shaped formation which is generally sickle shaped or semicircular and essentially runs bent at right angles to the longitudinal extension of the remaining needle. The distal end of the formation has an eye of a needle for receiving and guiding a ligature thread. The endoscopic work must be carried out very carefully since the inadequate guiding of the ligature thread leads to those previously mentioned entanglements and the related dangers, this lengthening the endoscopic operation and stressing the patient.
SUMMARY OF THE INVENTION
It is the object of the invention to improve the previously cited endoscopic instruments and which, while remaining simple in its construction, ensures a fast and simple insertion of at least one elongate medical assisting device into the instrument, prevents the undesired dislocation of the assisting device out of this instrument and also permits a secure handling of the assisting device in the body of the patient and a careful treatment of the patient.
The solution to this problem is given in patent claim 1.
This solution allows a quick and simple insertion of an assisting device, e.g. a ligature thread or catheter, into the instrument, since for this only a slight twisting of the hollow outer shank to bring its longitudinal slit to overlap with the longitudinally running recess of the inner shank needs to be made, so that the assisting device may be inserted into the recess without any difficulty. By way of a subsequent slight twisting and positioning of the outer shank, the recess of the inner shank is securely occluded so that the assisting device may not dislocate out of the recess. The assisting device is then securely located in the instrument and may be guided towards the location to be operated in the body of the patient and safely operated here without complications for the patient. The operation of the endoscopic instrument according to the invention is likewise simple since to insert an assisting device, the hollow outer shaft needs only to be adjusted by a slight twisting. Moreover the construction of the instrument as a whole remains simple so that it may be produced with relatively low manufacturing costs.
In one design of the endoscopic instrument according to the invention, the outer shank beginning from the distal end of the instrument, extends at least over a part length of the inner shank and the recess of the inner shank projects proximally from the outer shank. In this way a flexible assisting device, e.g. a catheter, may laterally enter the instrument just behind the outer shank, but reasonably far in front of the handle.
In a further design the inner shank is composed of a tube material with at least one longitudinally running recess formed in the tube wall. If for example two recesses are formed then for instance a ligature thread may be inserted into the one recess and a catheter inserted into the other.
In yet a further design, the inner shank in its form as a hollow shank, comprises at least one additional lumen for leading through an additional assisting device, e.g. an endoscope optic. In this way the operating location in the body of the patient may be inspected without using a separate optical endoscope which necessitates a second puncturing of the patient, this being thereby done away with.
Furthermore the outer shank and the inner shank may be separable from one another. In this way both parts may easily be individually cleaned and disinfected after use.
In another design of the endoscopic instrument according to the invention, the hollow outer shank, at its proximal end, is provided with a slotted adjusting ring which is rigidly attached to said outer shank. The adjusting ring comprises a latching device for fixing the outer shank to the inner shank at least in one position in which the recess of the inner shank is overlapped by the outer shank. In this way a simply constructed and operated adjusting device is produced.
In yet a further design of the instrument the handle of the inner shank comprises an elongate component flush with this shank, said component having a receiving groove for the ligature thread, said receiving groove extending in the longitudinal direction of the handle and being flush with the recess of the inner shank. The design of a receiving groove in the handle allows an easy insertion of the ligature thread into the recess or into the hollow space of the inner shank when the outer shank reaches as far as the handle.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is hereinafter described in more detail by way of the attached drawings. These show:
FIG. 1 a lateral view of a first emdodiment example,
FIG. 2 a lateral view of a first constructional unit of the embodiment example,
FIG. 3 a rear view of the constructional unit according to FIG. 2,
FIG. 4 a lateral view of a second constructional unit of the embodiment example,
FIG. 5 an axial longitudinal section through the embodiment example according to FIG. 1,
FIG. 6 a sectional representation taken along line VI--VI in FIG. 1,
FIG. 7 the embodiment example in a modified form,
FIGS. 8a to 8d an enlarged scale sectional representation taken along line VIII--VIII in FIG. 7,
FIG. 9 a further development of the embodiment form acccording to FIG. 8a,
FIG. 10 a view of a second embodiment example,
FIG. 11 an enlarged scale sectional representation taken along line XI--XI in FIG. 10,
FIG. 12 an embodiment example modified with respect to that of FIG. 11,
FIG. 13 a view of a third embodiment example,
FIG. 14 an enlarged scale sectional representation taken along line XIV--XIV in FIG. 13.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The instrument indicated generally at 1, e.g a ligature instrument comprises according to FIG. 1 a first constructional unit 2 as a thread receiver and a second constructional unit 3 which surrounds the first constructional unit and is in the form of a hollow outer shank for securing a ligature thread inserted into the thread receiver 2. The outer shank surrounds the thread receiver coaxially and in the case shown over its whole length.
In FIGS. 2 and 3 the thread receiver on its own is shown. It can be recognised that this receiver comprises essentially of three parts, that is to say an elongate shank 4, which forms the middle part of the thread receiver, a needle insert 5 fastened to the distal end of the shank 4 and an elongate handle 6 fastened to the proximal end of the shank 4. The middle shank 4 is provided with a recess 4a extending along its whole length, said recess receiving the mentioned ligature thread. For this purpose the shank 4 may be comprised of solid material into which the recess 4a in the form of a groove having an adequately dimensioned cross section is incorporated. Alternatively, and as is shown for example by way of FIG. 2, which is the preferred embodiment form, the shank 4 may also be formed from a hollow shank, that is composed of a tube which for instance is provided with a longitudinal slit over its whole length, through which the ligature thread is inserted into the hollow shank. The whole hollow space and the longitudinal slit of the shank then form the recess 4a.
The needle insert 5 comprises a straight first needle section 7 connecting flush with the shank 4 and a second needle section 8 which is bent at an angle to said first needle section. The second section 8 comprises a designated, generally known form (not shown), e.g. a sickle shape, semicircular shape or likewise. Moreover the free end of the second needle section 8 is provided with the usual eye of the needle 9 through which the ligature thread 20 is pulled (FIG. 5). The first needle section 7 according to FIG. 2 is provided with a longitudinal groove 10 which extends over a part length of this needle section and graduates flushly into the distal end of the recess 4a or into the inside of the hollow shank 4.
The handle 6 which connects flush with the proximal end of the hollow shank 4 comprises an elongate component and is provided with a receiving groove 11 extending in the longitudinal direction of the handle, said receiving groove receiving the ligature thread 20 which proximally emerges from the hollow shank 4 (FIG. 5). The receiving groove 11 is flush with the recess 4a of the shank 4 and extends, as is shown, over the whole length of the handle 6. However it is possible that this groove only extends over a part length of the handle 6 connecting to the shank 4.
The handle 6 is provided with a structure 12, 13 on its surface for a better gripping and handling of the ligature instrument 1. This structure may for instance be composed of a multitude of shallow grooves 12 at a distance from one another. These grooves may provided over the whole length of the handle 6. Alternatively it may also be provided that the structure comprises a knurling or diamond knurl 13 which likewise may extend over the whole length of the handle 6. It may also be the case that both structure designs are provided, as is shown in FIG. 3. It can be recognised that on the shank side, the handle first connects to the grooved structure 12 which then follows the knurling or diamond knurl 13. In a further alternative design, with regard to the structure, it may be proceded to provide the circumferential grooves 12, which are at a distance from one another, over the whole length of the handle 6 and to knurl or diamond knurl the distances between the circumferential grooves. Knurling is also understood to include axial and circumferential knurling.
In FIG. 4 the second constructional unit 13 is shown on its own. It comprises a hollow outer shank 14 which has essentially the same length as the shank 4 of the thread receiver. This outer shank is provided with a continuous longitudinal slit 15. This longitudinal slit runs parallel to the recess 4a or to the longitudinal slit of the previously mentioned shank 4 of the thread receiver in order to be able to insert a ligature thread in the thread receiver. The insertion position of the outer shank 14 can be best seen from FIG. 6, in which both the longitudinal slits 4a and 15 are flush with each other.
The hollow outer shank 14 is provided at its proximal end with a slotted adjusting ring 16 which is rigidly attached to said outer shank (FIGS. 1, 4, 5, and 6) in order to be able to twist the outer shank 14 from the insertion position according to FIG. 6 into an overlapping position and position said shank in the overlapping position in which the slit 4a of the internally lying shank 4 is covered, so that a ligature thread inserted into the shank 4 does not move out through the longitudinal slit 4a of this shank.
For securing both previously mentioned positions of the outer shank 14 which surrounds the inner shank 4, the adjusting ring 16 comprises a latching device 17. This comprises a spring tensioned latching ball 18, which latches into latching notches 19 of the inner shank 4 and thus secures both mentioned positions of the hollow outer shank 14. Although it is advantageous to provide two latching notches 19 in the inner shank 4, one latching notch 19 only may be provided. Then, that notch which would ensure a secure overlapping of the recess 4a or the longitudinal slit of the inner shank 4 by the outer shank 14 would be chosen.
The embodiment example according to FIG. 7 differs from that according to FIG. 1 in that the outer shank 14 is shorter than the inner shank 4. The outer shank begins distally together with the inner shank and ends at a desired distance A in front of the handle 6. However, the recess 4a or a correspondiing slit of the inner shank projects proximally from the outer shank 14 including the adjusting ring 16 and may likewise end at a certain distance in front of the handle 6, as can be deduced from FIG. 7. With this embodiment it is not necessary that the handle 6 comprises a slit or a recess which allows a lateral exit of the ligature thread 20 or another flexible or bendable assisting device, such as for example a catheter or a stent.
FIG. 8a represents a further design possibility for the recess 4a of the inner shank 4. If this shank is comprised of tube material, a circumferential section in the form of a channel may be incorporated in the tube wall receding into the inside of the tube. The channel then receives the ligature thread 20. Whilst FIG. 8a shows the unclosed channel 4a, this is closed in FIG. 8b by twisting the outer shank 14 about 90°, said outer shank with part of its wall overlapping the channel and thus securing the ligature thread in the channel.
FIG. 8c shows an inner shank 4 which additionally to the recess 4a, comprises a second recess 4b which for instance lies diametrically opposite the first recess. If the shank 4 is composed of a tube material, this second recess 4b is likewise incorporated receding into the tube wall of this shank. If the shank 4 is comprised of solid material, the second recess 4b is formed by machining e.g. by milling. A catheter 21 for example, which is to be positioned in the body of a patient may be inserted into the second recess. It is also possible to provide more than two recesses in the shank.
For overlapping the recesses 4a, 4b using the outer shank 14, this outer shank is twisted about the inner shank 4, this being firstly over the first recess 4a and then after insertion of the additional assisting means 21, over the second recess 4b. With regard to its position in FIG. 8c, the outer shank is then twisted about 270° in order to secure all assisting devices in their recesses.
FIG. 8d shows essentially the embodiment according to FIG. 8c with the exception that the outer shank 14 comprises two slits 15, 15b, so that each recess 4a, 4b is allocated to an insertion slit. While the one slit 14 preferally extends over the whole length of the shank 15, this is not the case with the other slit 15b. This slit extends roughly over half the shank length in order to ensure an adequate shank stability.
FIG. 9 shows a further embodiment of the inner shank 4 when this shank is composed of a tube material. Within the tube cross section an additional lumen 22, formed by a tube, may be provided and through which an endoscope optic (not shown) as an additional assisting device may be guided. Such an optic which is introduced into the instrument at the proximal side at a suitable location, simplifies the handling of the ligature thread or likewise in the body of the patient and does away with the need to make a second puncture in the body of the patient.
Instead of the more previously described adjusting ring 16 for the twist adjusting of the outer shank 14 about the inner shank 4, a threaded connection between both the shanks may also be provided. FIG. 9 shows such a connection. For this purpose the outer shank 14 is provided with an internal thread 23 at its proximal end region, said thread engaging with an external thread 24 of the inner shank 4, said external thread extending over an appropriate region of the inner shank. The thread 23, 24 is so formed that the frictional engagement between the thread turns is sufficient to hold the outer shank, with regard to the recess 4a or recesses, in each case in its open position as well as also in its closed position.
In a further formation of the endoscopic instrument the outer shank is designed separable from the inner shank 4, so that it may be pulled from this in the distal direction. As can be understood without further ado, the latching of the adjusting ring 16 as well as the thread connection 23, 24 permits a simple releasing of the shanks from one another. The slit 15 of the shank 14 has an appropriate width so that the needle bend 8 can pass the slit.
In FIGS. 10, 11, and 12 there is shown a second embodiment example of the endoscopic instrument 1 which is equipped with addition devices. The inner shank 4 manufactured from tube material is, apart from the already mentioned additional lumen 22 for an endoscope optic (not shown), provided in its inside with two further lumens 25 and 26 consisting of tubes, these lumens running through the shank 4 as flushing lumens. For this purpose the handle 6 comprises two laterally distanced connections 27 and 28 as well as an optic lumen 22b. Thus flushing liguid may run through the instrument 1 via the connection 27 to the location of operation and may again be suctioned out of the operation location via the connection 28. Otherwise the inner shank 4 comprises the previously described recess 4a in which the catheter is inserted (FIG. 11). When the catheter 21 has been inserted into the recess 4a the outer shank 14 is twisted about 90°, this being for example with the aid of the adjusting ring 16, so that the recess 4a is covered and the section of the catheter 21 located in this recess is secured against accidental dislocation out of the recess.
The embodiment form according to FIG. 12 differs from that according to FIG. 11 in that lumens 22, 25 and 26 of the inner shank 4 are not formed by additional tubes, but with regard to the cross section are formed by a particular wall contour of the inner shank 4. It can be recognised that the lumen 22 for an endoscope optic which can be passed through is formed by a channel-type arching 22a of the tube material of the shank 4. The apex of the arching 22a at the same time lies adjacent the apex of the recess 4a which receives the catheter 21. Space for the endoscope optic (not shown) is thereby created between the arching 22a and the outer shank 14. By way of the recess 4a and the arching 22a, which lie adjacent each other at their apexes, simultaneously, both flushing lumens 25 and 26 are formed in the inner shank 4. These flushing lumens are also connected to the connections 27 and 28. Otherwise the functional manner of this embodiment example corresponds to that of the first embodiment example.
In FIG. 13 and 14 there is shown a third embodiment example of the endoscopic instrument. This embodiment example differs from that according to FIGS. 10 and 11 in that instead of a lumen 22 for an endoscope optic which can be passed through, a second recess 4b is provided in the inner shank 4 in the already previously described design, and in that the outer shank 14 is equipped with a second insertion slit 15a for the second recess 4b. Whilst in the one recess 4a a catheter 21 may be inserted, a ligature thread 20 or other assisting device may be located in the other recess 4b. When both these assisting devices are inserted into the inner shank, the outer shaft 14, on operation of the adjusting ring 16, is twisted about approx. 90° so that both recesses are covered by the outer shank 14 and secured therein. The slit design in the outer shank 14 can be such that both slits 15, 15a extend only over part of the length of the shank in order to ensure the stability of the outer shank. It is however possible that one of the slits 15, 15a also may extend over the whole length of the outer shank 14; this is shown dashed in FIG. 13.
The complete or part covering of an assisiting device using the outer shank 14 such as a catheter inserted into the recess 4a of the inner shank 4, or with several recesses of a corresponding number of assisting devices, may be effected by the distal displacement of the outer shank should one or the slits 15 only extend over a part length of the outer shank, as is shown in FIG. 13. Depending on how far axially a catheter is inserted into the corresponding recess 4a, the remaining part length, i.e. the unslotted part length of the outer shank 14 may be sufficient to cover the catheter. For this the pulled back outer shank is displaced so far distally after the insertion of the catheter or likewise, that the recess 4a of the inner shank 4 and thus the catheter is covered by the outer shank 14 in this region, which is clear to the man skilled in the art in connection with FIG. 13. A positioning of the outer shank in its distal overlapping position may be effected by the latching device 17 of the adjusting ring 16. For this the inner shank 4 may comprise a latching notch (not shown) at a suitable location so that the outer shank is secured in a kept position.
The embodiment examples according to FIGS. 10 and 13 are applicable without a needle insert, so this is not shown. If it is necessary, a needle insert may be however mounted to the distal end of these instruments. Mainly the instrument according to the examples 10 to 14 are applied for inserting catheters.
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The endoscopic instrument for introducing elongate medical assisting devices into the body of a patient comprises an elongate shank which is provided at its proximal end with a handle for the instrument, whereby the shank comprises at least one recess for receiving and guiding an elongate assisting device, said recess beginning distally and extending at least partly along said shank's length. For improving the introduction of the assisting device into the body of the patient the shank is surrounded by a hollow outer shank which comprises at least one longitudinal slit extending from its distal end along at least a part length of the outer shank, whereby the outer shank is twistable or distally displaceable over the inner shank for overlapping the recess of said inner shank, and can be positioned in the overlapping position.
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FIELD OF THE INVENTION
[0001] This invention relates to acetylene removal catalysts and their improved process for hydrogenation of hydrocarbons. In another aspect, this invention relates to processes for hydrogenation of hydrocarbons generally and particularly selectively hydrogenating alkynes and/or diolefins to their corresponding monoolefins employing palladium/silver/alumina catalysts, impregnated with potassium compound. This invention also relates to improved processes for hydrogenation of hydrocarbons employing potassium fluoride impregnated palladium/silver/alumina catalysts in the presence of sulfur-containing impurities in a depropanizer feed. In the presence of sulfur-containing impurities, the catalyst of the present invention is more active and achieves higher ethylene selectivity.
BACKGROUND OF THE INVENTION
[0002] The selective hydrogenation of alkynes, which generally are present in small amounts in alkene-containing streams (e.g., acetylene contained in ethylene streams from thermal ethane crackers), is commercially carried out in the presence of supported palladium catalysts. In the case of the selective hydrogenation of acetylene to ethylene, preferably an alumina-supported palladium/silver catalyst is used in accordance with the disclosure in U.S. Pat. No. 4,404,124 and its division, U.S. Pat. No. 4,484,015. The operating temperature for this hydrogenation process is selected such that essentially all acetylene is hydrogenated to ethylene (and thus removed from the feed stream) while only an insignificant amount of ethylene is hydrogenated to ethane to minimize ethylene losses and to avoid a “runaway” reaction which is difficult to control, as has been pointed out in the above-identified patents.
[0003] It is also generally known to those skilled in the art that sulfur-containing impurities, such as H 2 S, carbonyl sulfide (COS), mercaptans (RSH), organic sulfides (R—S—R), organic disulfides (R—S—S—R), organic polysulfides (R—S n —R, where n>2), and the like, which can be present in an alkyne-containing feed or product stream, can poison and deactivate a palladium-containing catalyst. Since many plants have various sulfur impurities continuously present or at least present as intermittent spikes, it would be advantageous to be able to run both in the presence of and absence of such various sulfur impurities. Sulfur impurities are usually found in depropanizer and raw gas hydrogenation processes (but can occur in any hydrogenation process) as a result of plant and operational limitations. The feed stream being hydrogenated can contain either low levels and/or transient spikes of a sulfur impurity. Thus, the development of a catalyst composition for use in a front-end depropanizer ARU ethylene plant for the hydrogenation of highly unsaturated hydrocarbons such as diolefins (alkadienes) or alkynes to less unsaturated hydrocarbons such as monoolefins (alkenes), both in the presence of and in the absence of a sulfur impurity, would be a significant contribution to the art and to the economy.
[0004] Other aspects and features of the invention will become apparent from review of the detailed description and the claims.
DETAILED DESCRIPTION OF THE INVENTION
[0005] The catalyst which is employed in the selective hydrogenation process of this invention is a supported palladium catalyst composition which comprises a silver component and lower levels of a potassium component and optionally a fluorine component. This catalyst composition can be fresh or it can be a previously used and thereafter oxidatively regenerated. This catalyst can contain any suitable inorganic solid support material. Preferably, the inorganic support material is selected from the group consisting of alumina, titania, zirconia, and mixtures thereof. The presently more preferred support material is alumina, most preferably alpha-alumina. This catalyst generally contains palladium, a silver component, a fluorine component, and a potassium component. Wherein the weight % palladium is selected from one of the following ranges 0.01-1, 0.01-0.6, 0.01-0.2, 0.01-0.1, etc. Wherein the weight % of silver is selected from one of the following ranges 0.005-10, 0.01-10, 0.005-2, 0.01-2, etc. Wherein the weight % fluorine is selected from one of the following ranges 0.01-1.5, 0.05-0.4, etc. Wherein the weight % of potassium is selected from one of the following ranges, less than 0.3, less than 0.2, less than 0.1, etc. weight % potassium. Particles of this catalyst generally have a size of 1-10 mm (preferably 2-6 mm) and can have any suitable shape. Suitable shapes can be selected from spherical, cylindrical, extrudates, multilobe extrudates, etc. Generally, the surface area of this catalyst (determined by the BET method employing N 2 ) is 1-100 m 2 /g.
[0006] The above-described catalyst which is employed in the hydrogenation process of this invention can be prepared by any suitable, effective method. The potassium fluoride can be incorporated between the palladium and the silver impregnation steps after the palladium and silver impregnation steps or together with either the palladium or silver. The presently preferred catalyst preparation comprises the impregnation of a Pd/Ag/Al 2 O 3 catalyst material with an aqueous solution of potassium fluoride, followed by drying and calcining. The drying and calcining step occurs in an atmosphere of any inert gas containing from 0.1 to 100 volume % oxygen, at a temperature selected from one of the following ranges 300-800° C., 350-600° C., etc, generally for 0.1-20 hours. It is possible, to apply a “wet reducing” step (i.e., treatment with dissolved reducing agents such as hydrazine, alkali metal borohydrides, aldehydes such as formaldehyde, carboxylic acids such as forming acid or ascorbic acid, reducing sugars such as dextrose, and the like).
[0007] The thus-prepared catalyst composition which has been dried (and preferably also calcined, as described above) can then be employed in the process of this invention for hydrogenating at least one alkyne, preferably acetylene, to at least one corresponding alkene in both the presence and absence of at least one sulfur compound. Optionally, the catalyst is first contacted, prior to the alkyne hydrogenation, with hydrogen gas optionally diluted with 0-95 volume % of any gas substantially free of unsaturated hydrocarbons, generally at a temperature in the range of 20° C. to 100° C., for a time period of 1 to 20 hours. During this contacting with hydrogen before the selective alkyne hydrogenation commences, palladium and silver compounds which may be present in the catalyst composition after the drying step and the optional calcining step (described above) are substantially reduced to palladium and silver metal. When this optional reducing step is not carried out, the hydrogen gas present in the reaction mixture accomplishes this reduction of oxides of palladium and silver during the initial phase of the alkyne hydrogenation reaction of this invention.
[0008] The selective hydrogenation process of this invention is carried out by contacting highly unsaturated hydrocarbons, hydrogen gas, optionally in the presence of one or more sulfur-containing impurities with the inventive catalyst composition. These components are reacted under conditions effective in converting the highly unsaturated hydrocarbons to less unsaturated hydrocarbons in a front-end depropanizer ARU.
[0009] The term “highly unsaturated hydrocarbon” refers to a hydrocarbon having one (or more) triple bond(s) or two or more double bonds between carbon atoms in the molecule. Examples of highly unsaturated hydrocarbons include, but are not limited to, aromatic compounds such as benzene and naphthalene; alkynes such as acetylene, propyne (also referred to as methylacetylene), and butynes; diolefins such as propadiene, butadienes, pentadienes (including isoprene), hexadienes, octadienes, and decadienes; and the like and mixtures thereof. The term “less unsaturated hydrocarbon” refers to a hydrocarbon in which the one (or more) carbon-to-carbon triple bond(s) in a highly unsaturated hydrocarbon is (are) hydrogenated to a carbon-to-carbon double bond(s), or a hydrocarbon in which the number of carbon-to-carbon double bonds is one less, or at least one less, than that in a highly unsaturated hydrocarbon, or a hydrocarbon having at least one carbon-to-carbon double bond. Examples of less unsaturated hydrocarbons include, but are not limited to, monoolefins such as ethylene, propylene, butenes, pentenes, hexenes, octenes, decenes, and the like and mixtures thereof.
[0010] During the selective hydrogenation process of the present invention, a hydrocarbon feed containing at least one highly unsaturated hydrocarbon and hydrogen, optionally in the presence of sulfur-containing impurities, are fed to an Acetylene Hydrogenation Unit, where the catalyst composition of the present invention resides.
[0011] The highly unsaturated hydrocarbon includes diolefins, alkynes, and mixtures of two or more thereof.
[0012] Alkynes include acetylene, propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 3-methyl-1-butyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1-decyne, and mixtures thereof. Particularly preferred is acetylene. These alkynes are primarily hydrogenated to the corresponding alkenes, i.e., acetylene is primarily hydrogenated to ethylene, propyne is primarily hydrogenated to propylene, and the butynes are primarily hydrogenated to the corresponding butenes (1-butene, 2-butene).
[0013] Diolefins include propadiene, 1,2-butadiene, 1,3-butadiene, isoprene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,2-pentadiene, 2,3-dimethyl-1,3-butadiene, heptadienes, methylhexadienes, octadienes, methylheptadienes, dimethylhexadienes, ethylhexadienes, trimethylpentadienes, methyloctadienes, dimethylheptadienes, ethyloctadienes, trimethylhexadienes, nonadienes, decadienes, undecadienes, dodecadienes, cyclopentadienes, cyclohexadienes, methylcyclopentadienes, cycloheptadienes, methylcyclohexadienes, dimethylcyclopentadienes, ethylcyclopentadienes, dicyclopentadiene, and mixtures thereof. More preferably, the diolefin is propadiene, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-cyclopentadiene, dicyclopentadiene, and mixtures thereof. Particularly preferred is propadiene.
[0014] The temperature necessary for the selective hydrogenation of alkyne(s) to alkene(s) depends largely upon the activity and selectivity of the catalysts, the amounts of sulfur impurities in the feed, and can be any suitable temperature to achieve the desired extent of alkyne removal. Generally, a reaction temperature in the range of about 30° C. to about 200° C. is employed. Any suitable reaction pressure can be employed. Generally, the total pressure is in the range of 100 to 1,000 pounds per square inch gauge (psig). The gas hourly space velocity (GHSV) of the hydrocarbon feed gas can also vary over a wide range. Typically, the gas hourly space velocity will be in the range of about 1,000 to 20,000.
[0015] Regeneration of the catalyst composition can be accomplished by heating the catalyst composition in an atmosphere of any inert gas containing from 0.1 to 100 volume % oxygen at a temperature which preferably does not exceed 700° C. so as to burn off any sulfur compounds, organic matter and/or char that may have accumulated on the catalyst composition. Optionally, the oxidatively regenerated composition is reduced with hydrogen diluted with 0 to 95 volume % of any gas substantially free of unsaturated hydrocarbons before its redeployment in the selective alkyne hydrogenation of this invention.
[0016] The following examples are presented to further illustrate this invention and are not to be construed as limiting its scope.
EXAMPLE I
[0017] This example illustrates the preparation of various palladium-containing catalyst compositions to be used in a hydrogenation process.
[0018] Catalyst A (Control) was prepared in accordance with U.S. Pat. No. 5,489,565 and contained 0.014 weight % Pd, 0.044 weight % Ag, 0.3 weight % K, and 0.15 weight % F on aluminum oxide support.
[0019] Catalyst B (Control) was prepared in accordance with U.S. Pat. No. 5,587,348 and contained 0.013 weight % Pd, 0.044 weight % Ag, 0.3 weight % K, and 0.3 weight % F on aluminum oxide support.
[0020] Catalyst C (Invention) was prepared in accordance with U.S. Pat. No. 5,489,565 and contained 0.02 weight % Pd, 0.04 weight % Ag, 0.1 weight % K, and 0.05 weight % F on aluminum oxide support.
EXAMPLE II
[0021] This example illustrates the performance of the catalysts described hereinabove in Example I in a hydrogenation process in the absence and the presence of sulfur.
[0022] About 23 grams (i.e., about 20 cc) of each of the above described catalysts were placed in a stainless steel reactor tube having a 0.62 inch inner diameter and a length of about 18 inches. The catalyst (resided in the middle of the reactor; both ends of the reactor were packed with 6 mL of 3 mm glass beads) was reduced at about 100° F. for about 1 hour under hydrogen gas flowing at 200 mL/min at 200 pounds per square inch gauge (psig). Thereafter, a hydrocarbon-containing fluid, typical of a feed from the top of a depropanizer fractionation tower in an ethylene plant, containing approximately (all by weight unless otherwise noted) hydrogen, 2.1%; methane, 22%; ethylene, 54%; propylene, 21%; acetylene, 4300 ppm; propadiene, 4300 ppm; propyne, 4300 ppm; and carbon monoxide, 300 ppm (by volume) was continuously introduced into the reactor at a flow rate of 900 mL per minute at 200 psig. The reactor temperature was increased until the hydrogenation ran away, i.e., the uncontrollable hydrogenation of ethylene was allowed to occur. During the runaway, the heat of hydrogenation built up such that the reactor temperature exceeded about 250° F. The reactor was then allowed to cool to room temperature before data collection was started.
[0023] Feed (900 mL/min @ 200 psig) was passed over the catalyst continuously while holding the temperature constant before sampling the exit stream by gas chromatography. The catalyst temperature was determined by inserting a thermocouple into the thermowell and varying its position until the highest temperature was observed, the furnace was then raised a few degrees, and the testing cycle was repeated until 3 weight % of ethane was produced.
[0024] The cleanup temperature, T1, is defined as the temperature at which the acetylene concentration drops below 20 ppm. The T2, runaway temperature, is defined as the temperature at which 3 wt % of ethane is produced. At this temperature the uncontrolled hydrogenation of ethylene to ethane begins. And delta T is the difference between T2 and T1. This value can be viewed as a measure of selectivity or even a window of operability.
[0025] Each catalyst was exposed to the high carbonyl sulfide (COS) concentration at different temperatures. This was determined by predicting what the T1 cos would be. By exposing the catalyst to the high concentration of COS at a temperature of 10° F. less than the predicted T1 cos , the amount of time it took for the reaction to reach a steady state was minimized.
[0026] The T1 cos was determined as follows. First 12 ppm COS was added to the feed and the flow rate was lowered to 90 mL/min. A 300 mL (STP) portion of 5000 ppm COS in nitrogen was then introduced into the feed stream. After 5 minutes the flow rate was returned to 900 mL/min. The COS was introduced with a low flow rate to ensure there was sufficient contact time between the COS and the catalyst.
[0027] After over exposing the catalyst to COS, the reactor temperature was held constant until the acetylene concentration in the exit stream reached a steady state. At this point the reactor temperature was either lowered or raised to determine T1 cos . The entire run was conducted in a continuous mode, sulfur containing hydrocarbon feed always in contact with the catalyst. The reactor effluent, i.e., the product stream, was analyzed by gas chromatography. The results are shown in Table I. In addition, in Table I “hydrocarbon selectivities at T1” refers to the percent of acetylene that was transformed to its corresponding hydrocarbon at T1. Selectivities were determined on a mole basis.
TABLE 1 F:K Delta Selectivity to COS molar T1 T2 T C2 C4's C5's heavies C2= Run Catalyst (ppmv) ratio (° F.) (° F.) (° F.) (%) (%) (%) (%) (%) 101 A 0 1 151 225 74 14.5 12.2 4.3 3.3 65.8 102 A 12 1 248 * * 110.7 2.8 1.6 0 −15.1 103 B 0 2 149 218 69 16.1 10.6 6.1 3.9 63.3 104 B 12 2 203 * * 78.4 3.9 2.1 0 15.7 105 C 0 1 132 186 54 16.6 12.5 7.6 5.5 57.8 106 C 12 1 177 * * 75.5 4.6 0.8 0 19.1
[0028] Comparing run 101 to 103 there is little difference in the performance of catalyst A and B in the absence of sulfur. However runs 102 and 104 demonstrate that the additional fluorine on the catalyst improves the ethylene selectivity by 30%.
[0029] Comparing run 105 to 101 and 103, the only difference between the two runs in the absences of sulfur's. T1 for run 105 is lower. When sulfur is present, catalyst C (run 106) has an ethylene selectivity 39% better than catalyst A (run 102) and similar to catalyst B (run 104).
[0030] Thus these examples show that decreasing the total potassium concentration eliminates the need for additional fluorine on the catalyst.
[0031] While the foregoing discussion is intended to provide a detailed illustration of certain embodiments of the invention, it will be appreciated that additional embodiments are also possible under the claims provided herein. It will also be appreciated that numerical values and ranges are presented in approximate form such that small or inconsequential deviations from such values are intended to be within the spirit and scope of the values and ranges presented.
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This invention relates to acetylene removal catalysts and their use in the hydrogenating of highly unsaturated hydrocarbons to less unsaturated hydrocarbons in an olefin rich hydrocarbon stream in the presence of hydrogen and a catalyst composition under conditions effective to convert said highly unsaturated hydrocarbon to a less unsaturated hydrocarbon. Said catalyst composition comprises palladium, silver, potassium, and an inorganic support material, wherein the catalyst composition contains less than about 0.3 weight % potassium. In the presence of sulfur-containing impurities, the catalysts of the present invention yield a much smaller increase in T1 (cleanup temperature) and higher ethylene selectivity is achieved.
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DEDICATORY CLAUSE
The invention described herein was made in the course of or under Contract DAAH01-82-C-A235 or subcontract thereunder with the Government and may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalties thereon.
BACKGROUND OF THE INVENTION
Magnesium borohydride has been the subject matter of reports since about 1950. The preparative methods for magnesium borohydride up to about 1966 are discussed in a report titled, "Chemistry of Boranes IV. On Preparation, Properties, and Behavior Towards Lewis Bases of Magnesium Borohydride" by J. Plesek and S. Hermanek, appearing in Collection Czech. Chem. Comm/Vol. 31/(1966). These earlier reports (listed below) lead one to believe that the compound is now generally available, and comparable to sodium and lithium borohydrides possessing pronouncedly a salt like character (reports 2-6).
1. Barbaras G. D., Dillard C., Finholt A. E., Wartik T., Wilzbach K. E., Schlesinger H. I.: J. Am. Chem. Soc. 73,4585(1951).
2. Wiberg E., Bauer R.: Naturforsch. 5b, 397 (1950).
3. Wiberg E., Bauer R.: Z. Naturforsch. 7b, 58 (1952).
4. Wiberg E., Bauer R.: Chem. Ber. 85,593 (1952).
5. Wiberg E.: Angew. Chem. 65,16(1953).
6. Schrauzer G.: Naturwissenschaften 42,438 (1955).
This is not the case, however, according to J. Plesek, et al. who say "What papers used to call magnesium borohydride--that fact has now been established--were, at best, its adducts with various Lewis bases, or, in a few cases, mere solutions, in which borohydride anions and magnesium cations may be analytically proved. As the case stands, magnesium borohydride has not been hitherto dealt with as a chemical individuum."
J. Plesek, et al. also state in the above report that they found solvates of magnesium borohydride to be more or less readily prepared by all the routes reported, in varying degrees of purity. There is, however, one method only, which they found to afford desolvated magnesium borohydride, namely the following one accounted for by the equation:
MgH.sub.2 +B.sub.2 H.sub.6 +n(C.sub.2 H.sub.5).sub.2 O→Mg(BH.sub.4).sub.2 n(C.sub.2 H.sub.5).sub.2 O→Mg(BH.sub.4).sub.2 +n(C.sub.2 H.sub.5).sub.2 O
The adduct of magnesium borohydride with diethyl ether has no definite stoichiometric composition at room temperature. Most conveniently, it is prepared from magnesium hydride (synthesized by the direct combination of elements), and compressed diborane, by allowing the two reactants to stand in diethyl ether at room temperature. Description of properties of the ethereal solution of magnesium borohydride, of its desolvation, and of properties of the desolvated magnesium borohydride, is given under Experimental in the above report. Maximum attained purity amounted to 98 percent.
More recently, the preparation of ether soluble Mg(BH 4 ) 2 in an 85 to 90% yield has been reported by V. N. Konoplev, Russian J. Inorg. Chem. 25(7), 964 (1980). The unsolvated compound is obtained, purportedly, by vacuum pyrolysis of the intermediate liquid dietherate Mg(BH 4 ) 2 .2(C 2 H 5 ) 2 O (MBDE).
The magnesium borohydride described hereinabove is required to be transformed to a stable form or to be prepared by another method if it is to have the desired properties of long-term thermal stability as required for a solid gas generator of H 2 or D 2 for laser applications.
Therefore, an object of this invention is to provide an adduct of magnesium borohydride which has the desired chemical and physical properties for long-term thermal stability.
Another object of this invention is to provide a method for preparing adducts of magnesium borohydride which possess long-term thermal stability.
A further object of this invention is to provide a method for preparing high purity adducts of magnesium borohydride which possess long-term thermal stability and compatibility with an oxidizer salt and binder in a solid gas generator for H 2 and D 2 .
SUMMARY OF THE INVENTION
A low temperature process is disclosed for preparation of pure adducts of magnesium borohydride based on the addition of 1.8-1.9 mols of NH 3 per mol of Mg(BH 4 ) 2 .X(C 2 H 5 ) 2 O (wherein X≦2). In a benzene medium magnesium borohydride diammoniate (MBDA) forms as the insoluble product but when the reaction is conducted in an ether medium with the same quantities of reactants and under the same experimental conditions, insoluble magnesium borohydride triammoniate is formed.
From either reaction medium the pure adduct is readily isolated by filtration, solvent washing to remove excess Mg(BH 4 ) 2 .X(C 2 H 5 ) 2 O, and vacuum drying at ambient temperature. Yields are from about 95 to about 99% with purity levels typically of about 97%.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A direct low temperature process for the preparation of pure magnesium borohydride diammoniate and pure magnesium borohydride triammoniate is represented by the following process equations 1 and 2: ##STR3## Equation 2 is written as noted based on confirming explanatory data found in Table II which suggests that an equilibrium undoubtedly exists between formation of the ammoniate and the parent etherate. When employing either benzene or ether as the reaction medium and an excess of Mg(BH 4 ) 2 .X(C 2 H 5 ) 2 O (wherein X≦2), yields of the diammoniate and triammoniate adducts, respectively, are obtained in the range of about 95 to about 99 percent with purity levels typically of about 97%.
The starting material for the above conversions to the di- or tri- ammoniates of magnesium borohydride is the solvated product of Mg(BH 4 ) 2 with ether. The ratio of ether/Mg(BH 4 ) 2 is preferably in the range 0.5-3.0 with a ratio of about 2.0 being most preferred when the solvent medium is benzene due to solubility considerations. Ether solvated Mg(BH 4 ) 2 is obtained by the metathetical reaction or double decomposition of sodium tetrahydridoborate and anhydrous magnesium chloride in diethyl ether: ##STR4## The preparation of ether soluble Mg(BH 4 ) 2 with 33 to 100% excess NaBH 4 as reported by V. N. Konoplev in Russian J. of Inorg. Chem. 25(7), 964 (1980), is achieved in satisfactory yield by ball milling in lieu of high-speed stirring of the virtually insoluble reactants. Data on the synthesis of magnesium borohydride dietherate (MBDE) by the modified procedure is set forth in Table I, below. The failure of the first run subsequently was determined to have been due to the presence of water in the reactants and solvent. Reprocessing of the insoluble fraction of the reaction mixture from run 5 with additional fresh solvent did not produce significant additional MBDE suggesting that the reactants had been spent in an undefined manner (most probably hydrolysis). If the MBDE yield had been limited to approximately 60% by an equilibrium between product and reactants, further reaction would have been expected after removal of the MBDE formed initially.
TABLE I______________________________________Preparation of Mg(BH.sub.4).sub.2.2(C.sub.2 H.sub.5).sub.2 ORun Reactant, mols Ether, Reaction YieldNo. MgCl.sub.2 NaBH.sub.4 Liters Time, Hrs MBDE, %.sup.(a)______________________________________1 0.525 1.586 1.0 24 02 0.525 1.562 1.0 66 643 1.544 4.688 2.1 70 584 1.586 3.687 2.1 70 59.sup.(b)5 2.095 6.211 3.4 64(insolubles from run 5) 1.3 64 26 to 30 4.00 10.07 2.5 24 (minimum) 65.sup.(c)______________________________________ .sup.(a) Based on BH.sub.4.sup.- analysis .sup.(b) Yield for combined runs 4 and 5 raised to 61% when secondary recovery from additional processing of run 5 reaction solids is included. .sup.(c) The yields were determined only for combined runs 11-13 and run 16, and were based on product weight only.
In order to prepare a diammoniate, stoichiometric quantities of reactants [or excess Mg(BH 4 ) 2 ] must be used and the solvent must be innocuous and selective. Solvent screening tests using Mg(BH 4 ) 2 .2.5(C 2 H 5 ) 2 O with a deficiency of NH 3 established that Mg(BH 4 ) 2 .3NH 3 precipitated from diethyl ether solution, Mg(BH 4 ) 2 .2NH 3 from benzene solution, and that the more dense layer of the two-phase system in n-hexane only partially solidified. The upper concentration limit for MBDE in benzene, above which the triammoniate would form (due to increasing ether concentration), was not established. However, it was found that volume ratios of 6:1 benzene/MBDE gave the diammoniate. The preparative data for MBDA is summarized in Table II.
TABLE II__________________________________________________________________________Preparation of Magnesium borohydride diammoniateReactant, mols ProductRun Benzene NH.sub.3 /MBDE Yield Mg, NH.sub.3, BH.sub.4.sup.-,No. MBDE NH.sub.3 Ml Mol Ratio % % % %__________________________________________________________________________1 0.00418 0.00785 20 2 -- -- 38.2 --2 0.323 0.615 500 2 99.1 27.7 38.6 --3 3.14 6.00 5200 2 99.5 29.3 38.8 33.9.sup.a4 >7.4.sup.b <26.6.sup.c 6000 1.84 -- 32.1 41.3 34.4.sup.d 1.69 27.7 32.8 --5 10.5 16.2 6000 2.16 -- 27.3 43.0 --6 8.76 12.0 2800 1.92 96 28.6 38.5 33.1.sup.e7 9.00 15.3 3800 1.95 95 28.6 39.0 32.0.sup.d8 9.58 15.7 .sup. 3700.sup.f 1.88 93 28.5 37.5 34.9.sup.d9 11.1.sup.g 20.3 .sup. 6000.sup.g 1.91 128.sup.h 29.4 39.1 33.5.sup.__________________________________________________________________________ .sup.a calculated from AAS boron analysis .sup.b The material partially solidified, which suggested an ether/Mg ratio <2; 0.725 liters (C.sub.2 H.sub.5).sub.2 O was added to effect dissolution in benzene .sup.c The quantity added is unknown due to a significant loss of NH.sub. through the pressurerelief bubbler .sup.d Calculated from H.sub.2 obtained on acid hydrolysis .sup.e Basic iodate procedure .sup.f The filtrate from run 7 was used in lieu of benzene .sup.g Estimated amounts in recovered filtrates from previous runs .sup.h Based on ammonia added; the filtrates used as solvent presumably contained several moles of soluble Mg(BH.sub.4).sub.2.xNH.sub.3.y(C.sub.2 H.sub.5)O
In those instances wherein some higher ammoniates were also formed, it was possible to induce a redistribution reaction by treatment with MBDE in a benzene solution.
EXPERMENTAL
Reagents
Anhydrous magnesium chloride was purchased from either Aldrich or Ventron and used as received. The MgCl 2 purity ranged from 99% (Aldrich, prepared from the elements) to 93% (Ventron, reportedly prepared by dehydration of the hexahydrate). Sodium borohydride (98%, Ventron), was dried in a vacuum oven for 3 hours at 100. Benzene (Baker, reagent) was dried over P 2 O 5 (Baker, Granusic). Diethyl ether (Mallinkrodt, AR) and ammonia (Matheson) were used as received.
Apparatus
The reactor used to prepare MBDE was a ball mill fabricated from a 12-liter round bottom flask by converting the spherical shape to a cylinder of 22 cm diameter by 15 cm length with approximately hemispherical ends. To lift the balls, the cylindrical surface had eight equally spaced 8 mm indentations parallel to the axis of rotation of the cylinder. Each end of the ball mill carried a 58 mm tube that rested in a ball bearing assembly welded to the rim of a water bath that was used to heat the ball mill. One end was terminated in a medium fritted glass filter capped at the discharge end. The other end was terminated in a No. 50 o-ring joint used both to charge the mill and also to connect it subsequently to the rotary drive mechanism. The connection between the ball mill and drive incorporated a stainless-steel bellows that effected a seal while the drive torque was transmitted around the bellows from three radial pins to three pins oriented parallel to the axis of rotation. The ball mill was driven at approximately 100 rpm by the motor of a rotary evaporator which had the condenser (-10° C.) modified so that the solvent returned to the ball mill.
The reactor used to convert the intermediate MBDE to MBDA was a 12-liter round bottom flask modified by addition of a medium fritted glass filter at a 90-degree orientation to the flask neck. The neck of the flask carried a 45-degree adapter through which a rotatable gas inlet tube entered and which carried a short Vigreux column with ice-cooled reflux condenser.
Magnesium Borohydride Dietherate (MBDE)
In a nitrogen-filled glovebox, 381 g (4.00 mols) MgCl 2 , 381 g (10.1 mols) NaBH 4 , and 2.5 liters diethyl ether were added to the ball mill, which carried a 5-pound charge of 6 mm glass balls. The loaded mill then was positioned horizontally in the bearing assembly of the water bath, connected by means of a clamp to the rotary drive, and rotated at 95 rpm under reflux to effect reaction. The mill was vented to atmospheric pressure in a hood through a 10-foot length of 0.250-inch tubing. The characteristic odor of diborane and white deposits were noted at the vent. After 24 hours (longer reaction times did not improve the yield), the mill was disconnected from the rotary drive and quickly capped.
Filtration of the reaction slurry proved to be impractically slow and had the disadvantage that the mill had to be cleaned between runs in order to recover the balls. An alternate procedure, wherein the mill was capped with a nitrogen-filled 5 liter round bottom flask, was used. A disk of 8 mesh stainless steel screen placed in the No. 50 o-ring joint retained the 6 mm balls during transfer of the reaction slurry from the mill, which then could be recharged without cleaning. Slurries which were produced when 98% MgCl 2 was used were thin and poured readily; those from 93% MgCl 2 were thick and difficult to pour; and that from 75% MgCl 2 was a thick paste transferable only after dilution with ether (no MBDE could be isolated from this reaction mixture).
The MBDE is separated from the 2.5 liters of slurry by decantation (four times) after dilution to 5 liters with ether. All transfers are made pneumatically under dry nitrogen. The ether is stripped on a rotary evaporator at atmospheric pressure from the combined supernatant solutions and recycled.
The MBDE is isolated by vacuum stripping the distillation residue at 50° C. and 20 torr. The liquid product is analyzed for borohydride by the basic iodate procedure. Found, 12.1 to 14.7% BH 4 - ; calculated for Mg(BH 4 ) 2 .2(C 2 H 5 ) 2 O, 14.68%, BH 4 - . When additional ether was stripped from the product at 50° C. and 9 torr, partial solidification occurred. The solid isolated by trituration with benzene and filtration was analyzed for borohydride by acid hydrolysis. Found, 31.0% BH 4 - ; calculated for Mg(BH 4 ) 2 .0.546(C 2 H 5 ) 2 O, 31.0% BH 4 - .
Magnesium Borohydride Triammoniate
In one chamber of a double-chambered apparatus, a filtered solution of 1.0 g Mg(BH 4 ).2.5(C 2 H 5 ) 2 O (4.18 mmols) in 20 milliliters of diethyl ether was contacted with 174.2 cc (7.78 mmols) of gaseous NH 3 using conventional high-vacuum techniques. The resulting precipitate was isolated on the medium fritted filter separating the two chambers and washed three times by solvent distilled back from the filtrate. Analysis of the filtrate for magnesium, after hydrolysis, by Atomic Absorption Spectrometry (AAS) showed 1.73 mg-atoms, which suggested the NH 3 /Mg ratio in the solid to be 3.17. The solid was analyzed for NH 3 by the micro-Kjeldahl technique. Found 48.6% NH 3 ; calculated for Mg(BH 4 ) 2 .3NH 3 , 48.62% NH 3 .
Magnesium Borohydride Diammoniate (MBDA)
An experiment virtually identical to that used to prepare Mg(BH 4 ) 2 .3NH 3 was conducted, except that benzene was used as the solvent. The reactants used were 1.0 g of Mg(BH 4 ) 2 .2.5(C 2 H 5 ) 2 O (4.18 mmols) and 175.9 cc NH 3 (7.85 mmols). The filtrate contained 0.39 mg-atoms Mg suggesting a NH 3 /Mg ratio of 2.07 in the solid. Found, 38.2% NH 3 ; calculated for Mg(BH 4 ) 2 .2NH 3 , 38.6% NH 3 .
Using substantially the same type apparatus and techniques, the reaction was scaled up using 3.14 mols MBDE in 5.2 liters benzene and 6.00 mols NH 3 to give MBDA in a 99.5% yield. The analytical results on this material were as follows: Found, Mg, 29.3%, NH 3 , 38.8%, B, 24.7%; Na, 0.31%; Cl, 4.0%. Calculated for Mg(BH 4 ) 2 .2NH 3 : Mg, 27.61%; NH 3 , 38.68%; B, 24.55%.
Conventional laboratory techniques were used in further scaling the MBDA synthesis. A typical reaction is described. In a nitrogen-filled glovebox, 1770 g MBDE (not analyzed but assumed to be 8.76 mols) is diluted to 5 liters with benzene and pressure filtered. The filtrate is transferred to a 12 liter reactor and gaseous NH 3 from a cylinder on a balance is introduced over the surface of the magnetically stirred solution at a rate of approximately 1.5 g/min. Formation of a surface precipitate is immediate, but dissolution in the vortex is rapid for approximately 5 minutes. After about 1 hour, the NH3 addition is interrupted and the hot (˜60° C.) slurry is pumped to remove the free ether, which is collected in a -78° C. trap. Most of the benzene vapor is refluxed from a 0° C. condenser attached to the 12 liter reactor. When the temperature had fallen to ambient or lower, pumping was stopped and NH 3 addition was resumed. A total of 204 g NH 3 (12.0 mols) was added. The mixture was allowed to stir for 3.5 hours, while cooling to ambient under a nitrogen atmosphere. The slurry was pressure filtered and the solid was washed twice with 750 ml benzene under nitrogen and dried by pumping to 5×10 -3 torr at ambient temperature. The yield was 509 g (5.78 mols), which represented a 96% yield.
The product gave the following analyses: Found, Mg, 28.6%; NH 3 , 38.5%; BH 4 - , 33.1%, Na, 0.57%; Cl, 0.80%. Calculated for Mg(BH 4 ) 2 .2NH 3 : Mg, 27.61%; NH 3 , 38.68%; BH 4 - , 33.71%.
A thermally stable magnesium borohydride diammoniate prepared by the process of this invention has been tested in combination with an oxidizer selected from KNO 3 and LiNO 3 and a binder of polytetrafluoroethylene (Teflon) to perform as a H 2 generator for laser uses. A preferred composition containing 85% magnesium borohydride diammoniate, 7.5% LiNO 3 , and 7.5% polytetrafluoroethylene possessed high crush strength in pellet form, a requirement of the physical integrity of gas generator pellets, and a H 2 weight percent yield exceeding 12 percent when test fired using 0.5 and 1.0 inch-diameter pelletized composition in 100 to 600 grams test firings.
The preparation of Mg(BD 4 ) 2 .2ND 3 and Mg(BD 4 ) 2 .3ND 3 to give a pure deuterium generator would involve the use of ND 3 rather than NH 3 and NaBD 4 rather than NaBH 4 in the examples given under the "Description of The Preferred Embodiment", hereinabove.
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A direct low temperature process for the preparation of pure magnesium borohydride diammoniate or the deuterated analog thereof based on the addition of 90-95% of the stoichiometric amount of NH 3 to an excess of Mg(BH 4 ) 2 .X(C 2 H 5 ) 2 O in a benzene reaction solvent in accordance with equation 1: ##STR1## wherein X is a numeral from about 2.0 to about 2.5; or when the reaction is conducted in an ether reaction solvent with the same quantities of reactants and under the same experimental conditions, the triammoniate or the deuterated analog thereof is formed in accordance with equation 2: ##STR2## wherein X is a numeral from about 2.0 to about 2.5. In either case the pure product is readily isolated by filtration, solvent washing to remove excess Mg(BH 4 ) 2 .X(C 2 H 5 ) 2 O, and vacuum drying at ambient temperature. Yields are 95-99%; purities are typically about 97%.
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This invention has been filed under the Disclosure Document Program as Document No. 345,276 and is a continuation in part of Ser. No. 08/196,700 filed Feb. 15, 1994 now U.S. Pat. No. 5,460,121.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to safe-guarding the home environment from the unhealthy distribution of domesticated animal hair, dander, dirt, flea eggs, lice, and ticks, particularly by trapping and confining within its interior, the unwanted pollutants and debris.
2. Background--Discussion of the Prior Art
With the current economy requiring two incomes to support a higher standard of living, more couples find that their animals are left at home unattended for longer periods of time. Most families more or less live with the problem of animal hair since there are no effective devices available on the market to solve the problem. The first problem is the constant evidence of animal hair throughout the home. The second problem is that certain parts of the upholstered furniture become rubbing posts, leaving accumulations of hair as well as the dirt from the animal's body. While many pets are strictly confined to the house, there are many pets permitted to be outdoors. This outdoor freedom not only adds additional dirt to the body hair, but the animal can carry fleas, lice, and ticks to the interior of the living environment. The problem is particularly bad in the sub-tropics where flea and tick infestation is rather prevalent.
There are many devices on the market for self-grooming of animals. Among the prior art devices is a device that attaches to the lower part of a wall. This device only provides another additional location for hair deposits, mainly on the floor, along with soiling of the walls from the animal's body. It is well known that during any type of brushing action performed by hand or self-brushing by an animal, a significant amount of hair falls from even the best brush, but considerably more so from the animal's self-brushing efforts.
Prior art devices are basically directed to two types of self grooming devices, one type is identified as a walk-through or crawl-through device. These are devices that the animal may walk or crawl through and brush, rake, or scratch itself during the walk-through process. These are shown for example in U.S. Pat. Nos. 2,865,329 to Elliot, 2,976,841 to Scheffer, and 4,301,766 to Piccone. The patents to Elliot and Scheffer are very similar in construction and purpose. It was found that with a device similar to Scheffer, it was necessary to add catnip as an incentive to promote interest. The results, after one month of observation, revealed an occasional penetration of the animal's body to the shoulders, at most, while in the act of scratching or rubbing on the grooming medium. Close examination of the floor below the device showed animal hair available for dispersion by air movement.
The natural instinct most pets have to conceal, or hide themselves in various places or recesses, is irresistible as long as these places or recesses are not threatening to their inherent psychology. The prior art is basically directed to two types of self-grooming devices. U.S. Pat. No. 4,301,766 to Piccone discloses a furniture device for cats comprising a basic housing design being generally rectangular and defining a plurality of circular apertures in the sides. Each aperture is designed to receive a frame which is annular and includes a grooming device such as a brushing or combing device extending inwardly across the opening. Individual structures are attached to each other. Brushes or combs do not effectively hold all hair yielded by an animal's coat. As an animal enters an opening containing a brush, substantial hair will fall from the exterior of the device to the floor. If the animal exits through the same opening with the same brush, hair already attached to the brush can be rolled forward on the brush in small clumps and fall to the floor if the brushes are not keep clean. These brush widths are very limited in retaining hair because of their lack of depth. As the animal enters the cubicle, passes through the brush, and rests on the cubicle floor, the loose hairs on the cubicle floor will readily adhere to the animal's under body and be carried out when the animal exits. There is no brushing means at the bottom of the annular rings to grip the hair as the animal exits the cubicle. This device does not exhibit the ability to successfully confine any significant amounts of hair, dander, dirt, flea eggs, fleas, lice, or ticks.
U.S. Pat. No. 4,807,569 to Leopold discloses a grooming device comprising a toothed plate securable to a wall, corner or other supporting fixture. An aperture plate having holes positioned to correspond to the location of the teeth on the toothed plate mesh with the teeth and cover a portion of each tooth for providing added strength to and stiffening of each tooth when closed, a teeth straightening function upon opening and closing the two plates and a teeth cleaning function upon opening of the plates. Although the teeth do contain some animal hair, most of the hair falls to the floor below the device, ready to become scattered by a simple passage of a human stirring the air or by use of a ceiling fan.
U.S. Pat. No. 4,907,540 to Reynolds discloses a device for removal of loose hair and fur balls from a cat having a frame mounted to a wall. Attached to the frame are two planar surfaces with catnip receptacles and a plurality of bristles. The plurality of bristles are of appropriate number, placement and size to catch and hold a cat's loose fur.
U.S. Pat. No. 5,176,105 to Madden discloses a grooming apparatus having a base portion, and a twisted wire connected to the base portion. Brush bristles are retained by and extend radially from the spiral twist of the wire for brushing a live animal as it passes against the bristles. As in the other prior art devices, any hair, debris or pollutants that may fall from the animal, will remain on the floor until the animal, or a draft of air scatters it throughout the environment.
In summary, none of the prior art devices have provided a positive solution to the above mentioned animal problems that seriously affects the many living environments where animals are kept.
SUMMARY OF THE INVENTION
Generally, the present invention comprises a structure in the form of a mailbox configuration. The interior of the enclosure supports a complete array of brush bristles or a rubbing medium throughout both vertical sides and top. The base of the enclosure has a plurality of recessed, slotted openings, which will allow surplus hair, dander, dirt, flea eggs, fleas, lice and ticks that might fall from rubbing medium, or animal, to fall to the bottom of these slotted openings for complete confinement to prevent carry out. In addition, a strip of plush carpeting is attached at both ends of the enclosure's base, to further the confinement of debris to the interior of the device and not the living environment.
It is therefore an object of the invention to materially enhance the human living environment of animal owners by reducing the amount of hair, dander, dirt and other airborne pollutants carried by domestic animals and associated with allergies.
It is another object of the invention to provide a device that would receive the entire body of an animal to insure entrapment of pollutants and debris.
It is a still further object of the invention to provide a device that can be made in many sizes, inexpensively, to accommodate any requirement.
Still another object of the invention is to provide a device constructed as one integral piece, compromising the enclosure, rubbing medium, and a base having a plurality of recessed, elongated slots for debris confinement and "paw-gripping".
Yet another object of the invention is to provide a device that serves as a substitute rubbing medium to protect furniture or other areas of the home.
Other advantages of the present invention will be readily understood by reference to the following detailed description when considered in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view, partially in section, of a preferred embodiment of the invention.
FIG. 2 is a perspective view of a flexible rubbing medium of the invention.
FIG. 3 is a perspective view of a second embodiment of the invention.
FIG. 4 is a perspective view of a disassembled second embodiment of the invention.
FIG. 5 is a perspective view of a third embodiment of the invention.
FIG. 6 is a perspective view of a fourth embodiment of the invention.
FIG. 7 is a fifth embodiment of the invention showing a "donut-shaped" enclosure.
FIG. 8 is a perspective view, in section, of the embodiment shown in FIG. 7.
FIG. 9 is an exploded perspective view of the embodiment shown in FIG. 7.
FIG. 10 is a perspective view of rigid, preformed rubbing medium with ground anchors.
FIG. 11 is a perspective view of an expandable version of the invention.
FIG. 12 is an exploded perspective view showing several sizes in dashed lines.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1 and 2 are perspective views of the animal hair confinement enclosure of the present invention and comprises a rigid enclosure 10, open at both ends, a flexible rubbing medium 12 that is removable, a base 14, a slotted or perforated base floor 16 supported in the base housing 14. The front of base 14 contains a slot 17 to accommodate a removable debris tray or drawer 20. A rubbing medium void area 18 is located at each end of the enclosure 10 and a narrow strip of plush carpeting 22 is attached to each of the extreme ends of the perforated base floor 16.
Rigid enclosure 10, formed in the shape of a mailbox, is sufficiently long to receive the entire animal, except the tail, to ensure the confinement of all debris released by the animal's rubbing act. Enclosure 10 may be formed from plastic or metal or other practical material, and sized to fit the average cat or dog size. Larger versions may be formed to accommodate larger animals. To simplify the vacuuming and sanitizing of accumulated animal debris from the brushing or rubbing medium 12, medium 12 is made removable by simply sliding it from the enclosure 10. Base floor 16 is perforated or slotted to keep the floor 16 surface clear by passage of the animal debris through the slotted or perforated openings 19. The slotted or perforated openings 19 also provide a means for "paw-gripping".
Base 14 is designed to support the enclosure 10. the perforated base floor 16, and to house the debris tray 20. Debris tray 20, fits into tray guide 17, located below perforated base floor 16, and collects and confines the animal debris fallen from the brushing or rubbing medium 12 for easy disposal. The debris tray 20 may also be treated with flea powder to provide an added benefit of killing fleas and their eggs. The rubbing medium 12 is shorter than the enclosure 10 to provide a strip or void 18 at each end of enclosure 10 to prevent hair and debris from falling to the outside of the enclosure 10 when the animal is ribbing or scratching near the openings of the device.
Rubbing medium 12 shown in a flat condition in FIG. 2, may be made in a sheet of plastic or carpeting or suitable material with bristles 23 that are of sufficient stiffness to provide the brushing comfort desired by the animal and to pull the loose hairs or debris from the animal. The bristles 23 may also be designed to release hair and debris when the animal departs. The bristles 23 may also be formed integrally with the backing when molding rubbing medium 12 from certain materials.
FIGS. 3 and 4 are perspective views of a second embodiment in an assembled and an unassembled form. A rigid base 14 having a slotted base floor 16 along its entire length. Said slotted base floor formed from a plurality of elongated openings 19. A plurality of attachment dowel openings 31 positioned along a first edge of said base 14. A flexible brushing medium 12 is provided. A flexible hinge or living hinge 24 attaches said brushing medium to an opposite second edge of said base. A plurality of attachment dowels are positioned along an edge of said flexible brushing medium. Each attachment dowel can be removably positioned in a respective attachment dowel opening, such that when assembled forms an enclosure having a mailbox configuration. The flexible brushing medium 12 further including a reduced thickness portion 26 to insure correct bending, curving or shaping when assembled. Elongated openings 19 in base 14 keep the floor clear of hair or debris by containing any fallen hair or debris from an animal. Further, the openings 19 allow for paw gripping when in use by an animal. A brushing medium void area 18 is provided to limit hair and debris from falling outside the device when an animal is rubbing near the ends, such that the void area does not grip any hair or debris from an animal.
FIG. 5 is a perspective view of a third embodiment which comprises a tubular enclosure 10 and rubbing medium 12 as one integral unit, which may be inserted in or removed from the elongated guide tracks 31 of the base 14, a rubbing medium void area 18 and a strip of carpeting 22 the entire length of the base 14. This embodiment of enclosure 10 will house smaller animals such as hamsters, gerbils and mice in a practical manner. The rubbing medium 12 is an integral part of the enclosure 10 that traps and confines debris from the animal's rubbing motion. The base 14 is furnished with recessed, elongated tracks 31 for the attachment of the integrally made enclosure 10 and rubbing medium 12. The tracks 31 provide a convenient means for removing the tubular enclosure 10 for ease of cleaning. The plush carpet 22, extending the entire length of the base floor 14 is provided for debris retention and "paw-gripping".
FIG. 6 is a perspective view of a fourth embodiment of the invention which comprises a rigid, tube-like enclosure 10 rubbing medium 12 and base 14 formed as one integral unit. The embodiment features an opening 25 of the uppermost portion of the enclosure 10 and a strip of plush carpeting 22 the entire length of the base floor 16 with a rubbing medium void area 18. The opening 25 is an elongated section removed from the top of the tubular or pipe enclosure 10, partially exposing the interior for human viewing and amusement as the animal uses the rubbing medium or for timid animals that will not use a completely enclosed space.
FIGS. 7-9 are several views of a fifth embodiment which comprises a split circle or donut shaped enclosure 10 with a plurality of openings, including an open lure slot 32 and entrances 33. The circular shaped enclosure 10 comprises a circular base 14, a rubbing medium 12, permanently attached to the interior walls and top of enclosure 10, a carpet 22 fastened throughout the base floor 14, and an open slot 32 formed at the top end of the enclosure. A lure handle 34, for manipulating a lure 36 riding on a breakable string 35 is suspended through the open slot 32. As shown in FIG. 9, the enclosure 10 is shown in an exploded view with the inner enclosure portion 37, the outer enclosure portion 39, circular base 14, and rubbing medium 12, permanently installed therein to both sides and the top. Each of the parts of the enclosure 10, the inner enclosure portion 37 and the outer enclosure portion 39 are fastened to the base 14 with attachment blades 38 which are inserted into attachment blade openings 42 which are used as fasteners to firmly secure the enclosure 10 assembly to the base 14. A plush type carpet 22 is attached to the entire floor area of the base 14 for containing fallen debris from the rubbing animal as it embeds or adheres to the thick nap of the carpet. The carpet 22 also serves as a means for "paw-gripping".
FIG. 10 discloses a rigid, preformed enclosure or single sheet member 10 having opposite elongated sides 13 with an arcuate top 15 connected to the sides 13 having the shape of a mailbox configuration. A rubbing medium having a plurality of bristles 12 are connected to an interior surface of said enclosure. The enclosure further includes an open base or open bottom 14, and first and second open ends 17. Mounting brackets 42 are connected to the elongated sides 13 and removably receive a mounting peg 43 that allow the enclosure to be fixedly attached to a ground surface. Enclosure 10 may be anchored to the ground for outdoor domestic animals or animals in a zoo habitat for the benefit of maintaining a better coat by way of "self-scratching". This self-scratching allows for flea and tick removal, animal satisfaction, improvement in the animal's appearance and general well-being.
FIGS. 11 and 12 disclose an animal enclosure 10 which may be expanded to accommodate many sizes of animals. The enclosure 10 includes a base 14 having a plurality of recessed elongated tracks 30. Enclosure 10 comprises straight portions 45 such that each straight portion forms an elongated side of said enclosure 10. A curved portion 47 forming a top of said enclosure. Each curved portion 47 having a pair of elongated parallel bottom edges, an insert edge 50 positioned on each bottom edge along its entire length. A rubbing or brushing medium 12 having a plurality of bristles are positioned about the enclosure interior. A rubbing medium void area 18 is provided at each end of said enclosure. A slotted base floor 16 having a plurality of slotted openings 19 that contain any fallen hair and/or debris from the animal. FIG. 11 depicts the enclosure 10 with a curved portion 47 sized for a medium size animal. Each straight portion 45 having a T-shaped rail 51 on its bottom edge such that the rail 51 is slidably received in a respective elongated track 30. Further, each straight portion having a slot 49 positioned on a top edge along its entire length. Each slot 49 receives a respective insert edge 50 of said curved portion.
FIG. 12 depicts an exploded view of the enclosure 10 with curved portion 47 sized for a medium size animal and the other two sizes are shown in dashed lines. To adjust the size of said enclosure 10, a larger curved portion 47 can be selected and connected to a respective pair of said straight portions 45. Additionally, each straight portion of a selected pair of straight portions can be positioned in a respective elongated track 30, said tracks can be positioned on said base at alternate spacings to accommodate the selected curved portion. A larger spacing would accommodate a larger animal. Conversely, a narrower spacing between a pair of elongated tracks and a smaller curved portion would accommodate a smaller animal.
Thus it has been shown that the animal hair confinement enclosure of the present invention can perform all of the objectives outlined above more completely than any of the prior art devices. While the specification contains many specific details, these should not be construed as limitations on the scope of the invention, but rather as examples of embodiments herein detailed in accordance with the descriptive requirements of law, it should be understood that the details are to be interpreted as illustrative and not in a limiting sense.
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An expandable animal hair confinement device comprising, a base 14 containing a series of recessed slotted openings 30 employing a pair of vertical sides 45 with slideable rails 51. One of several arched cover portions 47 are mated to the vertical sides to house the entire body of an animal of a particular size. The base 14 contains a series of reccessed slotted openings 19, and the vertical sides 45, and arched covers 47 contain bristles 12 throughout one side of their surfaces.
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[0001] This application is a divisional of U.S. Ser. No. 11/385,331 filed on Mar. 21, 2006 which is a continuation of U.S. Ser. No. 10/448,851, filed May 30, 2003, which claims the benefit of U.S. Provisional Application No. 60/415,788 filed Oct. 3, 2002 and benefit of priority from German Application No. 10224892.3, filed Jun. 4, 2002.
FIELD OF THE INVENTION
[0002] The invention relates to the substituted thiophene compounds of formula I useful for treating and/or preventing various disorders. More particularly, the invention relates to the substituted thiophene compounds of formula I possessing potent inhibitory properties on the sodium/proton exchanger of subtype 3 (“NHE3”), which makes the compounds useful, in the form of a medicament, for the treatment of respiratory disorders and for the improving of the respiratory drive, for the treatment of acute and chronic disorders, ischemic and/or reperfusion disorders and disorders triggered by cellular proliferative or fibrotic events, and for the treatment of disorders of the central nervous system and lipid metabolism, and diabetes, blood coagulation and infection by parasites.
BACKGROUND OF THE INVENTION
[0003] NHE3 is found in the body of various species, for example, in the gall bladder, the intestine and the kidney (Larry Fliegel et al., Biochem. Cell. Biol. 76: 735-741, 1998), but can also be detected in the brain (E. Ma et al., Neuroscience 79: 591-603).
[0004] The NHE3 inhibitors known to date are derived from compounds of the acylguanidine type (EP825178), of the norbornylamine type (DE199 60 204), of the 2-guanidino-quinazoline type (WO 0179186) or of the benzamidine type (WO0121582, WO172742). Squalamine, which has also been described as NHE3 inhibitor (M. Donowitz et al. Am. J. Physiol. 276 (Cell Physiol. 45): C136-C144), is, according to current understanding, not, unlike the compounds of formula I, effective immediately, but rather via an indirect mechanism and thus reaches its maximum potency only after one hour. Such NHE3 inhibitors which act by a different mechanism are therefore suitable for use as combination partners for the present compounds according to the invention.
[0005] Clonidine, which is similar to the compounds described here, is known as a weak NHE inhibitor. However, its action on the NHE3 of the rat is, with a half-maximal inhibitory concentration (IC 50 ) of 620 μM, extremely moderate. In contrast, it shows a certain selectivity for the NHE2 (J. Orlowski et al. J. Biol. Chem. 268, 25536). It would therefore be more accurate to refer to clonidine as an NHE2 inhibitor. In addition to the weak NHE action, clonidine has a high affinity for the adrenergic alpha2 receptor and the imidazoline I1 receptor, mediating a strong hypotensive action (Ernsberger et al., Eur. J. Pharmacol. 134, 1, 1987).
[0006] Clonidine-like compounds having a thiophene ring instead of the phenyl ring are known from DE1941761. These known compounds differ from the structures of formula I described in the present invention in that they have considerably smaller radicals R7 and R8 and in particular by the fact that R7 and R8 are not capable of forming a joint ring.
[0007] By these differences in the substituents R7 and R8, it is possible to eliminate the undesirable clonidine-like cardiovascular effects described above, which are mediated by the alpha-adrenoceptor action. At the same time, owing to these differences in the substituents, the NHE-inhibiting properties of the compounds described herein are enhanced to the micromolar and submicromolar range, whereas the compounds known from DE1941761 show only extremely weak NHE-inhibiting effects, if any.
[0008] The present invention provides a different kind of NHE3 inhibitors.
SUMMARY OF THE INVENTION
[0009] A primary object of the present invention is to provide compounds of formula I
in which:
R 1 and R 2
independently of one another are H, F, Cl, Br, I, CN, NO 2 , —(X) n —C q H 2q -Z, cycloalkyl having 3, 4, 5 or 6 carbon atoms, alkenyl having 2, 3 or 4 carbon atoms, alkenylalkyl having 3 or 4 carbon atoms, ethynyl or alkylalkynyl having 3 or 4 carbon atoms; n is zero or 1; X is oxygen, NH, N—CH 3 , S(O) k ;
k is zero, 1 or 2;
q is zero, 1, 2, 3, 4, 5 or 6; Z is hydrogen or C m F 2m+1 ;
m is zero, 1, 2, 3 or 4;
R 3 is hydrogen, methyl, F, Cl, Br, I, CN, S(O) k —CH 3 , —NO 2 , —O—CH 3 ;
k is zero, 1 or 2;
R4 is hydrogen, cycloalkyl having 3, 4, 5, or 6 carbon atoms, alkenyl having 2, 3 or 4 carbon atoms, alkenylalkyl having 3 or 4 carbon atoms, ethynyl or alkylalkynyl having 3 or 4 carbon atoms, —C r H 2r —Y;
r is zero, 1, 2, 3 or 4; Y is hydrogen or trifluoromethyl;
R5 and R6 are hydrogen or together are a bond; R7 and R8
independently of one another are (C 3 -C 5 )-alkyl, (C 2 -C 5 )-alkenyl, (C 2 -C 5 )-alkynyl, (C 3 -C 6 )-cycloalkyl or (C 4 -C 6 )-cycloalkenyl
or
R7 and R8
together are an alkylene chain comprising 3 to 8 carbon atoms; where none, some or all of their hydrogen atoms may be replaced by fluorine atoms;
or
R7 and R8
together are a radical
where R5 and R6 together form a bond; R10 and R11
independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, CN, OH, —O—CH 3 , NO 2 , NH 2 or —CF 3 ;
R9 and R12
are hydrogen or F;
or one of the substituents R9 and R12
is hydrogen; and the other is F, Cl, Br, I, CN, NO 2 , COOH, CO—NR13R14, SO 2 —NR13R14, alkenyl having 2, 3 or 4 carbon atoms, alkenylalkyl having 3 or 4 carbon atoms, ethynyl, alkylalkynyl having 3 or 4 carbon atoms or —(X) n —C q H 2q -Z; R13 and R14
are identical or different hydrogen or alkyl having 1, 2, 3 or 4 carbon atoms;
or R13 and R14 together with the nitrogen to which they are attached form a saturated 5-, 6- or 7-membered ring; n is zero or 1; X is oxygen, NH, N—CH 3 , S(O) k ;
k is zero, 1 or 2;
q is zero, 1, 2, 3, 4, 5 or 6; and Z is hydrogen or C m F 2m+1 ;
m is zero, 1, 2, 3 or 4;
and their pharmaceutically acceptable salts, and their trifluoroacetic acid salts.
[0050] One embodiment relates to compounds of formula I in which
R1 and R2
independently of one another are H, F, Cl, Br, I, CN, NO 2 , —(X) n —C q H 2q -Z, cycloalkyl having 3, 4, 5 or 6 carbon atoms, alkenyl having 2, 3 or 4 carbon atoms, alkenylalkyl having 3 or 4 carbon atoms, ethynyl or alkylalkynyl having 3 or 4 carbon atoms; n is zero or 1; X is oxygen, NH, N—CH 3 , S(O) k ;
k is zero, 1 or 2;
q is zero, 1, 2, 3, 4, 5 or 6; Z is hydrogen or C m F 2m+1 ;
m is zero, 1, 2, 3 or 4;
R3 is hydrogen, methyl, F, Cl, Br, I, CN, S(O) k —CH 3 , —NO 2 , —O—CH 3 ; R4 is hydrogen, cycloalkyl having 3, 4, 5, or 6 carbon atoms, alkenyl having 2, 3 or 4 carbon atoms, alkenylalkyl having 3 or 4 carbon atoms, ethynyl or alkylalkynyl having 3 or 4 carbon atoms, —C q H 2q -Z;
q is zero, 1, 2, 3 or 4; Z is hydrogen or trifluoromethyl;
R5 and R6
are hydrogen or together are a bond;
R7 and R8
independently of one another are (C 3 -C 5 )-alkyl, (C 2 -C 5 )-alkenyl, (C 2 -C 5 )-alkynyl, (C 3 -C 6 )-cycloalkyl or (C 4 -C 6 )-cycloalkenyl
or
R7 and R8
together are an alkylene chain comprising 3 to 8 carbon atoms; where none, some or all of their hydrogen atoms may be replaced by fluorine atoms;
or
R7 and R8
together are a radical
where R5 and R6 together form a bond; R9, R10 and R11
independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, CN, OH, —O—CH 3 , NO 2 , NH 2 or —CF 3 ;
R9 and R12
are hydrogen;
or one of the substituents R9 and R12
is hydrogen; and the other is F, Cl, Br, I, CN, NO 2 , COOH, CO—NR13R14, SO 2 —NR13R14, alkenyl having 2, 3 or 4 carbon atoms, alkenylalkyl having 3 or 4 carbon atoms, ethynyl, alkylalkynyl having 3 or 4 carbon atoms or —(X) n —C q H 2q -Z; R13 and R14
are identical or different hydrogen or alkyl having 1, 2, 3 or 4 carbon atoms;
n is zero or 1; X is oxygen, NH, N—CH 3 , S(O) k ;
k is zero, 1 or 2;
q is zero, 1, 2, 3, 4, 5 or 6; and Z is hydrogen or C m F 2m+1 ;
m is zero, 1, 2, 3 or 4;
and their pharmaceutically acceptable salts, and their trifluoroacetic acid salts.
[0089] Preference is given to compounds of formula I, in which:
R1 and R2
independently of one another are H, F, Cl, Br, CH 3 , CF 3 , SO 2 CH 3 , SO 2 NH 2 ; but where at most one of the substituents R1 and R2 is hydrogen;
R3 is hydrogen, F or Cl; R4 is hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms, or cyclopropyl; R5 and R6
are hydrogen or together are a bond;
R7 and R8
together are an alkylene chain comprising 3, 4, 5, 6, 7 or 8 carbon atoms;
or
R7 and R8
together are a radical
where R5 and R6 together form a bond; R10 and R11
independently of one another are hydrogen, OH, fluorine or chlorine;
R9 and R12
are hydrogen;
or one of the substituents R9 and R12
is hydrogen; and the other is F, Cl, Br, CN, COOH, CO—NR13R14, SO 2 —NR13R14 or —(X) n —C q H 2q -Z; R13 and R14
are identical or different hydrogen or methyl;
n is zero or 1; X is oxygen, NH, N—CH 3 or S(O) k ;
k is zero, 1 or 2;
q is zero, 1, 2, 3 or 4; Z is hydrogen or CF 3 ;
and their pharmaceutically acceptable salts, and their trifluoroacetic acid salts.
[0116] Particular preference is given to compounds of formula I in which:
R1 and R2
independently of one another are F, Cl, Br, CH 3 or CF 3 ;
R3 is hydrogen; R4 is hydrogen, methyl, ethyl; R5 and R6
are hydrogen or together are a bond;
R7 and R8
together are an alkylene chain comprising 3, 4, 5, 6, 7 or 8 carbon atoms; or
R7 and R8
together are a radical
where R5 and R6 together form a bond; R10 and R11
independently of one another are hydrogen, OH or fluorine;
R9 and R12
are hydrogen;
or one of the substituents R9 and R12
is hydrogen; and the other is F, Cl, Br or —(X) n —C q H 2q -Z; n is zero or 1; X is oxygen, NH, N—CH 3 or S(O) k ;
k is zero, 1 or 2;
q is zero or 1; Z is hydrogen or CF 3 ;
and their pharmaceutically acceptable salts, and their trifluoroacetic acid salts.
[0141] Very particular preference is given to the following compounds of formula I, selected from the group consisting of:
trans-R,R-2-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine, trans-R,R-2-bromo-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine, 2-chloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine, 2-bromo-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine, 2-chloro-3N-(4-methyl-2-benzimidazolyl)-4-methyl-3-thienylamine, 2-chloro-3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine, 2-chloro-3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene, 2-bromo-3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene, 2-bromo-3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene, 2-chloro-3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene, 2-chloro-3N-(4-hydroxy-2-benzimidazolylamino)-4-methylthiophene, (1H-benzimidazol-2-yl)-(2-chloro-4-methylthiophen-3-yl)-methylamine, (2-bromo-4-methylthiophen-3-yl)-(5-fluoro-1H-benzimidazol-2-yl)-amine, 2,4-dichloro-3N-(2-benzimidazolylamino)thiophen, 2-bromo-4-chloro-3N-(2-benzimidazolylamino)thiophen, 2,4-dichloro-3N-(4-methyl-2-benzimidazolyl-amino)thiophen, trans-R,R-2,4-Dichlor-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamin, 2,4-dichloro-3N-(4-chlor-2-benzimidazolyl-amino)thiophen
and
2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene
and their pharmaceutically acceptable salts, for example the hydrochloride or the hydrobromide or the methanesulfonate of each of the compounds.
[0159] The compounds of formula I can be present in the form of their salts. Suitable acid addition salts are salts of all pharmacologically acceptable acids, for example halides, in particular hydrochlorides, hydrobromides, lactates, sulfates, citrates, tartrates, acetates, phosphates, methylsulfonates, benzenesulfonates, p-toluenesulfonates, adipinates, fumarates, gluconates, glutamates, glycerolphosphates, maleates, benzoates, oxalates and pamoates. This group also corresponds to the physiologically acceptable anions; but also trifluoroacetates.
[0160] If the compounds contain an acid group, they are capable of forming salts with bases, for example as alkali metal salts, preferably sodium or potassium salts, or as ammonium salts, for example as salts with ammonia or organic amines or amino acids. They can also be present as zwifterion.
[0161] If the compounds of formula I contain one or more centers of asymmetry, the compounds can independently be both S- and R-configured. The compounds can be present as optical isomers, as diastereomers, as racemates or as mixtures thereof.
[0162] The compounds of formula I can furthermore be present as tautomers or as a mixture of tautomeric structures. This refers, for example, to the following tautomers:
[0163] Alkyl radicals can be straight-chain or branched. This also applies when they carry substituents or are present as substituents of other radicals, for example in fluoroalkyl radicals or alkoxy radicals. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl (=1-methylethyl), n-butyl, isobutyl (=2-methylpropyl), sec-butyl (=1-methyl-propyl), tert-butyl (=1,1-dimethylethyl), n-pentyl, isopentyl, tert-pentyl, neopentyl or hexyl. Preferred alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. In alkyl radicals, one or more, for example 1, 2, 3, 4, 5, 6, 7, 8 or 9, hydrogen atoms may be substituted by fluorine atoms. Examples of such fluoroalkyl radicals are trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoroisopropyl. Substituted alkyl radicals may be substituted in any positions.
[0164] Alkenyl radicals may be straight-chain or branched. This also applies when they are present as substituents, for example in alkenylalkylene. The alkenyl radicals can be unsaturated in different positions. Examples of alkenyl radicals are ethenyl, propenyl or butenyl.
[0165] Alkynyl radicals can be straight-chain or branched. This also applies when they are present as substituents, for example in alkynylalkylene. The alkynyl radicals can be unsaturated in different positions. Examples of alkynyl radicals are ethynyl, propynyl or butynyl.
[0166] Examples of cycloalkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Substituted cycloalkyl radicals can be substituted in any positions. The cycloalkyl radicals may also be present branched as alkylcycloalkyl or cycloalkylalkyl.
[0167] Also described are methods for preparing compounds according to the invention. Thus, the substances described by formula I can be prepared in a manner known to the person skilled in the art from the isothiocyanate II parent compounds and the appropriate diamines III.
[0168] The thiourea derivative which is formed as an intermediate is cyclized using methyliodide (Synthesis, 1974, 41-42) or carbodiimide (Synthesis, 1977, 864-865) or using p-toluenesulfonyl chloride to give the corresponding compound of formula I. If the isothiocyanates II employed here are not commercially available, they can be prepared in a manner known from the literature from the corresponding aminothiophene derivatives, using methods known to the person skilled in the art, for example by treatment with thiophosgene (J. Med. Chem., 1975, 18, 90-99) or thiocarbonyl diimidazole (Justus Liebigs Ann. Chem., 1962, 657, 104).
[0169] In addition to the isothiocyanates II described above, it is also possible to successfully react the isocyanates IV
with amines of the type of formula III to give the compounds of formula I. Here, the urea derivative which is formed as an intermediate is cyclized using phosphorus oxychloride to give the corresponding compounds of formula I.
[0170] In the present invention, it was surprisingly possible to demonstrate that the compounds described are potent inhibitors of the sodium/proton exchanger (NHE), in particular the sodium/proton exchanger of subtype 3 (NHE3).
[0171] Owing to the NHE-inhibitory properties, the compounds of formula I are suitable for the prevention and treatment of diseases caused by an activation of NHE or by an activated NHE, and of diseases which are sequelae of damage caused by NHE.
[0172] Since NHE inhibitors act predominantly via influencing cellular pH regulation, they can be combined in a favorable manner with other compounds which also regulate the intracellular pH, suitable combination partners being inhibitors of the enzyme group of the carbonate dehydratases, inhibitors of the bicarbonate-ion-transporting systems, such as the sodium bicarbonate cotransporter (NBC) or the sodium-dependent chloride/bicarbonate exchanger (NCBE), and also NHE inhibitors having inhibitory action on other NHE subtypes, since they can modulate or enhance the pharmacologically relevant pH-regulating effects of the NHE inhibitors described herein.
[0173] The use of the compounds according to the invention relates to the prevention and treatment of acute and chronic diseases in veterinary and human medicine.
[0174] The pharmacological action of the compounds of formula I is characterized in that they induce an improvement in the respiratory drive and can therefore be used in the treatment of disturbed respiratory conditions for example in the following clinical conditions and diseases: disturbed central respiratory drive (e.g. central sleep apnea, sudden infant death, postoperative hypoxia), muscular-related respiratory disorders, respiratory disorders after long-term ventilation, respiratory disorders during adaptation in a high mountain area, obstructive and mixed forms of sleep apnea, acute and chronic lung diseases with hypoxia and hypercapnia.
[0175] The compounds additionally increase the muscle tone of the upper airways, so that snoring is suppressed. As a result, the compounds mentioned are advantageously used for preparing a medicament for the prevention and treatment of sleep apnea and muscular-related respiratory disturbances and for preparing a medicament for the prevention and treatment of snoring.
[0176] A combination of an NHE inhibitor of formula I with a carboanhydrase inhibitor (e.g. acetazolamide) can be advantageous, the latter producing metabolic acidosis and thereby already increasing respiratory activity, may prove to be advantageous as a result of increased action and decreased use of active compound.
[0177] Owing to their NHE3-inhibitory action, the compounds according to the invention spare cellular energy resources which, during toxic and pathogenic events, are rapidly depleted, thus resulting in cell damage or cell death. Here, the high-energy ATP-consuming resorption of sodium in the proximal tubulus is, under the influence of the compounds of formula I, temporarily switched off, and the cell is thus able to survive an acute pathogenic, ischemic or toxic situation. The compounds are therefore suitable by way of example for use as drugs for treating ischemic noxa, for example acute kidney failure.
[0178] Furthermore, the compounds are also suitable for treating all chronic renal disorders and forms of nephritis which, as a consequence of increased elimination of protein, result in chronic kidney failure. Accordingly, the compounds of formula I are suitable for preparing a medicament for the treatment of diabetic late damage, diabetic nephropathy and chronic renal disorders, in particular all inflammations of the kidney (nephritides) associated with increased elimination of protein/albumin.
[0179] It has been shown that the compounds used according to the invention have mild laxative action and, accordingly, can also be used advantageously as laxatives or for the prophylaxis of intestinal obstruction.
[0180] Furthermore, the compounds according to the invention can be used advantageously for the prevention and therapy of acute and chronic disorders of the intestinal tract triggered, for example, by ischemic states in the intestinal region and/or by subsequent reperfusion or by states and events of inflammation. Such complications can occur, for example, by lack of intestinal peristalsis, as is frequently observed, for example, after surgical interventions, in the case of bowel obstruction or in cases of strongly reduced intestinal motility.
[0181] Using the compounds according to the invention, it is possible to prevent gallstone formation.
[0182] The NHE inhibitors according to the invention are generally suitable for treating diseases caused by ischemia and by reperfusion.
[0183] As a result of their pharmacological properties, the compounds according to the invention are suitable for use as antiarrhythmics.
[0184] Owing to their cardioprotective component, the NHE inhibitors of formula I are highly suitable for infarct prophylaxis and infarct treatment and for treatment of angina pectoris, and they also inhibit, or strongly reduce, in a preventative manner, the pathophysiological processes which contribute to ischemically induced damage, in particular those which trigger ischemically induced cardiac arrhythmias. Owing to their protective action against pathological hypoxic and ischemic situations, the compounds of formula I used according to the invention can, as inhibitors of the cellular Na + /H + exchange mechanism, be used as medicaments for treating all acute or chronic damage caused by ischemia, or diseases induced primarily or secondarily by this damage.
[0185] This relates to their use as medicaments for surgical interventions. Thus, the compounds according to the invention can be used for organ transplantations, where the compounds can be used both for protecting the organs in the donor before and during removal, for protecting organs that have been removed, for example during treatment with or storage in physiological bath fluids, and also during transfer into the recipient organism pretreated with compounds of formula I.
[0186] The compounds are also useful medicaments with protective action during angioplastic surgical interventions, for example on the heart, but also in peripheral organs and vessels.
[0187] Since NHE inhibitors protect human tissue and organs not only effectively against damage caused by ischemia and reperfusion but also against the cytotoxic action of medicaments used in particular in cancer therapy and the therapy of autoimmune diseases, the combined administration with compounds of formula I is suitable for suppressing or reducing the cytotoxic effects of a therapy. By reducing the cytotoxic effects, in particular cardiotoxicity, by comedication with NHE inhibitors it is furthermore possible to increase the dose of the cytotoxic therapeutics and/or to prolong medication with such medicaments. The therapeutic benefit of such a cytotoxic therapy can be enhanced considerably by combination with NHE inhibitors.
[0188] The compounds of formula I are suitable in particular for improving the therapy with medicaments having an undesirable cardiotoxic component.
[0189] Owing to their protective action against ischemically induced damage, the compounds according to the invention are also suitable for use as medicaments for treating ischemias of the nervous system, in particular the central nervous system, where they can be used, for example, for treating stroke or cerebral edema.
[0190] The compounds of formula I are also suitable for the therapy and prophylaxis of diseases and disorders induced by overexcitability of the central nervous system, in particular for the treatment of epileptic disorders, centrally induced clonic and tonic spasms, states of psychological depression, anxiety disorders and psychoses. Here, the NHE inhibitors according to the invention can be used on their own or in combination with other substances having antiepileptic action or with antipsychotic active compounds, or carbonate dehydratase inhibitors, for example acetazolamide, and also with other inhibitors of NHE or of the sodium-dependent chloride/bicarbonate exchanger (NCBE).
[0191] In addition, the compounds of formula I according to the invention are also suitable for treating types of shock, such as, for example, of allergic, cardiogenic, hypovolemic and bacterial shock.
[0192] The compounds of formula I can also be used for the prevention and treatment of thrombotic disorders since, as NHE inhibitors, they are also capable of inhibiting platelet aggregation themselves. In addition, they can prevent or inhibit excessive release of mediators of inflammation and coagulation, in particular of the von Willebrand factor and thrombogenic selecting proteins which takes place following ischemia and reperfusion. It is thus possible to reduce and eliminate the pathogenic effect of significant thrombogenic factors. Accordingly, the NHE inhibitors of the present invention can be combined with other compounds having anticoagulative and/or thrombolytic action, such as, for example, recombinant or natural tissue plasminogen activator, streptokinase, urokinase, acetylsalicylic acid, thrombin antagonists, factor Xa antagonists, medicaments with fibrinolytic action, thromboxane receptor antagonists, phosphodiesterase inhibitors, factor VIIa antagonists, clopidogrel, ticlopidine, etc. Combined use of the present NHE inhibitors with NCBE inhibitors and/or with inhibitors of carbonate dehydratase, such as, for example, with acetazolamide, is particularly beneficial.
[0193] Furthermore, the compounds of formula I according to the invention have strong inhibiting action on cell proliferation, for example on fibroblast cell proliferation and proliferation of smooth vascular muscle cells. The compounds of formula I are therefore useful therapeutics for diseases in which cell proliferation is a primary or secondary cause and can therefore be used as antiatherosclerotics, as agents against chronic kidney failure and against neoplastic diseases. Thus, they can be used for treating organ hypertrophy and hyperplasia, for example of the heart and the prostate. Compounds of formula I are therefore suitable for the prevention and treatment of cardiac insufficiency (congestive heart failure=CHF) and for the treatment and prevention of prostate hyperplasia and prostate hypertrophy.
[0194] The compounds of formula I furthermore delay or prevent fibrotic disorders. Thus, they are excellent agents for treating fibroses of the heart, and also pulmonary fibrosis, liver fibrosis, kidney fibrosis and other fibrotic disorders.
[0195] Since there is significant elevation of NHE in essential hypertensives, the compounds of formula I are suitable for the prevention and treatment of high blood pressure and of cardiovascular disorders.
[0196] Here, they can be used for the treatment of high blood pressure and of cardiovascular disorders on their own or with a suitable combination and formulation cocomponent. Thus, it is possible, for example, to combine one or more diuretics having thiazide-like action, loop diuretics, aldosterone and pseudoaldosterone antagonists, such as hydrochlorothiazide, indapamide, polythiazide, furosemide, piretanide, torasemide, bumetanide, amiloride, triamterene, spironolactone or eplerone, with compounds of formula I. Furthermore, the NHE inhibitors of the present invention can be used in combination with calcium antagonists such as verapamil, diltiazem, amlodipine or nifedipine, and also with ACE inhibitors, such as, for example, ramipril, enalapril, lisinopril, fosinopril or captopril. Further favorable combination partners include beta-blockers such as metoprolol, albuterol etc., antagonists of the angiotensin receptor and its receptor subtypes, such as losartan, irbesartan, valsartan, omapatrilat, gemopatrilat, endothelin antagonists, renin inhibitors, adenosine receptor agonists, inhibitors and activators of calcium channels, such as glibenclamide, glimepiride, diazoxide, cromakalim, minoxidil and its derivatives, activators of the mitochondrial ATP-sensitive potassium channel (mitoK(ATP) channel), inhibitors of other potassium channels, such as inhibitors of Kv1.5 etc.
[0197] Owing to their antiphlogistic action, the NHE inhibitors can be used as antiinflammatory agents. Mechanistically interesting is the inhibition of the release of mediators of inflammation. Thus, the compounds can be used alone or in combination with an antiphlogistic agent for the prevention or treatment of chronic and acute inflammatory disorders. The combination partners used are advantageously steroidal and non-steroidal antiinflammatory agents.
[0198] Moreover, it has been found that compounds of formula I exert a beneficial influence on serum lipoproteins. They can therefore be used for the prophylaxis and regression of atherosclerotic changes by excluding a causal risk factor. This includes not only primary hyperlipidemias but also certain secondary hyperlipidemias as are encountered, for example, in diabetes. Additionally, the compounds of formula I reduce infarcts induced by metabolic anomalies considerably and, in particular, lead to a significant reduction in the size and severity of the infarct induced.
[0199] Accordingly, the compounds mentioned are used advantageously for preparing a medicament for the treatment of hypercholesterolemia, for preparing a medicament for the prevention of atherogenesis, for preparing a medicament for the prevention and treatment of atherosclerosis, for preparing a medicament for the prevention and treatment of diseases induced by elevated cholesterol levels, for preparing a medicament for the prevention and treatment of diseases induced by endothelial dysfunction, for preparing a medicament for the prevention and treatment of hypertension induced by atherosclerosis, for preparing a medicament for the prevention and treatment of thromboses induced by atherosclerosis, for preparing a medicament for the prevention and treatment of ischemic damage and post-ischemic reperfusion damage induced by hypercholesterolemia and endothelial dysfunction, for preparing a medicament for the prevention and treatment of cardiac hypertrophies and cardiomyopathies and congestive heart failure (CHF), for preparing a medicament for the prevention and treatment of coronary vascospasms and myocardial infarcts induced by hypercholesterolemia and endothelial dysfunction, for preparing a medicament for the treatment of the conditions mentioned in combination with hypotensive substances, preferably with angiotensin converting enzyme (ACE) inhibitors and angiotensin receptor antagonists. A combination of an NHE inhibitor of formula I with an active compound that lowers the lipid concentration in the blood, preferably an HMG-CoA reductase inhibitor (for example lovastatin or pravastatin), the latter having hypolipidemic action, thereby enhancing the hypolipidemic properties of the NHE inhibitor of formula I, has been found to be a favorable combination with increased action and reduced use of active compound.
[0200] Thus, compounds of formula I bring about effective protection against endothelial damage of various origins. Owing to this protection of the vessels against the syndrome of endothelial dysfunction, compounds of formula I are useful medicaments for the prevention and treatment of coronary vascospasms, peripheral vascular diseases, in particular intermittent claudication, of atherogenesis and atherosclerosis, of left-ventricular hypertrophy and of dilated cardiomyopathy, and of thrombotic disorders.
[0201] Moreover, NHE inhibitors of formula I are suitable for treating non-insulin-dependent diabetes (NIDDM) where for example insulin resistance is suppressed. Here, to enhance antidiabetic efficacy and quality of action of the compounds according to the invention, it may be favorable to combine these compounds with a biguanide such as metformin, with an antidiabetic sulfonylurea, such as glyburide, glimepiride, tolbutamide, etc., a glucosidase inhibitor, a PPAR agonist, such as rosiglitazone, pioglitazone, etc., with an insulin product in a different administration form, with a DB4 inhibitor, with an insulin sensitizer or with meglitinide.
[0202] In addition to the acute antidiabetic effects, the compounds of formula I counteract the development of late complications of diabetes, and they can therefore be used as medicaments for the prevention and treatment of diabetic late damage, such as diabetic nephropathy, diabetic neuropathy, diabetic retinopathy, diabetic cardiomyopathy and other disorders which occur as a result of diabetes. In this connection, they can be combined advantageously with the antidiabetic medicaments described above under the NIDDM treatment. A combination with a favorable administration form of insulin may be of particular importance.
[0203] In addition to the protective effects against acute ischemic events and subsequent likewise acute reperfusion events, the NHE inhibitors of formula I according to the invention also have direct therapeutically useful action against disorders and impairments of the entire mammalian organism which are associated with manifestations of the chronically progressing aging process and can also be independent of acute states of hypoperfusion, also occurring under normal, non-ischemic conditions. These pathological age-related manifestations, such as disease, illness and death, induced over the long time of aging, which are now accessible to treatment with NHE inhibitors, are disorders and disturbances caused to a substantial extent by age-related changes in vital organs and their function which become more and more important in the aging organism.
[0204] Disorders associated with age-related dysfunction and age-related symptoms of wear of organs are, for example, inadequate responsiveness and reactivity of the blood vessels to contraction and relaxation reactions. This age-related decline in vascular reactivity to constricting and relaxing stimuli, which are an essential process of the cardiovascular system and thus of life and health, can be significantly diminished or abolished by NHE inhibitors. An important function and a measure of the maintenance of vascular reactivity is the blocking or slowing of the age-related progression of endothelial dysfunction, which can be abolished highly significantly by NHE inhibitors. The compounds of formula I are thus outstandingly suitable for the treatment and prevention of the age-related progression of endothelial dysfunction, especially of intermittent claudication. Moreover, the compounds of formula I are thus outstandingly suitable for the treatment and prevention of cardiac insufficiency, of congestive heart failure (CHF), and for the treatment and in particular for the prevention of age-related types of cancer.
[0205] Consideration may likewise be given to combination with hypotensive medicaments, such as with ACE inhibitors, angiotensin receptor antagonists, diuretics, Ca 2+ antagonists, etc., or with metabolism-normalizing medicaments, such as cholesterol-lowering agents. The compounds of formula I are thus suitable for the prevention of age-related tissue changes and for prolonging life while maintaining a high quality of life.
[0206] The compounds of the invention are effective inhibitors of the cellular sodium/proton antiporter (Na/H exchanger) which, in numerous disorders (essential hypertension, atherosclerosis, diabetes, etc.), is also elevated in cells which are easily amenable to measurements, such as, for example, in erythrocytes, platelets or leukocytes. The compounds used according to the invention are therefore suitable as excellent and simple scientific tools, for example in their use as diagnostic aids for the determination and differentiation of particular types of hypertension, but also of atherosclerosis, of diabetes and of late complications of diabetes, of proliferative disorders, etc.
[0207] NHE3 inhibitors are furthermore suitable for treating disorders (human and veterinary) caused by bacteria and by protozoa. In the case of disorders caused by protozoa, particular mention may be made of malaria diseases of man and of coccidiosis in poultry.
[0208] Moreover, the compounds are suitable as agents for controlling sucking parasites in human and veterinary medicine and in crop protection. Here, the use as an agent against blood-sucking parasites in human and veterinary medicine is preferred.
[0209] The compounds of the formula I are characterised apart from their potent NHE inhibition values, their pharmacological properties and the absence of unwanted biological effects also by favorable pharmacokinetic properties, which let their use as medicaments appear particularly favorable.
[0210] The invention thus relates to medicaments for human, veterinary or phytoprotective use which comprise an effective amount of a compound of formula I and/or a pharmaceutically acceptable salt thereof alone or in combination with other pharmacologically active compounds or medicaments.
[0211] Medicaments comprising a compound I can be administered, for example, orally, parenterally, intramuscularly, intravenously, rectally, nasally, by inhalation, subcutaneously or by suitable transcutaneously administration with the preferred administration being dependent on the particular appearance of the disorder. Here, the compounds I can be used alone or together with pharmaceutical excipients, both in veterinary medicine and in human medicine and in crop protection.
[0212] Excipients suitable for the desired pharmaceutical formulation are familiar to the skilled worker on the basis of his expert knowledge. Besides solvents, gel formers, suppository bases, tablet excipients and other active ingredient carriers, it is possible to use, for example, antioxidants, dispersants, emulsifiers, antifoams, masking flavors, preservatives, solubilizers or colorants.
[0213] For a form for oral use, the active compounds are mixed with the additives suitable for this purpose, such as carriers, stabilizers or inert diluents, and converted by conventional methods into suitable dosage forms such as tablets, coated tablets, two-piece capsules, aqueous, alcoholic or oily solutions. Examples of inert carriers which can be used are gum arabic, magnesia, magnesium carbonate, potassium phosphate, lactose, glucose or starch, especially corn starch. Preparation can moreover take place both as dry and as wet granules. Examples of suitable oily carriers or solvents are vegetable or animal oils such as sunflower oil or fish liver oil.
[0214] For subcutaneous, percutaneous or intravenous administration, the active compounds used are converted into a solution, suspension or emulsion, if desired with the substances customary for this purpose, such as solubilizers, emulsifiers or other excipients. Examples of suitable solvents are: water, physiological saline or alcohols, for example ethanol, propanol, glycerol, and also sugar solutions, such as glucose or mannitol solutions, or else a mixture of the various solvents mentioned.
[0215] Suitable as pharmaceutical formulation for administration in the form of aerosols or sprays are, for example, solutions, suspensions or emulsions of the active compound of formula I in a pharmaceutically acceptable solvent, such as, in particular, ethanol or water, or a mixture of such solvents.
[0216] The formulation may, if required, also comprise other pharmaceutical excipients such as surfactants, emulsifiers and stabilizers, and a propellant gas. Such a preparation normally contains the active compound in a concentration of about 0.1 to 10, in particular of about 0.3 to 3% by weight.
[0217] The dosage of the active compound of formula I to be administered and the frequency of administration depend on the potency and duration of action of the compounds used; also on the nature and severity of the disease to be treated, and on the sex, age, weight and individual response of the mammal to be treated.
[0218] On average, the daily dose of the compound of formula I for a patient weighing about 75 kg is at least 0.001 mg/kg, preferably 0.1 mg/kg, up to a maximum of 30 mg/kg, preferably 1 mg/kg, of body weight. For acute situations, for example immediately after suffering apnea in high mountain regions, it may even be necessary for the dosages to be higher. Especially on i.v. use, for example for an infarct patient in an intensive care unit, up to 200 mg/kg per day may be necessary. The daily dose can be divided into one or more, for example up to 4, individual doses.
[0219] The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages, and specific objects attained by its use, reference should be made to the following description in which there are illustrated and described preferred embodiments of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0220] For the purpose of describing the specific compounds of the present invention, it is understood that if the compounds are enantiomerically pure, the configuration and/or the sign of the optical rotation is given, and if these data are missing, the compounds are racemates or not optically active.
[0221] The Retention Times (Rt) Given Below Refer to LCMS Measurements with the Following Parameters:
[0222] Analytical Methods:
A stationary phase: Merck Purospher 3μ 2 × 55 mm mobile phase: 95% H 2 O (0.1% HCOOH) → 95% acetonitrile (0.1% HCOOH); 5 min → 95% acetonitrile (0.1% HCOOH); 2 min → 95% H 2 O (0.1% HCOOH); 1 min; 0.45 ml/min. B stationary phase: YMC J'sphere H80 ˜4μ 2.1 × 33 mm mobile phase: 95% H 2 O (0.1% HCOOH) → 95% acetonitrile (0.08% HCOOH); 2.5 min → 95% acetonitrile (0.08% HCOOH); 0.5 min → 95% H 2 O (0.1% HCOOH); 0.5 min; 1.3 ml/min. C stationary phase: YMC J'sphere H80 2 × 33 mm, 4μ, 2.1 × 20 mm mobile phase: 90% H 2 O (0.05% TFA) → 95% acetonitrile; 1.9 min; → 95% acetonitrile 0.5 min; 1 ml/min. D stationary phase: Merck Purospher 3μ 2 × 55 mm mobile phase: 95% H 2 O (0.1% HCOOH)→ 95% acetonitrile (0.1% HCOOH); 3.4 min → 95% acetonitrile (0.1% HCOOH); 1 min → 95% H 2 O (0.1% HCOOH); 0.2 min; 0.75 ml/min. E stationary phase: Merck Purospher 3μ 2 × 55 mm mobile phase: 95% H 2 O (0.05% CF3COOH)→ 95% acetonitrile (0.05% CF3COOH); 3.4 min → 95% acetonitrile (0.05% CF3COOH); 1 min; 0.75 ml/min. F stationary phase: YMC J'sphere H80, 4μ, 2.1 × 20 mm mobile phase: 96% H 2 O (0.05% CF3COOH) → 95% acetonitrile; 2 min; → 95% acetonitrile 0.4 min; 1 ml/min. Preparative HPLC was carried out under the following conditions: stationary phase: Merck Purospher RP18 (10 μM) 250 × 25 mm mobile phase: 90% H 2 O (0.05% TFA)→ 90% acetonitrile; 40 min; 25 ml/min
Example 1
3N-(5-Fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0223]
a) 4-Methyl-3-thienyl isothiocyanate
is obtained by reacting equimolar amounts of 3-amino-4-methylthiophene and N,N′-thiocarbonyldiimidazole in anhydrous tetrahydrofuran (THF) by stirring the reaction mixture at room temperature for 5 hours and then allowing the mixture to stand at room temperature overnight. 4-Methyl-3-thienyl isothiocyanate is isolated by distillative removal of the solvent under reduced pressure using a rotary evaporator, dissolving the residue in ethyl acetate and washing the organic phase repeatedly with water. The organic phase is dried over sodium sulfate and the organic solvent is then distilled off under reduced pressure using a rotary evaporator, giving 4-methyl-3-thienyl isothiocyanate as a brown oily residue. 4-Methyl-3-thienyl isothiocyanate can be used without further purification.
b) N-(2-Amino-5-fluorophenyl)-N′-(4-methyl-3-thienyl)thiourea
[0226] 0.02 mol of 4-fluoro-1,2-diaminobenzene is added to a solution of 0.02 mol of 4-methyl-3-thienyl isothiocyanate in 60 ml of anhydrous THF. The reaction mixture is stirred at room temperature for 2 hours and then allowed to stand overnight, and the solvent is then distilled off under reduced pressure using a rotary evaporator and the oily residue is purified on a silica gel column using a mixture of identical proportions of toluene and ethyl acetate.
[0227] Brown crystalline solid. M.p. 180° C.
c) 3N-(5-Fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0229] A molar excess (about 1.5 to 4 mol) of methyl iodide is added to 1.5 g (0.0053 mol) of N-(2-amino-5-fluorophenyl)-N′-(4-methyl-3-thienyl)thiourea in 50 ml of anhydrous ethanol, and the mixture is boiled at reflux for 5 hours. The mixture is allowed to stand at room temperature overnight and the ethanol is then distilled off under reduced pressure using a rotary evaporator, water is added to the residue and the pH is adjusted to 8-9 using saturated aqueous sodium bicarbonate solution. The mixture is extracted repeatedly with ethyl acetate, the organic phase is washed with water and dried over sodium sulfate, the solvent is distilled off under reduced pressure using a rotary evaporator and the residue is purified by silica gel column chromatography using a solvent mixture of identical proportions of ethyl acetate and toluene (hereinbelow referred to as “mixture 2”) as mobile phase. The oily product obtained after distillative removal of the organic solvent is dissolved in ethyl acetate and made highly acidic using a saturated solution of hydrogen chloride in dry diethyl ether, and the precipitate that crystallizes out is, after relatively long standing, filtered off. Crystalline solid, m.p. 192+/−2° C.
Example 2
2-Chloro-3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and 2,5-dichloro-3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0230]
[0231] A solution of 0.24 g (0.0018 mol) of N-chlorosuccinimide in 15 ml of glacial acetic acid is added dropwise to a solution of 0.5 g (0.0018 mol) of 3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride in 25 ml of glacial acetic acid, the reaction mixture is stirred at room temperature for about 2 to 3 hours and the solvent is distilled off under reduced pressure using a rotary evaporator. Water is added to the residue and the mixture is then made alkaline using 2N NaOH and extracted with ethyl acetate, the organic phase is washed with water and dried over sodium sulfate and the solvent is distilled off under reduced pressure using a rotary evaporator. The resulting oily residue is, by medium pressure column chromatography, using a solvent mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid (hereinbelow referred to as “mixture 17”) as mobile phase, separated and treatment with a solution of hydrogen chloride gas gives:
[0232] 2-chloro-3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride from fraction 1 and 2: colorless to slightly yellowish crystalline product, m.p. 200-202° C., 2,5-dichloro-3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride from fraction 3: colorless to slightly yellowish crystalline product, m.p. 286-288° C.
Example 3
3N-(5,6-Dichloro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0233]
a) N-(2-Amino-4,5-dichlorophenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 4,5-dichloro-1,2-diaminobenzene. Crystalline solid, m.p. 310-320° C.
b) 3N-(5,6-Dichloro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-amino-4,5-dichlorophenyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide.
[0236] Crystalline solid, m.p. 290-294° C.
Example 4
3N-(2-Benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0237]
a) N-(2-Aminophenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 1,2-diaminobenzene. Crystalline solid having a 1st m.p. of 177-182° C., followed by another crystallization and 2nd m.p. 285-290° C.
b) 3N-(2-Benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-aminophenyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide.
[0240] Crystalline solid following recrystallization from ethyl acetate/ethanol, m.p. 194-200° C.
Example 5
3N-(-4-Fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0241]
a) 3-Fluoro-1,2-diaminobenzene
is obtained as an oily amorphous product by hydrogenation of 3-fluoro-2-nitrophenyl hydrazine (prepared by reaction of 2,6-difluoronitrobenzene with hydrazine hydrate) using hydrogen and 10% palladium on carbon catalyst in methanol at room temperature and atmospheric pressure.
b) N-(2-Amino-3-fluorophenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 3-fluoro-1,2-diaminobenzene. Crystalline solid, point of decomposition>240° C.
c) 3N-(-4-Fluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-amino-3-fluorophenyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide. Amorphous precipitate which crystallizes under acetone. Crystalline solid, m.p. 220-230° C.
Example 6
3N-(4,6-Difluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0245]
a) N-(2-Amino-3,5-difluorophenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 3,5-difluoro-1,2-diaminobenzene. Crystalline solid, 1st melting point: 178-182° C., another crystallization with 2nd m.p.: 299-301° C.
b) 3N-(4,6-Difluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-amino-3,5-difluorophenyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide. Amorphous precipitate which crystallizes under ethyl acetate. Crystalline solid, m.p. 232-234° C.
Example 7
3N-(4,5,6,7-Tetrafluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0248]
a) N-(2-Amino-3,4,5,6-tetrafluorophenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 3,4,5,6-tetrafluoro-1,2-diaminobenzene. Crystalline solid, m.p.: 286-290° C.
b) 3N-(3,4,5,6-Tetrafluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-amino-3,4,5,6-tetrafluorophenyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide. Amorphous precipitate which crystallizes under ethyl acetate. Crystalline solid, m.p. 225-228° C.
Example 8
3N-(4-Methyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0251]
a) N-(2-Amino-3-methylphenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 3-methyl-1,2-diaminobenzene. Crystalline solid, m.p. 184-186° C.,
b) 3N-(4-Methyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-amino-3-methylphenyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide. Amorphous precipitate which crystallizes under acetone. Crystalline solid, point of decomposition: 320° C.
Example 9
trans-3N-(3a,4,5,6,7,7a-Hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride (racemate)
[0254]
a) trans-N-(2-Aminocyclohexyl)-N′-(4-methyl-3-thienyl)thiourea (racemate)
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and racemic trans-1,2-diaminocyclohexane. Crystalline solid, m.p. 205-210° C.,
b) trans-3N-(3a,4,5,6,7,7a-Hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride (racemate)
[0257] 0.6 g of racemic trans-N-(2-aminocyclohexyl)-N′-(4-methyl-3-thienyl)thiourea is suspended in 60 ml of toluene and dissolved by heating at 90° C. The mixture is allowed to cool to 70° C., a solution of 0.376 g of dicyclohexylcarbodiimide in 5 ml of anhydrous toluene is added dropwise and the mixture is stirred for a total of about 10 hours at 70° C. and for 2-3 days at room temperature. The crystalline solid is filtered off, the solvent is removed under reduced pressure using a rotary evaporator and the resulting oily residue is dissolved in a little ethyl acetate. Following addition of an anhydrous solution of hydrogen chloride in diethyl ether, a viscous precipitate is formed which, after addition of a little ethanol, crystallizes. Crystalline solid, m.p.: 261-264° C.
Example 10
trans-R,R-3N-(3a,4,5,6,7,7a-Hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0258]
a) trans-R,R—N-(2-Aminocyclohexyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and trans-R,R-1,2-diaminocyclohexane by separation by silica gel column chromatography, eluting with a solvent mixture consisting of 10 parts of ethyl acetate, 5 parts of n-heptane, 5 parts of methylene chloride, 5 parts of methanol and 1 part of 26% strength aqueous ammonia (hereinbelow referred to as “mixture 4”), as an amorphous oily product in addition to a crystalline product having a higher molecular weight of m.p. 94-100° C.
[0260] The amorphous product is processed further without further purification.
b) trans-R,R—N-(3a,4,5,6,7,7a-Hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) by reacting R,R—N-(2-aminocyclohexyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide in anhydrous ethanol as solvent and reaction medium. Amorphous precipitate which is chromatographed on silica gel using mixture 4 as mobile phase and crystallized under acetone. Crystalline solid, m.p. 235-238° C.
Example 11
trans-S,S-3N-(3a,4,5,6,7,7a-Hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0262]
a) trans-S,S-3N-(2-Aminocyclohexyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and trans-S,S-1,2-diaminocyclohexane by separation by silica gel column chromatography using mixture 4 as mobile phase, as an amorphous oily product in addition to a product of higher molecular weight of m.p. 94-102° C. The amorphous product is processed further without further purification.
b) trans-S,S—N-(3a,4,5,6,7,7a-Hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
is obtained analogously to the procedure described in example 1c) by reacting S,S—N-(2-aminocyclohexyl)-N′-(4-methyl-3-thienyl)thiourea and methyl iodide in anhydrous ethanol as solvent and reaction medium. Amorphous precipitate which is chromatographed on silica gel using mixture 4 as mobile phase and crystallizes under acetone. Crystalline solid, m.p. 225-230° C.
Example 12
2-Chloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and 2,5-dichloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0265]
are obtained analogously to the procedure described in example 2 from 3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-chlorosuccinimide in glacial acetic acid. Column chromatography on silica gel using mixture 17 as mobile phase results in the separation of 2,5-dichloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride (colorless crystalline compound, m.p.: 291° C.) from 2-chloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride (colorless crystalline compound, m.p. 257-259° C.).
Example 13
2-Chloro-3N-(4-methyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0266]
is obtained analogously to the procedure described in example 2 from 3N-(4-methyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-chlorosuccinimide in glacial acetic acid. Following column chromatography on silica gel using mixture 17 as mobile phase, 2-chloro-3N-(4-methyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride is obtained as a colorless to slightly yellowish crystalline product. M.p. 255-259° C.
Example 14
2-Chloro-3N-(4,5,6,7-tetrafluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0267]
is obtained analogously to the procedure described in example 2: from 3N-(4,5,6,7-tetrafluoro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-chlorosuccinimide in glacial acetic acid. Crystalline product. M.p. 233-235° C.
Example 15
trans-2-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride (racemate)
[0268]
is obtained analogously to the procedure described in example 2: from 3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride (racemate) and N-chlorosuccinimide in glacial acetic acid. Crystalline product. M.p. 258-260° C.
Example 16
trans-R,R-2-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and trans-R,R-2,5-dichloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0269]
are obtained analogously to the procedure described in example 2: from trans-R,R-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-chlorosuccinimide in glacial acetic acid following chromatographic separation of the two crystalline products in the following order:
a) trans-R,R-2,5-dichloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl) -4-methyl-3-thienylamine hydrochloride, decomposition with foaming starting at 80° C., b) trans-R,R-2-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl) -4-methyl-3-thienylamine hydrochloride, crystalline product. M.p. 260-262° C.
Example 17
trans-S,S-2-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0272]
is obtained analogously to the procedure described in example 2: from trans-S,S-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-chlorosuccinimide in glacial acetic acid following chromatographic separation. Colorless crystalline product, m.p. 258-260° C.
Example 18
2-Bromo-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and 2,5-dibromo-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0273]
are obtained analogously to the procedure described in example 2: from 3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-bromosuccinimide (instead of N-chlorosuccinimide) in glacial acetic acid. Following column chromatography on silica gel using a mixture of 5 parts of dichloromethane, 3 parts of n-heptane, 1 part of glacial acetic acid and 1 part of ethanol (hereinbelow referred to as “mixture 1”) as mobile phase and treatment with a solution of hydrogen chloride gas in ether, 2-bromo-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride, a crystalline product of m.p. 228-231° C., and 2,5-dibromo-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride, a crystalline product of m.p. 208-210° C., are obtained by fractional crystallization in ethyl acetate.
Example 19
trans-R,R-2-Bromo-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and trans-R,R-2,5-dibromo-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride
[0274]
are obtained analogously to the procedure described in example 19: from trans-R,R-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-bromosuccinimide in glacial acetic acid. Following column chromatography on silica gel using mixture 1 as mobile phase, and treatment with a solution of hydrogen chloride gas in ether, trans-R,R-2-bromo-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride, crystalline product, m.p. 215-218° C. and trans-R,R-2,5-dibromo-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride, crystalline product, m.p. 218-220° C. are obtained following fractional crystallization in ethyl acetate.
Example 20
3N-(4-Chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0275]
a) N-(2-Amino-3-chlorophenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the reaction described in example 1b) from 4-methyl-3-thienyl isothiocyanate and 3-chloro-1,2-diaminobenzene (prepared by catalytic hydrogenation of 3-chloro-2-nitroaniline using Pt on activated carbon under atmospheric pressure at room temperature). Crystalline solid, m.p. 298-305° C.,
b) 3N-(4-Chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride
is obtained analogously to the procedure described in example 1c) from N-(2-amino-3-chlorophenyl)-N′-(4-methyl-3-thienyl)-thiourea and methyl iodide. Amorphous precipitate which crystallizes under ethyl acetate. Crystalline solid, point of decomposition 240-245° C.
Example 21
2-Chloro-3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0278]
is obtained analogously to the procedure described in example 2 from 3N-(4-chloro-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride and N-chlorosuccinimide in glacial acetic acid. Following silica gel column chromatography using a mixture of 10 parts of methylene chloride and 1 part of methanol as mobile phase, 2-chloro-3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride is, After crystallization under ethyl acetate, obtained as a colorless to slightly yellowish solid. M.p. 270-272° C.
Example 22
2-Bromo-3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0279]
is obtained analogously to the procedure described in example 2 from 3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride and N-bromosuccinimide (instead of N-chlorosuccinimide) in glacial acetic acid. Following silica gel column chromatography using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid as mobile phase and treatment with a solution of hydrogen chloride gas in ether, 2-bromo-3N-(4-chloro-2-benzimidazolylamino)-4-methylthiophene hydrochloride is obtained by fractionated crystallization in ethyl acetate in the presence of hydrogen-chloride-saturated ether. Crystalline product of m.p. 278-280° C.
Example 23
(2-Bromo-4-methylthiophene-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)amine hydrochloride
[0280]
[0281] (5-Fluoro-1H-benzimidazol-2-yl)-(4-methylthiophene-3-yl)amine (300 mg) (example 1) was dissolved in glacial acetic acid (50 ml). At room temperature, N-bromosuccinimide (207 mg) dissolved in glacial acetic acid (10 ml), was slowly added dropwise, with vigorous stirring. After the addition had ended, stirring was continued for another 10 min and the glacial acetic acid was then distilled off under reduced pressure, and the residue was dissolved in ethyl acetate and washed with saturated potassium carbonate solution. The organic phase was dried over magnesium sulfate, filtered and concentrated. The residue was purified by preparative chromatography and the product-containing fractions were combined, freed from acetonitrile, made basic and extracted three times with ethyl acetate. The organic phases were combined, dried (MgSO 4 ) and filtered. Following removal of the solvent under reduced pressure, water and 2N hydrochloric acid were added to the residue and the mixture was freeze-dried. This gave 245 mg of the desired product.
[0282] LCMS-Rt (B): 0.95 min
[0283] MS (ES + , M+H + ): 326.09
Example 24
2-Bromo-3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene hydrochloride and 2,5-dibromo-3N-(4-fluoro-2-benzimidazolylamino)-4-methyl-thiophene hydrochloride
[0284]
[0285] A solution of 0.161 g of N-bromosuccinimide in 6 ml of glacial acetic acid is added to a solution of 0.214 g of 3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene hydrochloride in 6 ml of glacial acetic acid, and the mixture is stirred at room temperature for 30 minutes. After removal of the solvent by distillation, water is added to the residue and the mixture is made alkaline using 2N NaOH and extracted with ethyl acetate. The organic phase is dried, the solvent is distilled off and the residue is separated by silica gel column chromatography using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid. The hydrochlorides of the two compounds are obtained by distilling off the fractionated solutions, dissolving the residue in ethyl acetate and precipitating the product by addition of hydrogen-chloride-saturated diethyl ether. Crystallization was promoted by gentle warming.
Example 24a
2-Bromo-3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene hydrochloride: colorless crystals; m.p. 212° C. (decomposition).
Example 24b
2,5-Dibromo-3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene hydrochloride: colorless crystals; m.p. 242-244° C. (decomposition).
Example 25
3N-(5-Methoxy-2-benzimidazolylamino)-4-methylthiophene
[0286]
a) N-(2-Amino-4-methoxyphenyl)-N′-(4-methyl-3-thienyl)thiourea
[0288] A mixture of 5.89 g of 4-methylthiophene 3-isothiocyanate and 5 g of 4-methoxy-1,2-diaminobenzene in 60 ml of anhydrous THF is stirred at room temperature for 2 hours, and the solvent is distilled off. Water is added to the residue, the mixture is extracted with ethyl acetate, the dark solution is treated with activated carbon and the organic solvent is re-evaporated. With gentle warming, the residue is treated repeatedly with diisopropyl ether and the solid is filtered off. Brown crystalline solid, m.p. 143-146° C.
b) A mixture of 2.83 g of N-(2-amino-4-methoxyphenyl)-N′-(4-methyl-3-thienyl)thiourea,
[0290] 8.5 g of methyl iodide, and 100 ml of anhydrous ethanol is boiled under reflux for 5 hours, and the solvent is then distilled off and water is added to the residue. Using 2N aqueous sodium hydroxide solution, the mixture is made alkaline and then extracted with ethyl acetate, the organic phase is treated with water and then with activated carbon and the product is purified by silica gel column chromatography using a mobile phase mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid. This gives 3N-(5-methoxy-2-benzimidazolylamino)-4-methylthiophene as an amorphous product.
Example 26
3N-(5-Methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0291]
is obtained by precipitating a solution of 0.2 g of 3N-(5-methoxy-2-benzimidazolyl-amino)-4-methylthiophene (example 25) in 10 ml of ethyl acetate using a saturated solution of hydrogen chloride gas and diethyl ether, giving a crystalline precipitate. M.p.: 222-225° C.
Example 27
2-Chloro-3N-(5-methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0292]
[0293] For about 2 to 2½ hours, a mixture of 0.519 g of 3N-(5-methoxy-2-benzimidazolyl-amino)-4-methylthiophene hydrochloride, 0.046 g of N-chlorosuccinimide and 10-15 ml of glacial acetic acid is heated at 45° C. The glacial acetic acid is then distilled off, water is added to the residue and the mixture is adjusted to pH 9-10 using 2N NaOH. The mixture is extracted with ethyl acetate, the solvent is evaporated and the residue is chromatographed on silica gel on a medium-pressure column using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid. The base obtained after removal of the solvent by distillation is, in ethyl acetate, converted into the hydrochloride using saturated ethereal hydrogen chloride solution, and the product is crystallized under ethyl acetate. Crystalline solid m.p.: 182-186° C.
Example 28
2,5-Dichloro-3N-(5-methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0294]
[0295] Analogous work-up of a reaction mixture of 3N-(5-methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride, N-chlorosuccinimide and glacial acetic acid for about 2 to 2½ hours at 55° C. gave 2,5-dichloro-3N-(5-methoxy-2-benzimidazolylamino)-4-methylthiophene. Crystalline solid, m.p.: 278-282° C.
Example 29
3N-(4-Methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0296]
a) 3-Methoxy-1,2-diaminobenzene
was obtained as a brown oil by hydrogenation of 2-methoxy-6-nitroaniline using hydrogen gas and Raney nickel as catalyst at room temperature and a pressure of 3 bar. The product was converted into the thiourea without further purification.
b) N-(2-Amino-3-methoxyphenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the procedure described in example 25a) from 3-methoxy-1,2-diaminobenzene and 4-methyl-3-thienyl isothiocyanate in anhydrous THF, followed by medium-pressure chromatography on silica gel using a mixture of 1 part of toluene and 1 part of ethyl acetate. Crystalline solid, m.p.: 148-153° C. Solidification of the melt and next m.p. at 260° C.
c) 3N-(4-Methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
is obtained analogously to the procedures described in examples 25 and 26 from N-(2-amino-3-methoxyphenyl)-N′-(4-methyl-3-thienyl)thiourea by heating with methyl iodide in THF, analogous work-up and treatment of the benzimidazole with HCl in ether. Crystalline solid, m.p.: 230-235° C.
Example 30
2-Chloro-3N-(4-methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0300]
[0301] A mixture of 0.1 g of 3N-(4-methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride, 0.046 g of N-chlorosuccinimide and 10-15 ml of glacial acetic acid is heated at 40° C. for about 2 to 2½ hours. The glacial acetic acid is then distilled off, water is added to the residue and the pH is adjusted to 9-10 using 2N NaOH. The mixture is extracted with ethyl acetate, the solvent is evaporated and the residue is chromatographed on silica gel on a medium-pressure column using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid. The resulting base is, in ethyl acetate, converted into the hydrochloride using saturated ethereal hydrogen chloride solution. Colorless to light-yellow crystalline solid, m.p.: 248-250° C.
Example 31
[0000]
3N-(4-Chloro-6-trifluoromethyl-2-benzimidazolylamino)-4-methyl-thiophene hydrochloride
a) N-(2-Amino-3-chloro-5-trifluoromethylphenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the procedure described in example 25a) by reacting 3-chloro-5-trifluoromethyl-1,2-diaminobenzene and 4-methyl-3-thienyl isothiocyanate in anhydrous THF at room temperature for 3 days. The solvent is distilled off and water is added to the residue, and the mixture is then extracted with ethyl acetate, the solvent is again distilled off and the amorphous residue is crystallized under diisopropyl ether. M.p.: >310° C.
b) 3N-(4-chloro-6-trifluoromethyl-2-benzimidazolylamino)-4-methylthiophene hydrochloride
is obtained analogously to the procedures described under examples 25 and 26 from N-(2-amino-3-chloro-5-trifluoromethylphenyl)-N′-(4-methyl-3-thienyl)thiourea by boiling with methyl iodide in THF under reflux conditions for 5 hours, analogous work-up and purification by medium-pressure silica gel column chromatography using a mixture of identical parts by volume of ethyl acetate and toluene. The solvent is evaporated and the residue is then dissolved in ethyl acetate, giving, by addition of a saturated solution of hydrogen chloride in diethyl ether, 3N-(4-chloro-6-trifluoromethyl-2-benzimidazolyl-amino)-4-methylthiophene hydrochloride as a crystalline precipitate. Solid, m.p.: 210-213° C.
Example 32
2-Chloro-3N-(4-chloro-6-trifluoromethyl-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0305]
[0306] A mixture of 0.34 g of 3N-(4-methoxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride, 0.151 g of N-chlorosuccinimide and 20 ml of glacial acetic acid is stirred at room temperature for ½ hour and heated at 60° C. for one hour. The glacial acetic acid is then distilled off, water is added to the residue and the pH is adjusted to 9-10 using 2N NaOH. The mixture is extracted with ethyl acetate, the solvent is evaporated and the residue is chromatographed on silica gel on a medium-pressure column using a mixture of identical parts of toluene and ethyl acetate. The solvent is distilled off and the resulting base is then, in ethyl acetate, converted into the hydrochloride using saturated ethereal hydrogen chloride solution. Colorless to light-yellow crystalline solid. mp.: 247-250° C.
Example 33
3N-(4-Carboxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0307]
a) N-(2-Amino-3-carboxyphenyl)-N′-(4-methyl-3-thienyl)thiourea
is obtained analogously to the procedure described in example 25a) from 3-carboxy-1,2-diaminobenzene and 4-methyl-3-thienyl isothiocyanate in anhydrous THF, followed by medium-pressure chromatography on silica gel using a mixture of 12 parts of methylene chloride and 1 part of methanol. Amorphous product.
b) 3N-(4-Carboxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
is obtained by boiling a solution of 1.12 g of N-(2-amino-3-carboxyphenyl)-N′-(4-methyl-3-thienyl)thiourea and 3.1 g of methyl iodide in 60 ml of ethanol under reflux. The solvent is evaporated, water is added to the residue, the pH is adjusted to 5 using 2N aqueous HCl and the precipitate is filtered off. Crystalline solid, point of decomposition: 265-285° C.
Example 34
2-Chloro-3N-(4-carboxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0310]
is obtained analogously to the procedure described in example 32 from 0.2 g of 3N-(4-carboxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride and 0.103 g of N-chlorosuccinimide in 20-25 ml of glacial acetic acid and precipitation of the corresponding hydrochloride using HCl-saturated diethyl ether in ethyl acetate and subsequent crystallization under diisopropyl ether and ethyl acetate. Point of decomposition 170° C.
Example 35
3N-[4-(1-Piperidinocarbonyl)-2-benzimidazolylamino]-4-methylthiophene hydrochloride
[0311]
[0312] 0.215 g of N,N′-carbonyldiimidazole is added to a mixture of 0.330 g of 3N-(4-carboxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride, 30 ml of anhydrous THF and 5 ml of anhydrous dimethylacetamide. The mixture is stirred at room temperature for about 4 hours, when the evolution of carbon dioxide has ceased, and 0.411 g of piperidine is then added. The solution is stirred at room temperature for 2 hours and, after standing overnight, the solvent is distilled off under reduced pressure. The residue is triturated with water, the solid is filtered off and dissolved in ethyl acetate, the insoluble fraction is removed by filtration and the solvent is distilled off under reduced pressure. Foam-like amorphous product.
Example 36
2-Chloro-4-methyl-3N-[4-(1-piperidinocarbonyl)-2-benzimidazolylamino]-thiophene hydrochloride
[0313]
[0314] A mixture of 0.2 g of 3N-[4-(1-piperidinocarbonyl)-2-benzimidazolylamino]-4-methyl-thiophene hydrochloride and 0.086 g of N-chlorosuccinimide in about 20 ml of glacial acetic acid is stirred at room temperature for 1½ hours and at 35° C. for about 30 min, the solvent is distilled off and the residue is, after addition of water, made alkaline using 2N NaOH. Following extraction with ethyl acetate, the solvent is evaporated and the residue is purified by medium-pressure silica gel column chromatography using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid. The solvent is distilled off, the residue is dissolved in ethyl acetate and the mixture is acidified using a solution of ether saturated with hydrogen chloride. The amorphous residue is crystallized under a mixture of ethyl acetate with a little acetone and a little ethanol. Amorphous solid, point of decomposition from 100° C.
Example 37
2-Chloro-3N-(4-fluoro-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0315]
[0316] 0.132 g of N-chlorosuccinimide is added to 0.234 g of 3N-(4-fluoro-2-benzimidazolyl-amino)-4-methylthiophene hydrochloride in about 20 ml of glacial acetic acid and the mixture is stirred at room temperature for 30 minutes and at 50-60° C. for another 1½ hours. The acetic acid is distilled off under reduced pressure, water is then added to the residue and the pH is adjusted to about 10-11 using 2N NaOH, and the mixture is extracted with ethyl acetate, which is then distilled off. The residue is chromatographed on a silica gel column under medium-pressure conditions using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid. After concentration, the residue is dissolved in a little ethyl acetate and the hydrochloride is precipitated by addition of hydrogen-chloride-saturated diethyl ether. Colorless to light-yellow crystalline solid. M.p.: 268-270° C.
Example 38
2-Chloro-3N-(4-hydroxy-2-benzimidazolylamino)-4-methylthiophene hydrochloride
[0317]
[0318] A suspension of 0.13 g of 2-chloro-3N-(4-methoxy-2-benzimidazolylamino)-4-methyl-thiophene hydrochloride in about 20 ml of anhydrous methylene chloride is added to a suspension of 0.29 g of activated anhydrous aluminum chloride in 10 ml of anhydrous methylene chloride, and the reaction mixture is stirred at 55° C. for 2 hours. After cooling, the reaction mixture is poured into ice-water and extracted with ethyl acetate, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is chromatographed on a silica gel column under medium-pressure conditions using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid, and the eluate is concentrated under reduced pressure. The residue is dissolved in ethyl acetate and the hydrochloride is precipitated by addition of hydrogen-chloride-saturated diethyl ether. Crystalline solid. M.p. 246-248° C.
Example 39
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene
[0319]
is obtained by adding 2N NaOH to a solution of 3 g of 2-chloro-3N-(2-benzimidazolyl-amino)-4-methylthiophene hydrochloride in 200 ml of water until a pH of 10 is set. The crystals are filtered off and washed repeatedly with water. Yield: 2.52 g. Colorless crystal powder. M.p. 182-185° C.
Example 40
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene hydrobromide
[0320]
[0321] 0.25 g of 2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene is dissolved in 10 ml of ethanol, 0.1 ml of 48% strength HBr is then added and the mixture is stirred at room temperature for a little while. The solvent is distilled off and the residue is crystallized under ethyl acetate. Yield: 0.29 g. Colorless crystals, point of decomposition: 252-254° C.
Example 41
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene adipic acid salt
[0322]
is obtained analogously to the procedure described in example 40 from 2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene using one equivalent of adipic acid. Colorless crystals. M.p. 155-157° C.
Example 42
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene oxalic acid salt
[0323]
is obtained analogously to the procedure described in example 40 by reacting 2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene with one equivalent of oxalic acid in ethyl acetate. Colorless crystals. M.p.: 220-222° C.
Example 43
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene phosphoric acid salt
[0324]
is obtained analogously to the procedure described in example 40 from 2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene using one equivalent of phosphoric acid. Colorless crystals. Decomposition range: 113-175° C.
Example 44
(1H-Benzimidazol-2-yl)-(2-chloro-4-methylthiophen-3-yl)methylamine
[0325]
[0326] Finely powdered dry potassium carbonate (66 mg) was added to a solution of 2-chloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine (125 mg, from example 39) and dry methanol (20 ml). Methyl iodide (74 mg) was then added dropwise with exclusion of moisture and vigorous stirring, and the mixture was kept under reflux for three days. The solvent was removed under reduced pressure and the residue was then partitioned between ethyl acetate and water, the ethyl acetate phase was dried with magnesium sulfate, the magnesium sulfate was filtered off and the filtrate was evaporated to dryness. The product was then purified by preparative HPLC. The product-containing fractions were combined and, after removing the acetonitrile under reduced pressure, freeze-dried. For further purification, the product was finally chromatographed on silica gel using ethyl acetate/heptane (¼). The product-containing fractions were combined and then evaporated to dryness, and the residue was taken up in HCl and freeze-dried. This gave 5 mg of a solid.
[0327] LCMS-Rt (A): 2.04 min
[0328] MS (ES + , M+H + ): 278.05
Example 45
(5,6-Difluoro-1H-benzimidazol-2-yl)-(4-methylthiophen-3-yl)amine trifluoroacetic acid salt
[0329]
[0330] 3-Isothiocyanato-4-methylthiophene (1.08 g), dissolved in absolute tetrahydrofuran (30 ml), was added dropwise to a solution of 1,2-diamino-4,5-difluorobenzene (1 g) in absolute tetrahydrofuran (20 ml). The mixture was then stirred at room temperature for 2 hours and allowed to stand overnight. Methyl iodide (0.44 ml) was added and the mixture was then stirred for 8 hours and allowed to stand overnight. The tetrahydro-furan was then removed under reduced pressure, the residue was partitioned between ethyl acetate and water, the phases were separated and the ethyl acetate phase was dried over magnesium sulfate. The residue was absorbed under silica gel and chromatographed on silica gel using the mobile phase n-heptane:ethyl acetate=1:1. This gave 229 mg of the desired compound as the free base.
[0331] An impure fraction from the above chromatography was purified by preparative HPLC. Following freeze-drying, 42.2 mg of the desired compound were isolated as trifluoroacetic acid salt.
[0332] LCMS-Rt (A): 1.98 min
[0333] MS (ES + , M+H + ): 266.13
Example 46
(2-Chloro-4-methylthiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)amine hydrochloride
[0334]
[0335] At room temperature, a solution of N-chlorosuccinimide (124.6 mg) in glacial acetic acid (5 ml) was added dropwise to a solution of (5,6-difluoro-1H-benzimidazol-2-yl)-(4-methylthiophen-3-yl)amine (225 mg) in glacial acetic acid (5 ml). The mixture was then stirred at room temperature for 3.5 hours. The glacial acetic acid was then removed and the residue was taken up in water and adjusted to pH 10 using 2 M aqueous sodium hydroxide solution. The aqueous phase was extracted three times with ethyl acetate, the combined organic phases were dried over magnesium sulfate and the solvent was removed. The residue was purified by preparative chromatography and the product-containing fractions were combined, freed from acetonitrile, made basic and extracted three times with ethyl acetate. The organic phases were combined, dried (MgSO 4 ), filtered and concentrated. The residue was taken up in water, acidified with 10% strength hydrochloric acid and freeze-dried. This gave 81 mg of the desired product as a solid.
[0336] LCMS-Rt (A): 2.15 min
[0337] MS (ES + , M+H + ): 300.11
Example 47
(2-Bromo-4-methylthiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine
[0338]
[0339] At room temperature, a solution of N-bromosuccinimide (8 mg) in glacial acetic acid (0.5 ml) was added dropwise to a solution of (5,6-difluoro-1H-benzimidazol-2-yl)-(4-methylthiophen-3-yl)amine trifluoroacetic acid salt (15 mg, example 45) in glacial acetic acid (0.5 ml) in a ReactiVial, and the mixture was stirred at room temperature for 0.5 h. The acetic acid was then removed under reduced pressure and saturated potassium carbonate solution and ethyl acetate were added to the residue. The organic phase was removed and the aqueous phase was then extracted twice with ethyl acetate. The combined organic phases were dried using magnesium sulfate and the drying agent was then filtered off. The residue that remained after removal of the solvent under reduced pressure was purified by preparative chromatography. The product-containing fractions were combined and freed from acetonitrile, saturated sodium bicarbonate solution was added to the residue and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried (MgSO 4 ) and filtered. After removal of the ethyl acetate under reduced pressure, the residue was coevaporated with toluene and then dried under high vacuum. This gave 8.1 mg of the desired compound.
[0340] LCMS-Rt (D): 1.45 min
[0341] MS (ES + , M+H + ): 343.96
Example 48
[(2-Chloro-4-methylthiophen-3-yl)-(4,5,6,7-tetrahydro-1H-benzimidazol-2-yl)]amine hydrochloride
[0000]
a) 1,4-Dioxaspiro[4.5]dec-6-ylamine
[0343] The amine required as precursor was prepared in accordance with GB1131191. 2-Chlorocyclohexanone was reacted with phthalimide to give 2-(2-oxocyclohexyl)isoindole-1,3-dione, which was ketalized with ethylene glycol in the presence of para-toluenesulfonic acid, giving 2-(1,4-dioxaspiro[4.5]dec-6-yl)isoindole-1,3-dione. Treatment with hydrazine hydrate to remove the phthalimide radical gave the desired 1,4-dioxaspiro[4.5]dec-6-ylamine.
b) 1-(1,4-Dioxaspiro[4.5]dec-6-yl)-3-(4-methylthiophen-3-yl)thiourea
[0345] A solution of 3-isothiocyanato-4-methylthiophene (296.2 mg, see example 1a) in absolute tetrahydrofuran (10 ml) was added dropwise to a solution of 1,4-dioxa-spiro[4.5]dec-6-ylamine (300 mg) in absolute tetrahydrofuran (10 ml), the mixture was stirred at room temperature for 2 hours and the solvent was then removed under reduced pressure. The residue was purified by preparative chromatography and the product-containing fractions were combined, freed from acetonitrile, made basic and extracted three times with ethyl acetate. The organic phases were combined, dried (MgSO4) and filtered. This gave 428 mg of the desired product.
[0346] LCMS-Rt (A): 3.57 min
[0347] MS (ES + , M+H + ): 313.19
c) 1-(1,4-Dioxaspiro[4.5]dec-6-yl)-2-methyl-3-(4-methylthiophen-3-yl)isothiourea
[0349] 1-(1,4-Dioxaspiro[4.5]dec-6-yl)-3-(4-methylthiophen-3-yl)thiourea (393 mg) was dissolved in absolute tetrahydrofuran (8.5 ml), and a solution of methyl iodide (179 mg) in absolute tetrahydrofuran (0.5 ml) was added. The mixture was then stirred at 70° C. in sand bath for 2 days. Ethyl acetate was then added to the reaction mixture, and the mixture was washed twice with water. The organic phase was dried over magnesium sulfate and the solvent was removed after filtration. The residue was purified by preparative chromatography and the product-containing fractions were combined, freed from acetonitrile, made basic and extracted three times with ethyl acetate. The organic phases were combined, dried (MgSO 4 ) and filtered. This gave 59 mg of the desired product which was used directly for the next step.
[0350] LCMS-Rt (C): 1.05 min
[0351] MS (ES + , M+H + ): 327.4
d) N-(1,4-Dioxaspiro[4.5]dec-6-yl)-N′-(4-methylthiophen-3-yl)guanidine
[0353] In a ReactiVial, a 7 M solution of ammonia in methanol (2 ml) was added to 1-(1,4-dioxaspiro[4.5]dec-6-yl)-2-methyl-3-(4-methylthiophen-3-yl)isothiourea (58.8 mg), and the mixture was heated in a sand bath at about 100° C. for 16 hours. Removal of the solvent gave a residue of 51 mg of an oily product which was directly reacted further.
[0354] LCMS-Rt (C): 1.00 min
[0355] MS (ES + , M+H + ): 296.4
e) N-(2-Chloro-4-methylthiophen-3-yl)-N′-(1,4-dioxaspiro[4.5]dec-6-yl)guanidine
[0357] N-(1,4-Dioxaspiro[4.5]dec-6-yl)-N′-(4-methylthiophen-3-yl)guanidine (49 mg) was dissolved in glacial acetic acid (3 ml), and a solution of N-chlorosuccinimide (20.3 mg) in glacial acetic acid (5 ml) was added slowly. The mixture was stirred for a number of hours and then allowed to stand at room temperature over the weekend, after which the glacial acetic acid was removed under reduced pressure, the residue was taken up in water and the mixture was adjusted to pH 10 using 2N sodium hydroxide solution. The basic phase was extracted three times with ethyl acetate and the combined organic phases were dried over magnesium sulfate, filtered and concentrated. The residue was purified by preparative chromatography and the product-containing fractions were combined, freed from acetonitrile, made basic and extracted three times with ethyl acetate. The organic phases were combined, dried (MgSO 4 ) and filtered. Removal of the solvent under reduced pressure gave 24 mg of the desired product which was used directly for the next step.
[0358] LCMS-Rt (C): 1.09 min
[0359] MS (ES + , M+H + ): 330.4
f) ((2-Chloro-4-methylthiophen-3-yl)-(4,5,6,7-tetrahydro-1H-benzoimidazol-2-yl))amine hydrochloride
[0361] N-(2-Chloro-4-methylthiophen-3-yl)-N′-(1,4-dioxaspiro[4.5]dec-6-yl)guanidine (24 mg) was dissolved in 2N hydrochloric acid (1 ml) and stirred at room temperature for 30 min. Concentrated hydrochloric acid (1 ml) was then added, and the mixture was stirred for another two hours. The mixture was then diluted with a little water and freeze-dried. Toluene was added to the residue and then distilled off under reduced pressure. This step was repeated twice, giving 22 mg of the desired product as a solid.
[0362] LCMS-Rt (B): 0.95 min
[0363] MS (ES + , M+H + ): 268.07
Example 49
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene benzenesulfonate
[0364]
[0365] 2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene (250 mg) was dissolved in THF (5 ml), and benzenesulfonic acid (150 mg), dissolved in THF (5 ml), was added with stirring. After 3 h, the reaction mixture was left in the fridge overnight. The precipitate was filtered off with suction and dried at 75° C. under high vacuum, giving the desired product. Colorless crystals. M.p.: 235° C.
Example 50
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene methane-sulfonate
[0366]
was obtained analogously to the procedure described in example 49 from 2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene using one equivalent of methanesulfonic acid. Colorless crystals. M.p.: 227° C.
Example 51
2-Chloro-3N-(2-benzimidazolylamino)-4-methylthiophene benzoate
[0367]
was obtained analogously to the procedure described in example 49 from 2-chloro-3N-(2-benzimidazolylamino)-4-methylthiophene using one equivalent of benzoic acid. For the precipitation, the reaction mixture was concentrated to half of its original volume, and ether (30 ml) was then added. Colorless crystals, m.p.: 198° C.
Example 52
2,4-Dichloro-3N-(2-benzimidazolylamino)thiophene hydrochloride
[0368]
a) Methyl 3-acetylaminothiophene 2-carboxylate
[0370] With simultaneous heating in an oil bath, 567 ml of acetic anhydride are added dropwise to a mixture of 942 g of methyl 3-aminothiophene-2-carboxylate and 1000 ml of toluene, and the mixture is then boiled under reflux conditions for 1½ hours and subsequently cooled in an ice bath to about 0° C. The crystals are filtered off and washed twice with a little isopropanol and twice with diisopropyl ether. Methyl 3-acetylaminothiophene-2-carboxylate can be obtained from the filtrate by further concentration and crystallization. M.p. 93-95° C.
b) Methyl 3-acetylamino-4,5-dichlorothiophene-2-carboxylate
[0372] With magnetic stirring at a reaction temperature of 20-30° C., 17.9 g of sulfuryl chloride SO 2 CO 2 are added dropwise to a solution of 19.9 g of methyl 3-acetylaminothiophene-2-carboxylate in 100 ml of chloroform. The mixture is then stirred at 40° C. for another 2 hours and boiled under reflux conditions for another 15 minutes. The solvent is distilled off under reduced pressure, ethyl acetate is then added to the residue and the crystals are, after standing, filtered off. M.p. 136-138° C.
c) Methyl 3-acetylamino-4 chlorothiophene-2-carboxylate
[0374] A mixture of 25 g of methyl 3-acetylamino-4,5-dichlorothiophene-2-carboxylate, about 10 g of triethylamine, 300 ml of methanol and 1 g of palladium on carbon is, at room temperature and under atmospheric pressure, hydrogenated until the uptake of hydrogen has stopped. The catalyst is filtered off and the mixture is then concentrated by distillation under reduced pressure until crystallization begins, water is then added and the solid is filtered off. Colorless crystals from isopropanol. M.p. 142-147° C.
d) Methy 3-amino-4-chlorothiophene-2-carboxylate
[0376] In a mixture of 50 ml of methanol and 50 ml of concentrated hydrochloric acid, 7 g of methyl 3-acetylamino-4-chlorothiophene-2-carboxylate are stirred at 60° C. for 4 hours, under reflux for 5 hours and at room temperature for another 3 days. Any precipitate that has formed is removed by filtration, and about ⅓ of the volume of the solvent is removed by distillation under reduced pressure. Following addition of about 100 ml of water, the mixture is stirred at room temperature for another 15 minutes and the colorless crystals are filtered off and dried in a stream of air. M.p.: 62-64° C.
e) 3-Amino-4-chlorothiophene
[0378] 18.02 g of methyl 3-amino-4-chlorothiophene-2-carboxylate are added to a solution of 11.1 g of KOH and 160 ml of water and the mixture is then boiled under reflux for 3 hours and, after cooling, added dropwise to a solution, which is at 60° C., of 15 ml of concentrated hydrochloric acid and 30 ml of water. This results in a vigorous evolution of CO 2 . After further stirring at 60° C. for about 40 minutes, the mixture is allowed to cool, a layer of 50-100 ml of methyl tert-butyl ether is added, the mixture is made alkaline using concentrated aqueous sodium hydroxide solution and the aqueous phase is extracted in a separating funnel. The aqueous phase is extracted two more times with methyl tert-butyl ether, and the combined organic extracts are washed once with water in a separating funnel. The organic phase is dried, the solvent is distilled off and the oily-amorphous residue is chromatographed on a silica gel column using a mixture of 1 part of ethyl acetate and 1 part of toluene.
f) 4-Chloro-3-thienyl isothiocyanate
[0380] 1.46 g of thiocarbonyldiimidazole are added to a solution of 1.1 g of 3-amino-4-chlorothiophene in 20 ml of anhydrous THF, and the mixture is stirred at room temperature for one hour. The solid is distilled off under reduced pressure, the residue is dissolved in ethyl acetate, the organic phase is treated twice with water in a separating funnel and then dried, and the solvent is again distilled off under reduced pressure. This gives 4-chloro-3-thienyl isothiocyanate as a dark oil which is then reacted further without further purification steps.
g) N-(2-Aminophenyl)-N′-(4-chloro-3-thienyl)thiourea
[0382] 0.86 g of 1,2-diaminobenzene (o-phenylenediamine) is added to a solution of 1.4 g of 4-chloro-3-thienyl isothiocyanate in 40 ml of anhydrous THF, the mixture is stirred at room temperature for about 20 hours and the solvent is distilled off under reduced pressure. The residue is treated with water and extracted with ethyl acetate, the solvent is distilled off again and the residue is purified using medium-pressure silica gel column chromatography using a 1:1 mixture of ethyl acetate and toluene. Brown-yellow solid.
h) 4-Chloro-3N-(2-benzimidazolylamino)thiophene
[0384] A solution of 0.169 g of sodium hydroxide in 5 ml of water, followed by a solution of 0.363 g of p-toluenesulfonyl chloride in 10 ml of THF, is added to a solution of 0.5 g of N-(2-aminophenyl)-N′-(4-chloro-3-thienyl)thiourea in 25 ml of anhydrous THF. The mixture is stirred at room temperature for 3 hours, the solvent is then distilled off under reduced pressure and the residue is treated with water and extracted with ethyl acetate. After removal of the solvent by distillation, the product is purified by medium-pressure silica gel chromatography using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid as eluent.
[0385] For characterization, a small portion of the 4-chloro-3N-(2-benzimidazolylamino)-thiophene was, in ethyl acetate, using ethereal hydrogen chloride solution, converted into 4-chloro-3N-(2-benzimidazolylamino)thiophene hydrochloride and characterized. Colorless crystals. M.p.: 256-260° C.
i) 2,4-Dichloro-3N-(2-benzimidazolylamino)thiophene hydrochloride
[0387] A solution of 0.16 g of N-chlorosuccinimide in 5 ml of glacial acetic acid is added to a solution of 0.3 g of 4-chloro-3N-(2-benzimidazolylamino)thiophene in 10 ml of glacial acetic acid. The reaction mixture is stirred at 40° C. for 15 minutes and at room temperature for about 4 hours, the acetic acid is then distilled off under reduced pressure and the residue is treated with water. The mixture is made alkaline using aqueous sodium hydroxide solution and then extracted with ethyl acetate, the extract is washed with water, the organic phase is dried and the solvent is distilled off under reduced pressure. The residue is purified under medium-pressure conditions by column chromatography using a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid as eluent and then precipitated from ethyl acetate by addition of a solution of hydrogen chloride in diethyl ether. Colorless crystalline product. M.p. 264-268° C.
Example 53
2-Bromo-4-chloro-3N-(2-benzimidazolylamino)thiophene hydrochloride
[0388]
[0389] A solution of 0.356 g of N-bromosuccinimide in 6 ml of glacial acetic acid is added dropwise to a solution of 0.5 g of 4-chloro-3N-(2-benzimidazolylamino)thiophene in 15 ml of glacial acetic acid, and the mixture is stirred at room temperature for another 15 minutes. The solvent is distilled off and the residue is treated with water and made alkaline using aqueous sodium hydroxide solution. Following extraction with ethyl acetate, the organic phase is washed with water, dried and concentrated under reduced pressure. The residue is chromatographed on silica gel using medium-pressure conditions and a mixture of 20 parts of ethyl acetate, 10 parts of n-heptane and 3 parts of glacial acetic acid as eluent. Following distillative removal of the solvent, the residue is taken up in ethyl acetate and 2-bromo-4-chloro-3N-(2-benzimidazolyl-amino)thiophene hydrochloride is precipitated by addition of a solution of hydrogen chloride gas in diethyl ether. Colorless crystalline product. M.p.: 264-266° C.
Example 54
(2,4-Dichloro-thiophen-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)-amine-hydrochloride
[0000]
a) 1-(2-Amino-4-fluoro-phenyl)-3-(4-chloro-thiophen-3-yl)-thiourea
[0391] 4-Fluoro-1,2-phenylendiamine (900 mg) was dissolved in THF (25 ml) and 4-chloro-3-thienylisothiocyanat (example 52c), dissolved in THF (15 ml), was added with stirring. The solution was stirred for about 3 h at room temperature and stood overnight. Then the reaction mixture was concentrated und the residue purified by preparative HPLC. The product containing fractions were combined, the acetonitrile was removed, the aqueous residue made basic and three times extracted with ethyl acetate. The organic layers were combined, dried (MgSO4) and filtered. After removal of the solvent the desired product (625 mg) was obtained.
[0392] LCMS-Rt (F): 1.28 min
[0393] MS (ES + , M+H + ): 302.0
b) (4-Chloro-thiophen-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)-amine
[0395] 1-(2-Amino-4-fluoro-phenyl)-3-(4-chloro-thiophen-3-yl)-thiourea (625 mg) was dissolved in THF and a solution of NaOH (0.207 g) in water (9 ml) was added. Within 5 min a solution of p-toluenesulfonyl chloride (0.395 g) in THF (10 ml) was added dropwise. After stirring for one hour at room temperature water and ethyl acetate were added to the reaction mixture. The organic layer was separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were dried (MgSO4), treated with charcoal, filtered and the solvent evaporated to yield the desired product (135 mg).
[0396] LCMS-Rt (F): 0.90 min
[0397] MS (ES + , M+H + ): 268.0
c) (2,4-Dichloro-thiophen-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)-amine hydrochloride
[0399] (4-Chloro-thiophen-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)-amine (85 mg) was dissolved in acetic acid (4 ml) and under vigorous stirring at room temperature a solution of N-chlorosuccinimide (42 mg) in acetic acid (4 ml) was added. After stirring for 45 min. at room temperature, stirring was continued for 5 h at 50° C. After the addition of further N-chlorosuccinimide (4 mg) stirring was continued for one hour at 50° C. Then the reaction mixture was treated with toluene (20 ml) and solvent mixture distilled off. The residue was dissolved in ethyl acetate and washed with saturated potassium carbonate solution. The organic layer was dried (MgSO4), filtered and concentrated. The residue was purified by preparative HPLC, the product containing fractions were combined, the acetonitrile was removed, the aqueous residue made basic and extracted three times with ethyl acetate. The organic layers were combined, dried (MgSO4) and filtered. After removal of the solvent water and 2 N HCl were added to the residue. After freeze drying the desired product (17 mg) was obtained.
[0400] LCMS-Rt (E): 2.65 min
[0401] MS (ES + , M+H + ): 301.93
Example 55
(2-Bromo-4-chloro-thiophen-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)-amine hydrochloride
[0402]
[0403] (4-Chloro-thiophen-3-yl)-(5-fluoro-1H-benzoimidazol-2-yl)-amine (50 mg, example 54b) was dissolved in acetic acid (4 ml) and at room temperature with vigorous stirring N-bromosuccinimide (33 mg) dissolved in acetic acid (4 ml) was slowly added. After stirring for 45 min at room temperature toluene (20 ml) was added and the solvent mixture distilled off. The residue was dissolved in ethyl acetate and washed with saturated potassium carbonate solution. The organic layer was dried (MgSO4), filtered and concentrated. The residue was purified by preparative HPLC, the product containing fractions were combined, the acetonitrile was removed, the aqueous residue set basic and three times extracted with ethyl acetate. The organic layers were combined, dried (MgSO4) and filtered. After removal of the solvent water and 2 N HCl were added to the residue. After freeze drying the desired product (27 mg) was obtained.
[0404] LCMS-Rt (E): 2.29 min
[0405] MS (ES + , M+H + ): 347.87
Example 56
(2,4-Dichloro-thiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine-hydrochloride
[0000]
a) 1-(2-Amino-4,5-difluoro-phenyl)-3-(4-chloro-thiophen-3-yl)-thiourea
[0407] To 1,2-diamino-4,5-difluorobenzene (1.02 g) in THF abs. (15 ml) 4-chloro-3-thienylisothiocyanate (1.25 g, example 52c) dissolved in THF abs. (15 ml) was added. Following the analogous description in example 54a) the desired product was obtained (773 mg).
[0408] LCMS-Rt (F): 1.32 min
[0409] MS (ES + , M+H + ): 320.0
b) (4-Chloro-thiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine
[0411] To 1-(2-amino-4,5-difluoro-phenyl)-3-(4-chloro-thiophen-3-yl)-thiourea (773 mg) in THF (20 ml) a solution of NaOH (240 mg) in water (9 ml) was added followed by a solution of p-toluenesulfonyl chloride (528 mg) in THF (10 ml). Following the analogous description in example 54b) the desired product (275 mg) was obtained.
[0412] LCMS-Rt (F): 0.95 min
[0413] MS (ES + , M+H + ): 286
c) (2,4-Dichloro-thiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine-hydrochloride
[0415] To (4-chloro-thiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine (125 mg) in acetic acid (8 ml) a solution of N-chlorosuccinimide (59 mg) in acetic acid (2 ml) was added. Following the analogous description in example 54c) the desired product (58 mg) was obtained.
[0416] LCMS-Rt (E): 2.97 min
[0417] MS (ES + , M+H + ): 319.88
Example 57
(2-Bromo-4-chloro-thiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine-hydrochloride
[0418]
[0419] To (4-chloro-thiophen-3-yl)-(5,6-difluoro-1H-benzoimidazol-2-yl)-amine (125 mg, example 55b) in acetic acid (8 ml) N-bromosuccinimide (78 mg) dissolved in acetic acid was added under vigorous stirring at room temperature. Following the analogous description in example 55) the desired product (77 mg) was obtained.
[0420] LCMS-Rt (E): 2.39 min
[0421] MS (ES + , M+H + ): 365.86
Example 58
4-Chloro-3N-(4-methyl-2-benzimidazolyl-amino)thiophene Hydrochloride
[0422]
a) N-(2-Amino-3-methylphenyl)-N′-(4-chloro-3-thienyl)thiourea
was obtained as described in example 52 g) by using 4-chloro-3-thienylisothiocyanate and 1,2-diamino-3-methylbenzene and chromatographical purification (silica gel, ethyl acetate/n-heptane/glacial acetic acid=20:10:3). Brownish-yellowish solid, Mp.: 193-196° C.
b) e) 4-Chloro-3N-(4-methyl-2-benzimidazolylamino)thiophene
was obtained as described in example 52h) by using N-(2-Amino-3-methylphenyl)-N′-(4-chloro-3-thienyl)thiourea and chromatographical purification (silica gel, dichloromethane/methanol=10:1). The amorphous, foamy material was dissolved in ethyl acetate and treated with a solution of gaseous HCl in diethyl ether forming 4-chloro-3N-(4-methyl-2-benzimidazolylamino)thiophen hydrochloride. Crystalline material, m.p. 325-327° C.
Example 59
2,4-Dichlor-3N-(4-methyl-2-benzimidazolyl-amino)thiophen Hydrochloride
[0425]
was obtained as described in example 52i) by reaction of 4-chloro-3N-(4-methyl-2-benzimidazolylamino)thiophene and N-chlorosuccinimide in pure acetic acid and by analogous purification. Crystalline material, m.p. 296-298° C.
Example 60
trans-(3aS,7aS)-4-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine Hydrochloride
[0426]
a) trans-S,S-3N-(2-Amino-cyclohexyl)-N′-(4-chloro-3-thienyl)-thiourea
was obtained as described in example 1b) by reaction of 4-chloro-3-thienyl-isothiocyanate and trans-S,S-1,2-diaminocyclohexane. Chromatographical purification (silica gel, ethyl acetate/dichloromethane/n-heptane/methanol/aqueous ammonia [35%]=10:5:5:5:1) results in a dark amorphous material which was used for further syntheses without further purification.
b) trans-(3aS,7aS)-4-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine
was obtained as described in example 52h) by using trans-S,S-3N-(2-amino-cyclohexyl)-N′-(4-chloro-3-thienyl)-thiourea and p-Toluolsulfonylchloride. Chromatographical purification (silica gel, dichloromethane/methanol=10:1) results in an amorphous material which can be transformed to the corresponding trans-S,S-4-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine hydrochloride by dissolving in ethyl acetate and treatment with a solution of gaseous HCl in diethylether. Crystalline material, m.p. 196-200° C.
Example 61
trans-(3aR,7aR)-4-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine Hydrochloride
[0429]
a) trans-(1R,2R)-3N-(2-Amino-cyclohexyl)-N′-(4-chloro-3-thienyl)-thiourea
was obtained as described in example 1b) by reaction of 4-chloro-3-thienyl-isothiocyanate und trans—(1R,2R)-(−)-1,2-diaminocyclohexane. Chromatographical purification (silica gel, ethyl acetate/dichloromethane/n-heptane/methanol/aqueous ammonia [35%]=10:5:5:5:1) results in a dark amorphous material which was used for further syntheses without further purification.
b) trans-(3aR,7aR)-4-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine
was obtained as described in example 52h) by using of trans-R,R-3N-(2-amino-cyclohexyl)-N′-(4-chloro-3-thienyl)-thiourea and p-toluolsulfonylchloride. Chromatographical purification (silica gel, ethyl acetate/dichloromethane/n-heptane/methanol/aqueous ammonia [35%]=10:5:5:5:1) results in an amorphous material which can be transformed to the corresponding trans-R,R-4-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine hydrochloride by dissolving the material in ethyl acetate and treatment with a solution of gaseous HCl in diethylether. Crystalline material, m.p. 240-244° C.
Example 62
cis-4-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine Hydrochloride
[0432]
a) cis-3N-(2-Amino-cyclohexyl)-N′-(4-chloro-3-thienyl)-thiourea
was obtained as described in example 1b) by reaction of 4-chloro-3-thienyl-isothiocyanate und cis-1,2-diaminocyclohexane. Chromatographical purification (silica gel, ethyl acetate/dichloromethane/n-heptane/methanol/aqueous ammonia [35%]=10:5:5:5:1) results in a dark amorphous material which was used for further syntheses without further purification.
b) cis-4-Chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine
was obtained as described in example 52h) by using 3N-(cis-2-Amino-cyclohexyl)-N′-(4-chlor-3-thienyl)-thioharnstoff and p-Toluenesulfonyl chloride. Chromatographical purification (silica gel, ethyl acetate/dichloromethane/n-heptane/methanol/aqueous ammonia [35%]=10:5:5:5:1) results in an amorphous brownish material which can be transformed to the corresponding 4-chloro-3N-(cis-3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine hydrochloride by dissolving in ethyl acetate and treatment with a solution of gaseous HCl in diethylether. Crystalline material, m.p. 228-231° C.
Example 63
trans-R,R-2,4-Dichloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine Hydrochloride
[0435]
was obtained as described in example 52i) by reaction of trans-R,R-4-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine and N-chlorosuccinimide chlorosuccinimide in pure acetic acid and by analogous purification. Crystalline material, m.p. 296-298° C.
Example 64
cis-2,4-Dichloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine Hydrochloride
[0436]
was obtained as described in example 52i) by reaction of cis-4-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamine and N-chlorosuccinimide in pure acetic acid and by analogous purification. Crystalline material, m.p. 270-274° C.
Example 65
4-Chloro-3N-(4-chloro-2-benzimidazolylamino)thiophene Hydrochloride
[0437]
a) 1-N-(2-Amino-3-chlorophenyl)-3-N-(4-chloro-3-thienyl)thiourea
was obtained as described in example 1b) by reaction of 4-chloro-3-thienyl-isothiocyanate und 3-chloro-1,2-diaminobenzene. The compound crystallizes after stirring in diisopropylether. Solid crystalline material with 2 melting points: 1 st m.p. 152-155° C.; 2 nd m.p. (after recrystallization of molten material)>310° C.
b) 4-Chloro-3N-(4-chloro-2-benzimidazolylamino)thiophene
was obtained as described in example 52h) using 1-N-(2-amino-3-chlorophenyl)-3-N-(4-chloro-3-thienyl)thiourea and p-toluenesulfonyl chloride. After chromatographic purification (silica gel, toluene/ethyl acetate=3:1) the product was transformed to 4-chloro-3N-(4-chloro-2-benzimidazolylamino)thiophene hydrochloride by dissolving in ethyl acetate and treatment with a solution of gaseous HCl in diethylether. Crystalline material, m.p. 276-280° C.
Example 66
2,4-Dichloro-3N-(4-chloro-2-benzimidazolyl-amino)thiophene Hydrochloride
[0440]
was obtained as described in example 52i) by reaction of 4-chloro-3N-(4-methyl-2-benzimidazolylamino)thiophene and N-chlorosuccinimide in pure acetic acid and by analogous purification. Crystalline material, m.p. 294-297° C.
[0441] Analogously to the compounds listed in the working examples, it is possible to prepare the following thiophene derivatives:
2-bromo-4-chloro-3N-(4-methyl-2-benzimidazolyl-amino)thiophen hydrochloride, 2-bromo-4-chloro-3N-(4-chlor-2-benzimidazolyl-amino)thiophen hydrochloride, trans-R,R-2-bromo-4-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamin hydrochloride, trans-(3aS,7aS)-2-bromo-4-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2-benzimidazolyl)-3-thienylamin hydrochloride, 2,4-dibromo-3N-(2-benzimidazolyl)-3-thienylamine hydrochloride, 2,4-dimethyl-3N-(2-benzimidazolyl)-3-thienylamine hydrochloride, 2,4-dimethyl-3N-(4-methyl-2-benzimidazolyl)-3-thienylamine hydrochloride, 2,4-dimethyl-3N-(5-fluoro-2-benzimidazolyl)-3-thienylamine hydrochloride, 2-chloro-3N-(4-butoxy-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride, 2-chloro-3N-(4-trifluoromethyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride, 2-chloro-3N-(4-methylsulfonyl-2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride.
Pharmacological Data:
Test Description:
[0452] In this test, the recovery of the intracellular pH (pHi) after an acidification, which starts when the NHE is capable of functioning, even under bicarbonate-free conditions, was determined. For this purpose, the pHi was determined using the pH-sensitive fluorescent dye BCECF (Calbiochem, the precursor BCECF-AM is employed). The cells were initially loaded with BCECF. The BCECF fluorescence was determined in a “ratio fluorescence spectrometer” (Photon Technology International, South Brunswick, N.J., USA) with excitation wavelengths of 505 and 440 nm and an emission wavelength of 535 nm, and was converted into the pHi using calibration plots. The cells were incubated in NH 4 Cl buffer (pH 7.4) (NH 4 Cl buffer: 115 mM NaCl, 20 mM NH 4 Cl, 5 mM KCl, 1 mM CaCl 2 , 1 mM MgSO 4 , 20 mM Hepes, 5 mM glucose, 1 mg/ml BSA; a pH of 7.4 is established with 1 M NaOH) even during the BCECF loading. The intracellular acidification was induced by addition of 975 μl of an NH 4 Cl-free buffer (see below) to 25 μl aliquots of the cells incubated in NH 4 Cl buffer. The subsequent rate of pH recovery was recorded in the case of NHE1 for two minutes, in the case of NHE2 for five minutes and in the case of NHE3 for three minutes. To calculate the inhibitory power of the tested substances, the cells were initially investigated in buffers in which complete or absolutely no pH recovery took place. For complete pH recovery (100%), the cells were incubated in Na + -containing buffer (133.8 mM NaCl, 4.7 mM KCl, 1.25 mM CaCl 2 , 1.25 mM MgCl 2 , 0.97 mM Na 2 HPO 4 , 0.23 mM NaH 2 PO 4 , 5 mM Hepes, 5 mM glucose, a pH of 7.0 is established with 1 M NaOH). To determine the 0% value, the cells were incubated in an Na + -free buffer (133.8 mM choline chloride, 4.7 mM KCl, 1.25 mM CaCl 2 ,1.25 mM MgCl 2 , 0.97 mM K 2 HPO 4 , 0.23 mM KH 2 PO 4 , 5 mM Hepes, 5 mM glucose, a pH of 7.0 is established with 1 M KOH). The substances to be tested were made up in the Na+-containing buffer. Recovery of the intracellular pH at each tested concentration of a substance was expressed as a percentage of the maximum recovery. Using the Sigma-Plot program, the IC 50 value of the substance in question was calculated for the individual NHE subtypes using the percentages for pH recovery.
[0453] Results:
Example IC 50 [μM] 16 0.27 (rNHE3) trans-R,R-2-chloro-3N-(3a,4,5,6,7,7a-hexahydro-1H-2- benzimidazolyl)-4-methyl-3-thienylamine hydrochloride 12 0.12 (rNHE3) 2-chloro-3N-(2-benzimidazolyl)-4-methyl-3-thienylamine hydrochloride 54: 0.22 (hNHE3) 2-bromo-4-chloro-3N-(2-benzimidazolylamino)thiophen hydrochloride 53: 0.14 (hNHE3) 2,4-dichloro-3N-(2-benzimidazolylamino)thiophen hydrochloride 56: 0.22 (hNHE3) 2,4-dichloro-3N-(4-methyl-2-benzimidazolyl- amino)thiophen hydrochloride 60: 0.19 (hNHE3) trans-R,R-2,4-dichloro-3N-(3a,4,5,6,7,7a-hexahydro-1H- 2-benzimidazolyl)-3-thienylamin hydrochloride 63: 0.54 (hNHE3) 2,4-dichloro-3N-(4-chloro-2-benzimidazolyl- amino)thiophen hydrochloride 38: 0.84 (hNHE3) 2-chloro-3N-(4-hydroxy-2-benzimidazolyl-amino)-4- methylthiophen hydrochloride 18: 0.12 (hNHE3) 2-bromo-3N-(2-benzimidazolyl)-4-methyl-3-thienylamin hydrochloride 19: 0.56 (hNHE3) trans-R,R-2-bromo-3N-(3a,4,5,6,7,7a-Hexahydro-1H-2- benzimidazolyl)-4-methyl-3-thienylamin hydrochloride 2: 0.62 (hNHE3) 2-chloro-3N-(5-fluoro-2-benzimidazolyl)-4-methyl-3- thienylamin hydrochloride 44: 1.59 (hNHE3) (1H-benzimidazol-2-yl)-(2-chloro-4-methyl-thiophen-3- yl)-methyl-amine
While there have been described and pointed out fundamental novel features of the invention as applied to a preferred embodiment thereof, it will be understood that various omissions and substitutions and changes, in the form and details of the packages and methods illustrated, may be made by those skilled in the art without departing from the invention. For example, it is expressly intended that all combinations of those elements and/or method steps which perform substantially the same function in substantially the same way to achieve the same results are within the scope of the invention.
[0454] The invention is not limited by the embodiments described above which are presented as examples only but can be modified in various ways within the scope of protection defined by the appended patent claims.
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Substituted thiophenes, processes for their preparation, their use as medicament or diagnostic agent. The substituted thiophene derivatives have the following backbone structure:
Medicaments comprising compounds of this type are of use for preventing or treating various disorders, such as, respiratory disorders and snoring, acute and chronic disorders, disorders induced by ischemic and/or reperfusion events and by proliferative or fibrotic events, disorders of the central nervous system and lipid metabolism, diabetes, blood coagulation and infection by parasites.
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BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to the manufacture of electrical and electronic circuits and particularly to the fabrication of printed circuits. More specifically, this invention is directed to conductive ink which may be employed to define paths for current flow between components of an electrical or electronic device. Accordingly, the general objects of the present invention are to provide novel and improved methods and materials of such character.
(2) Description of the Prior Art
Conductive inks are well known in the art. The typical conductive-silver-ink formulation contains a thermosetting binder which serves as a carrier for the silver particles. The binder may, for example, comprise an epoxy/urethane mixture. The conductive ink is applied to a nonconductive substrate by any suitable technique, to establish a current path or paths between components of an electrical or an electronic device, and the binder is thereafter cured by the application of heat.
The conductive inks disclosed in the prior art exhibit characteristics which make their use under certain conditions disadvantageous. Some devices, such as conductors, in which the conductive pathway is defined by a conductive ink, must be capable of withstanding "super soak" conditions, ninety-six hours at 95% relative humidity and 65° Celsius, without degradation. Prior art conductive inks exhibit poor moisture durability. The bond between these inks and the various nonconductive substrates over which they are applied, to form a conductive pathway, is known to degrade under "super soak" conditions.
The prior art also discloses the use of conductive inks along with a circuit which has been etched from a copper to nonconductive substrate laminate. Here the laminate has undergone various wet processing manufacturing steps such as etching and stripping operations. Because of these manufacturing steps the now exposed cured adhesive which had been used to bond the copper to the substrate has been subjected to chemical attack. Application of prior art conductive ink has shown poor adhesion to the old chemically attacked adhesive.
SUMMARY OF THE INVENTION
The present invention overcomes the above-discussed disadvantages and other deficiencies of the prior art by providing a novel and improved conductive ink. A conductive ink in accordance with the present invention is characterized by the establishment of a bond with the substrate, to which it has been applied, which has enhanced moisture durability. Also, a conductive ink in accordance with the present invention is characterized by establishment of an improved bond to an exposed cured adhesive layer, on a nonconductive substrate, which has been subjected to chemical attack.
In accordance with the present invention, a low molecular weight multifunctional isocyanate, preferably a difunctional isocyanate, is added to the binder material of a conductive ink. In accordance with the preferred embodiment, toluene diisocyanate or isophorone diisocyanate is used. The multifunctional isocyante is added in quantities which comprise less than 10% by weight of the binder. The isocyanate employed, in accordance with the present invention, is characterized by an isocyanate to hydroxyl ratio, which is a function of the composition of the binder, in the range of 0.01:1 to 1.5:1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A conductive ink in accordance with the present invention will comprise a binder, in the form of a thermosetting adhesive, electrically conductive particles, for example, silver, and a multifunctional isocyanate having a low molecular weight. In formation of the ink, the isocyanate will typically be added to a previously prepared conductive ink with the amount added, as a percent by weight of the binder, being a function of the characteristics of the binder.
In one preferred embodiment of the present invention, isophorone diisocyanate, having a molecular weight of 222, was dissolved in a screening solvent, butyl cellosolve acetate, with the isophorone diisocyanate being in a concentration of 10% by volume of the solution. This solution was then added to a commercially available conductive ink, comprised of silver particles and an epoxy/urethane binder. This commercially available conductive ink is sold under the name Uniset 927-13 by Amicon Corporation, 25 Hartwell Ave., Lexington, Mass. 02173.
Three testing samples of the above composition were prepared with the isophorone diisocyanate to binder weight ratios of 3:100, 5:100 and 10:100 respectively. These testing samples and a control sample of the conductive ink were applied to a testing surface. This surface comprised a nonconductive substrate which had been previously bonded to copper and was subsequently etched clean. The above samples were applied over this previously cured adhesive surface in the form of a thixotropic paste by screen printing.
The testing surface along with the four screen printed samples of conductive ink were subjected to "super soak" conditions to determine at what point in time there was a failure of bond integrity, per a standard I.P.C. tape test. The following are the results of the test: the control sample with 0% isophorone diisocyanate failed at two hours; the sample with 3% by weight of the isophorone diisocyanate failed at 6 hours; the sample with 5% by weight of the isophorone diisocyanate failed after 64 hours; and the 10% by weight of isophorone diisocyanate had not failed at the termination of the standard 96 hour test. All four samples retained their functional flexibility, scratch resistance and electrical conductivity prior to experiencing bond failure. A further test with the same test results was run substituting tolylene diisocyanate, with a molecular weight of 174.16, for isophorone diisocyanate.
It is theorized that by adding an excess of the isocyanate a nonequilibrium of active hydroxyl sites is created. The isocyanate in the conductive ink binder would then migrate to the surface of the substrate and cross-link the old cured adhesive surface with the thermosetting binder. It is further theorized, that the reactivity differential between the isocyanate groups on the isophorone diisocyanate results in one group only reacting with the cured adhesive layer and the other only reacting with the adhesive binder, thus cross-linking the two. These theories are neither confirmed nor suggested as the only theories and should not be taken in any manner to limit the scope of the present invention.
It has been found that the present invention may comprise, depending on processing conditions and with particular interest in preventing toxic vapors a multi-functional or difunctional isocyanate, either monomeric aliphatic or aromatic, with a molecular weight ranging from 150-350 and having low vapor pressure relative to other low molecular weight isocyanates at standard temperature and pressure. Furthermore, preferred ratio of isocyanate to hydroxyl sites is 0.01:1 to 1.5:1. The following is a partial list of multifunctional isocyanates that may be employed with the present invention: toluene diisocyanate, hexamethylene diisocyanate, triphenylmethane-p, p', p"'-triisocyanate, diphenylmethane-p, p' diisocyanate, dianisidine diisocyanate, thiophosphoric acid tris (p-isocyanatophenyl ester) and trimethyl-hexamethylene diisocyanate.
The above isocyanates may be added to any conductive ink wherein the binder is an epoxy, urethane, polyester, or adduct or combinations of these materials. The cured adhesive layer may also be one of the above compounds or compositions. These adhesive systems are characterized as easily hydrolyzed and thus are subject to chemical attack after wet processing or if subject to high humidity conditions and will lose bond integrity as a result. Any binder having hydroxyl functionality or the ability to form hydroxyl groups may be used in the present invention.
While the preferred embodiments have been shown and described, various substitutions and modifications may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation.
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An improved method of manufacturing electrical and electronic circuits is provided wherein an improved conductive ink is employed to define the pathways of current flow. This improved conductive ink is comprised of conductive particles, thermosetting binder and a multifunctional isocyanate. The isocyanate provides cross-linking between the conductive ink binder and the surface upon which the ink is applied and establishes a bond with enhanced moisture durability.
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FIELD OF THE INVENTION
[0001] The present invention relates to an arthropod-controlling composition.
BACKGROUND OF THE INVENTION
[0002] Many arthropod-controlling compositions are on the market at present. However, the objected harmful arthropods have many kinds and the situations for controlling them are in many ways. Therefore, the arthropod-controlling composition having practically high effectiveness and safety is desired.
[0003] Though pyrethroid insecticides having rapid knock-down efficacy are excellent agents for controlling harmful arthropods, progress of pyrethroid resistance to some arthropods has been reported in various places recently. Under these circumstances, non-pyrethroid compounds having excellent knock-down efficacy are earnestly desired.
[0004] On the other hand, it is known that some α-pyrone compounds are effective for controlling harmful acarina and houseflies in Japanese Unexamined Patent Publication No. sho-51-19126. However, the compounds described in the publication do not necessarily give a sufficient effect.
SUMMARY OF THE INVENTION
[0005] The present invention provides 4-hydroxy-6-methyl-3-(3-methylbutanoyl)-2-pyrone shown by the formula:
[0006] an arthropod-controlling composition comprising it as an active ingredient and a method for controlling arthropods by using it.
DETAILED DESCRIPTION OF THE INVENTION
[0007] Examples of the arthropods against which 4-hydroxy-6-methyl-3-(3-methylbutanoyl)-2-pyrone (hereinafter referred as to The Pyrone Compound) exhibits a control effect include the following Insecta, Acarina, Chilognatha, Epimorpha and Isopoda:
[0008] Hemiptera Insects:
[0009] Delphacidae (planthoppers) such as Laodelphax striatellus (small brown planthopper), Nilaparvata lugens (brown planthopper), Sogatella furcifera (white-backed rice planthopper) and so on; Deltocephalidae (leafhoppers) such as Nephotettix cincticeps (green rice leafhopper), Recilia dorsalis (zig-zag rice leaf hopper), Nephotettix virescens (green rice leafhopper) and so on; Aphididae (aphids); stink bugs; Aleyrodidae (whiteflies); scales; Tingidae (lace bugs); Psyllidae (suckers) and so on.
[0010] Lepidoptera Insects:
[0011] Pyralidae such as Chilo suppressalis (rice stem borer), Cnaphalocrocis medinalis (rice leafroller), Plodia interpunctella (Indian meal moth) and so on; Noctuidae such as Spodoptera litura (tobacco cutworm), Pseudaletia separata (rice armyworm), Mamestra brassicae (cabbage armyworm) and so on; Pieridae such as Pieris rapae crucivora (common cabbageworm) and so on; Tortricidae such as Adoxophyes spp. and so on; Carposinidae; Lyonetiidae; LymLantriidae; Plusiinae; Agrotis spp. such as Agrotis segetum (turnip cutworm), Agrotis ipsilon (black cutworm) and so on; Helicoverpa spp.; Heliothis spp.; Plutella xylostella; Parnara guttata (rice skipper); Tinea pellionella (casemaking clothes moth); Tineola bisselliella (webbing clothes moth) and so on. Diptera insects:
[0012] Culex Spp. such as Culex pipiens pallens (common mosquito), Culex tritaeniorhynchus and so on, Aedes spp. such as Aedes aegypti, Aedes albopictus and so on; Anopheles spp. such as Anopheles sinensis and so on; Chironomidae (midges); Muscidae such as Musca domestica (housefly), Muscina stabulans (false stablefly), Fannia canicularis (little housefly) and so on; Calliphoridae; Sarcophagidae; Anthomyiidae such as Delia platura (seedcorn maggot), Delia antiqua (onion maggot) and so on; Tephritidae (fluit flies); Drosophilidae; Psychodidae (moth flies); Tabanidae; Simuliidae (black flies); Stomoxyidae (stable flies); Phoridae; Ceratopogonidae (biting midges) and so on.
[0013] Coleoptera Insects (Beetles):
[0014] Corn rootworms such as Diabrotica virgifera (western corn rootworm), Diabrotica undecimpunctata howardi (southern corn rootworm) and so on; Scarabaeidae (scarabs) such as Anomala cuprea (cupreous chafer), Anomala rufocuprea (soybean beetle) and so on; Curculionidae (weevils) such as Sitophilus zeamais (maize weevil), Lissorhoptrus oryzophilus (ricewater weevil), ball weevil, Callosobruchus chinensis (adzuki bean weevil) and so on; Dermestidae such as Authrenus verbasci (varied carpet beetle), Attagenus unicolor japonicus (black carpet beetle) and so on; Tenebrionidae (darkling beetles) such as Tenebrio molitor (yellow mealworm), Tribolium castaneum (red flour beetle) and so on; Chrysomelidae (leaf beetles) such as Oulema oryzae (rice leaf beetle), Phyllotreta striolata (striped flea beetle), Aulacophora femoralis (cucurbit leaf beetle) and so on; Anobiidae; Epilachna spp. such as Epilachna vigintioctopunctata (twenty-eight-spotted ladybird) and so on; Lyctidae (powderpost beetles), Bostrychidae (false powderpost beetles), Cerambycidae, Paederus fuscipes (robe beetle) and so on.
[0015] Dictyoptera Insects:
[0016] [0016] Blattella germanica (German cockroach); Periplaneta fuliginosa (smokybrown cockroach); Periplaneta americana (American cockroach); Peiplaneta brunnea (brown cockroach); Blatta orientalis (oriental cockroach) and so on;
[0017] Thysanoptera Insects (Thrips):
[0018] [0018] Thrips palmi, Flankliniella occidentalis (western flower thrips), Thrips hawaiiensis (flower thrips) and so on.
[0019] Hymenoptera Insects:
[0020] Formicidae (ants); Vespidae (hornets); Polistes spp. (long-legged wasps); Bethylidae; Tenthredinidae (sawflies) such as Athalis rosae ruficornis (cabbage sawfly) and so on.
[0021] Orthoptera Insects:
[0022] Gryllotalpidae (mole crickets); Acrididae (grasshoppers) and so on. Siphonaptera insects (fleas):
[0023] [0023] Ctenocephalides canis (dog flea); Ctenocephalides felis (cat flea); Pulex irritans ; and so on.
[0024] Anoplura Insects (Lice):
[0025] [0025] Pediculus corporis (body louse); Pediculus humanus (head louse); Pthirus pubis (crab louse) and so on.
[0026] Isoptera Insects:
[0027] [0027] Reticulitermes speratus; Coptotermes formosanus (Formosan subterranean termite); and so on.
[0028] Harmful Acarina:
[0029] Ixodidae (Ticks):
[0030] [0030] Boophilus microplus; Haemaphysalis longieonis and so on Tetranychidae (spider mites):
[0031] [0031] Tetranychus cinnabarinus (carmine spider mite); Tetranychus urticae (two-spotted spider mite); Tetranychus kanzawai (Kanzawa spider mite); Panonychus citri (citrus red mite); Panonychus ulmi (European red mite) and so on.
[0032] House-Dust Mites:
[0033] Acaridae such as Tyrophagus putrescentiae (copra mite), Aleuroglyphus ovatus (brown legged grain mite) and so on; Dermanyssidae such as Dermatophagoides farinae (American house dust mite), Dermatophagoides pteronyssinus and so on; Glycyphagidae such as Glycyphagus privatus, Glycyphagus domesticus, Glycyphagus destructor and so on; Cheyletidae such as Chelacaropsis malaccensis, Cheyletus fortis and so on; Tarsonemidae; Chortoglyphus spp.; Haplochthonius spp. and so on.
[0034] Chilognatha (millipedes) such as Oxydus spp.; Chilopoda (centipedes) such as red centipede; wood lice such as Porcellio spp., Porcellionides spp.; and pill bugs such as Armadilldium spp.; and so on.
[0035] As The Pyrone Compound, which is an active ingredient of the present controlling agent, gives an efficacy by contacting the objective harmful arthropods including insects and acarina, it is usually to be formulated as described below for use.
[0036] Namely, The Pyrone Compound or its solution can be formulated to the present controlling agent such as oil solution, emulsifiable concentrate, wettable powder, flowable (aqueous suspension or aqueous emulsion), granule, dust and so on, by mixing with solid carrier, liquid carrier or liquefied gaseous carrier and optionally surfactant, the other formulation auxiliaries.
[0037] The present controlling agent described above contains usually 0.001 to 95% by weight of The Pyrone Compound as an active ingredient.
[0038] Examples of the solid carrier used in the formulation described above include fine granules or granules of inorganic carriers such as clays (e.g. kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, Fubasami clay, acid clay, etc.), talc, ceramics, sericite, quartz, calcium carbonate and so on; synthetic resins such as polyethylene, polypropylene and so on; and carriers originated from plants such as wood powder, activated carbon and so on. Examples of the liquid carrier include water, alcohols (e.g. methanol, ethanol, higher alcohols, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (e.g. hexane, cyclohexane, kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitrites (e.g. acetonitrile, isobutyronitrile, etc.), ethers (e.g. diisopropyl ether, dioxane, etc.), acid amides (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (e.g. dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils (e.g. soybean oil, cottonseed oil, etc.) and so on. Examples of the liquefied gaseous carrier include fluorocarbon, fluorohydrocarbon, LPG (liquefied petroleum gas), dimethyl ether and carbon dioxide and so on.
[0039] Examples of the surfactant optionally used in the formulation include alkyl sulfate salts, alkylsulfonate salts, alkylarylsulfonate salts, alkyl aryl ethers, polyoxyethylenealkyl aryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives and so on.
[0040] The other formulation auxiliaries are exemplified by sticking agent, dispersant, stabilizer and so on. Examples of sticking agent and dispersant include casein, gelatin, polysaccharides (e.g. starch powder, gum arabic, cellulose derivatives, alginic acid etc.), lignin derivatives, bentonite, sugars and synthetic water-soluble polymers (e.g. polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.). Examples of stabilizer include phenol type antioxidants such as BHT (2,6-di-tert-butyl-4-methyphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), amine type antioxidants such as diphenylamine, organic sulfur type antioxidants such as 2-mercaptobenzimidazole, PAP (acid isopropyl phosphate), vegetable oils, mineral oils, surfactants, fatty acids, esters of fatty acid and so on.
[0041] The flowable formulations (aqueous suspension or aqueous emulsion) usually comprise The Pyrone Compound, dispersant, suspension assistant (for example, protective colloid or a compound giving thixotropy), suitable auxiliaries (for example, antifoamer, rust preventive agent, stabilizer, developing agent, penetrating assistant, antifieezing agent, bactericide, fungicide, etc.) and water. Examples of the protective colloid include gelatin, casein, gums, cellulose ethers, polyvinyl alcohol and so on, and examples of the compound giving thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acids and so on. Use of the oil which can rarely dissolve The Pyrone Compound in place of water can give suspension-in-oil formulation.
[0042] The formulations of emulsifiable concentrate, wettable powder, flowable and so on obtained above are usually diluted with water and so on, and applied at 0.1 to 10000 ppm of the concentration of The Pyrone Compound. The formulations of oil solution, granule, dust and so on are usually applied to harmful arthropods by distributing or spraying as they are.
[0043] Further, The Pyrone Compound or its formulation can be used after making the forms below.
[0044] A mixture of The Pyrone Compound or its liquid formulation and a propellant can be charged into a pressure container with a spray nozzle to afford an aerosol of the present controlling agent. Further, The Pyrone Compound or its liquid formulation can be impregnated into a base material of mosquito-coil, mosquito-mat, ceramic board and so on to afford a heating volatile formulation such as mosquito-coil and mosquito-mat for electric heater; a heating fumigant formulation such as self-combustible fumigant, chemical reaction type fumigant and porous ceramic board fumigant; a non-heating volatile formulation such as resin volatile formulation and paper volatile formulation; a smoking formulation such as fogging; and an ULV formulation of the present controlling agent. Furthermore, a liquid formulation of The Pyrone Compound can be charged into a container with an absorptive wick in the upper part to afford a bottle containing insecticidal liquid for volitilization by heating the absorptive wick.
[0045] These present controlling agents include The Pyrone Compound as an active ingredient in an amount of 0.001% to 95% by weight.
[0046] Examples of the propellant for aerosols include propane, butane, isobutane, dimethyl ether, methyl ethyl ether and methylal.
[0047] An example of the base material of the mosquito-coil is a mixture of raw plant powder such as wood powder and Pyrethrum marc and a binding agent like Tabu powder (powder of Machilus thunbergil ), starch or gluten.
[0048] An example of the base material of the mosquito-mat for electric heating fumigation is a plate of compacted fibrils of cotton linters or a mixture of pulp and cotton linters.
[0049] The base material of the self-combustible fumigant includes, for example, an exothermic agent (e.g. nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose, wood powder, etc.), a pyrolytic stimulating agent (e.g. alkali metal salt, alkaline earth metal salt, dichromate, chromate, etc.), an oxygen source (e.g. potassium nitrate, etc.), a combustion assistant (e.g. melanin, wheat starch, etc.), a bulk filler (e.g. diatomaceous earth, etc.) and a binding agent (e.g. synthetic glue, etc.).
[0050] The base material of the chemical reaction type fumigant includes, for example, an exothermic agent (e.g. alkali metal sulfide, polysulfide, hydrogensufide and hydrated salt, calcium oxide, etc.), a catalytic agent (e.g. carbonaneous substance, iron carbide, activated clay, etc.), an organic foaming agent (e.g. azodicarbonamide, benzenesulfonylhydrazide, dinitrosopenta-methylenetetramine, polystyrene, polyurethane, etc.) and a filler (e.g. natural or synthetic fibers, etc.).
[0051] An example of the base material of the resin volatile formulation is thermoplastic resin, and examples of the base material of the paper volatile formulation include filter paper and Japanese paper.
[0052] The present controlling agent can be used simultaneously with the other insecticide, the other acaricide, repellent or synergist under non-mixed conditions or pre-mixed conditions.
[0053] Examples of the insecticides and acaricides include organophosphorus compounds such as fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate], fenthion [O,O-dimethyl O-(3-methyl-4-(methythio)phenyl)phosphorothioate], diazinon [O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate], DDVP [2,2-dichlorovinyl dimethyl phosphate], cyanophos [O-4-cyanophenyl O,O-dimethyl phosphorothioate], dimethoate [O,O-dimethyl S-(N-methylcarbamoylmethyl)dithiophosphate], phenthoate [ethyl 2-dimethoxyphosphinothioylthio(phenyl)acetate], malathion [diethyl (dimethoxyphosphinothioylthio)succinate], and azinphos-methyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O, O-dimethyl phosphorodithioate]; carbamate compounds such as BPMC (2-sec-butylphenyl methylcarbamate), benfracarb [ethyl N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl)aminothio]-N-isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate] and carbaryl [1-naphthyl N-methylcarbamate]; pyrethroid compounds such as etofenprox [2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methyl-butyrate], esfenvalerate [(S)-α-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin [(RS)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS)-α-cyano-3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS)-α-cyano-3-phenoxybenzyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-carboxylate], cycloprothrin [(RS)-α-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate], fluvalinate [α-cyano-3-phenoxybenzyl N-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate], bifenthrin [2-methylbiphenyl-3-ylmethyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], 2-methyl-2-(4-bromodifluoro-methoxyphenyl)propyl 3-phenoxybenzyl ether, tralomethrin [(S)-α-cyano-3-phenoxybenzyl (1R-cis)-3-{(1RS)(1,2,2,2-tetrabromoethyl)}-2,2-dimethyl-cyclopropanecarboxylate], silafluofen [(4-ethoxyphenyl){3-(4-fluoro-3-phenoxyphenyl)propyl}dimethylsilane], d-phenothrin [3-phenoxybenzyl (1R-cis, trans)-chrysanthemate], cyphenothrin [(RS)-α-cyano-3-phenoxybenzyl (1R-cis, trans)-chrysanthemate], d-resmethrin [5-benzyl-3-furylmethyl (1R-cis,trans)-chrysanthemate], acrinathrin [(S)-α-cyano-3-phenoxybenzyl (1R,cis(Z))-2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl}cyclopropane-carboxylate], cyfluthrin [(RS)-α-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], tefluthrin [2,3,5,6-tetrafluoro-4-methylbenzyl (1RS-cis(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], transfluthrin [2,3,5,6-tetrafluorobenzyl (1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], tetramethrin [3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis,trans-chrysanthemate], allethrin [(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1RS)-cis,trans-chrysanthemate], prallethrin [(S)-2-methyl-4-oxo-3-(2-propynyl) cyclopent-2-enyl (1R)-cis,trans-chrysanthemate], empenthrin [(RS)-1-ethynyl-2-methyl-2-pentenyl (1R)-cis,trans-chrysanthemate], imiprothrin [2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl (1R)-cis,trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate], d-furamethrin [5-(2-propynyl) furfuryl (1R)-cis,trans-chrysanthemate] and 5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate; nitroimidazolidine derivatives such as imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine); N-cyanoamidine derivatives such as N-cyano-N′-methyl-N′-(6-chloro-3-pyridylmethyl) acetamidine; nitenpyram [N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovynylidenediamine]; thiacloprid [1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazoline]; thiamethoxam [3-((2-chloro-5-thiazolyl)methyl)-5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine]; 1-methyl-2-nitro-3-((3-tetrahydrofuryl)methyl)guanidine; 1-(2-chloro-5-thiazolyl)methyl-3-methyl-2-nitroguanidine; nitroiminohexahydro-1,3,5-triazine derivatives; chlorinated hydrocarbons such as endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC [1,2,3,4,5,6-hexachlorocyclohexane] and 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylurea compounds such as chlorfluazuron [1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea], teflubenzuron [1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea] and flufenoxuron [1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea]; juvenile hormone like compounds such as pyriproxyfen [4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether], methoprene [isopropyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate] and hydroprene [ethyl (2E,4E)-11-methoxy-3,7, 11-trimethyl-2,4-dodecadienoate]; thiourea derivatives such as diafenthiuron [N-(2,6-diisopropyl-4-phenoxyphenyl)-N′-tert-butylcarbodiimide]; phenylpyrazole compounds; 4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifuoromethylpyrrol-3-carbonitrile [chlorfenapil]; metoxadiazone [5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2(3H)-one], bromopropylate [isopropyl 4,4′-dibromobenzilate], tetradifon [4-chlorophenyl 2,4,5-trichlorophenyl sulfone], chinomethionat [S,S-6-methylquinoxaline-2,3-diyldithiocarbonate], pyridaben [2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one], fenpyroximate [tert-butyl (E)-4-[(1, 3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate], tebufenpyrad [N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactins complex [tetranactin, dinactin and trinactin], pyrimidifen [5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidin-4-amine], milbemectin, abamectin, ivermectin and azadirachtin [AZAD]. Examples of the synergists include bis-(2,3,3,3-tetrachloropropyl) ether (S-421), N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MGK-264) and α-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene (piperonyl butoxide).
[0054] The application amount and concentration of the present controlling agent can be suitably designed according to the type of the formulations, time, place, and method of application, kind of noxious pests and damage.
EXAMPLES
[0055] The present invention will be further illustrated in more details by the production examples and test examples, although the present invention is not limited in any sense to these examples. Parts represent parts by weight in the following examples.
Production Example 1
[0056] Twenty parts of The Pvrone Compound are dissolves in 65 parts of xylene, mixed with 15 parts of emulsifier Soipol 3005X (registered trademark of Toho Chemical Co., Ltd.), and stirred sufficiently to give 20% emulusifiable concentrate.
Production Example 2
[0057] Forty parts of The Pyrone Compound are mixed first with 5 parts of Sorpol 5060 (registered trademark of Toho Chemical Co., Ltd.) and then with 32 parts of Carplex #80 (registered trademark of Shionogi & Co., Ltd.; fine powder of synthetic hydrated silicon oxide) and 23 parts of 300-mesh diatomaceous earth, and stirred with a juice mixer to give 40% wettable powder.
Production Example 3
[0058] One and a half (1.5) parts of The Pyrone Compound are mixed with 98.5 parts of AGSORB LVM-MS 24/48 (granular carrier of calcined montmorillonite having the particle diameter of 24- to 48-mesh provided by OIL DRI Corp.) sufficiently to give 1.5% granule.
Production Example 4
[0059] A mixture of 10 parts of The Pyrone Compound, 10 parts of phenylxylylethane and 0.5 part of Sumidule L-75 (tolylenediisocyanate provided by Sumika Bayer Urethane Co., Ltd.) is added to 20 parts of a 10% aqueous solution of gum arabic, and stirred with a homomixer to give an emulsion having the mean particle diameter of 20 μm. The emulsion is further mixed with 2 parts of ethylene glycol and allowed to react on a water bath of 60° C. for 24 hours to give a microcapsule slurry. On the other hand, a thicking agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate provided by Sanyo Chemical Co., Ltd.) in 56.3 parts of ion-exchanged water.
[0060] Forty-two and a half parts (42.5 parts) of the above microcapsule slurry and 57.5 parts of the above thicking agent solution are mixed to give 10% microencapsulated formulation.
Production Example 5
[0061] A mixture of 10 parts of The Pyrone Compound and 10 parts of phenylxylylethane is added to 30 parts of a 10% aqueous solution of polyvinyl alcohol and stirred with a homomixer to give an emulsion having the mean particle diameter of 3 μm. On the other hand, a thicking agent solution is prepared by dispersing 0.2 part of xanthan gum and 0.4 part of Veegum R (aluminum magnesium silicate provided by Sanyo Chemical Co., Ltd.) in 49.4 parts of ion-exchanged water.
[0062] Fifty parts of the above emulsion and 50 parts of the above thicking agent solution are mixed to give 10% flowable formulation.
Production Example 6
[0063] Five parts of The Pyrone Compound are mixed with 3 parts of Carplex #80 (registered trademark of Shionogi & Co., Ltd.; fine powder of synthetic hydrated silicon oxide), 0.3 parts of PAP and 91.7 parts of 300-mesh talc, and stirred with a juice mixer to give 5% dust.
Production Example 7
[0064] A half (0.5) part of The Pyrone Compound was dissolved in 10 parts of dichloromethane and mixed with 89.5 parts of Isoper M (isoparaffin provided by Exxon Chemical Corp.) to give 0.5% oil solution.
Production Example 8
[0065] An aerosol vessel was filled with 0.1 g of The Pyrone Compound and 49.9 g of Neotiozol (Chuokasei Company). The vessel was then equipped with a valve, and 25 g of dimethyl ether and 25 g of LPG were charged and shaken. The aerosol vessel was equipped with an actuator and to give oil-based aerosol.
Production Example 9
[0066] An aerosol vessel was filled with 0.2 g of The Pyrone Compound and 49.8 g of Neotiozol (Chuokasei Company). The vessel was then equipped with a valve, and 25 g of dimethyl ether and 25 g of LPG were charged and shaken. The aerosol vessel was equipped with an actuator and to give oil-based aerosol.
Production Example 10
[0067] An aerosol vessel was filled with 0.4 g of The Pyrone Compound and 49.6 g of Neotiozol (Chuokasei Company). The vessel was then equipped with a valve, and 25 g of dimethyl ether and 25 g of LPG were charged and shaken. The aerosol vessel was equipped with an actuator and to give oil-based aerosol.
Production Example 11
[0068] An aerosol vessel was filled with 0.8 g of The Pyrone Compound and 49.2 g of Neotiozol (Chuokasei Company). The vessel was then equipped with a valve, and 25 g of dimethyl ether and 25 g of LPG were charged and shaken. The aerosol vessel was equipped with an actuator and to give oil-based aerosol.
Production Example 12
[0069] An aerosol vessel was filled with 1.6 g of The Pyrone Compound and 48.4 g of Neotiozol (Chuokasei Company). The vessel was then equipped with a valve, and 25 g of dimethyl ether and 25 g of LPG were charged and shaken. The aerosol vessel was equipped with an actuator and to give oil-based aerosol.
Production Example 13
[0070] An aerosol vessel is filled with 50 parts of purified water and a dissolved mixture of 0.6 part of The Pyrone Compound, 0.01 part of BHT, 5 parts of xylene, 3.39 parts of deodorized kerosene and 1 part of Atmos 300 (registered trademark of Atlas Chemical Co.). The vessel is then equipped with a valve and 40 parts of propellant (liquefied petroleum gas) is charged through the valve into the aerosol vessel under pressure to give water-based aerosol.
Production Example 14
[0071] A solution prepared by dissolving 0.5 g of The Pyrone Compound in 20 ml of acetone is homogeneously mixed with 99.5 g of a carrier for a mosquito-coil (mixture of Tabu powder, Pyrethrum marc and wood powder at the ratio of 4:3:3). After 120 ml of water is added, the mixture is kneaded sufficiently, molded and dried to give mosquito-coil.
Production Example 15
[0072] One hundred and twenty grams (120 g) of water dissolving 0.3 g of Malachite Green dye and 0.2 g of sodium dehydroacetate were added to a carrier for a mosquito-coil (mixture of Tabu powder, Pyrethrum marc and wood powder at the ratio of 5:3:2), kneaded sufficiently, molded and dried to give a base material for mosquito-coil. One hundred milligrams (100 mg) of The Pyrone Compound were dissolved in 5 ml of acetone. A quarter milliliter (0.25 ml) of the solution was painted on 0.5 g of the above base material for mosquito-coil and sufficiently air-dried to give 1% mosquito-coil.
Production Example 16
[0073] One hundred and twenty grams (120 g) of water dissolving 0.3 g of Malachite Green dye and 0.2 g of sodium dehydroacetate are added to a carrier for a mosquito-coil (mixture of Tabu powder, Pyrethrum marc and wood powder at the ratio of 5:3:2), kneaded sufficiently, molded and dried to give a base material for mosquito-coil. In 0.7 g of deodorized kerosene, 0.3 g of The Pyrone Compound is dissolved. One gram (1 g) of the solution is painted on 29 g of the above base material for mosquito-coil and sufficiently air-dried to give 1% mosquito-coil.
Production Example 17
[0074] A solution prepared by dissolving 1 g of The Pyrone Compound in 20 ml of acetone is homogeneously mixed with 99 g of a carrier for a mosquito-coil (mixture of Tabu powder, Pyrethrum marc and wood powder at the ratio of 5:3:2) and 120 ml of water dissolving 0.3 g of Malachite Green dye and 0.2 g of sodium dehydroacetate. The mixture is kneaded sufficiently, molded and dried to give mosquito-coil.
Production Example 18
[0075] Acetone is added to 0.2 g of The Pyrone Compound, 0.1 g of BHT and 0.4 g of piperonyl butoxide to make the total 10 ml. A half milliliter (0.5 ml) of the obtained solution is impregnated with a base material (a plate of compacted fibrils of a mixture of pulp and cotton linters: 2.5 cm×1.5 cm, 0.3 cm in thickness) for mosquito-mat homogeneously to give a mosquito-mat for electric heater.
Production Example 19
[0076] One-fifth part (0.2 part) of The Pyrone Compound and 0.1 part of BHT are dissolved in 99.7 parts of deodorized kerosene to give a solution. The solution is charged in a vessel of polyvinyl chloride. In the vessel is inserted an absorptive wick which is inorganic powder solidified with a binder and then calcined, the upper portion of which wick can be heated with a heater, to give a part of electric heating fumigation device using a liquid.
Production Example 20
[0077] A solution prepared by dissolving 100 mg of The Pyrone Compound in an appropriate amount of acetone is impregnated with a porous ceramic plate (4.0 cm×4.0 cm, 1.2 cm in thickness) to give a heating fumigant.
[0078] Next, a method for preparing The Pyrone Compound is shown as Reference preparation example.
Reference Preparation Example
[0079] Ten grams (10.0g, 79.3 mmol) of 4-hydroxy-6-methyl-2-pyrone were suspended in 100 ml of toluene at room temperature. To the suspension, 1.22 g (10.0 mmol) of N,N-dimethylaminopyridine, 8.79 g (86 mmol) of isovaleric acid and 18.5 g (89.7 mmol) of dicyclohexylcarbodiimide were added subsequently. The mixed solution was stirred for 1 hour at room temperature, and then heated to 70° C. and stirred for 20 hours under heating. After the mixed solution was allowed to stand at room temperature, the precipitated insoluble dicyclohexylurea was filtered off, and washed with 1N hydrochloric acid once and 10% brine twice. The organic layer was dried over magnesium sulfate and evaporated under reduced pressure to give a crude oily product.
[0080] The crude oily product was subjected to silica gel column chromatography (eluent:hexane/ethyl acetate=6/1) to give 7.0lg of The Pyrone Compound (yield 42%).
[0081] 1H-NMR (CDCl 3 /TMS): 0.96 (6H, d), 2.22 (1H, m), 2.27 (3H, s), 2.96 (2H, d), 5.93 (1H, s), 16.99 (1H, s).
[0082] The effect of the present controlling agent is shown in the following Test Examples. For showing an efficacy of the present controlling agent enough, 4-hydroxy-6-methyl-3-(2-methylpropanoyl)-2-pyrone (hereinafter, referred to as Reference compound 1) described in Japanese Unexamined Patent Publication No. sho-51-19126 (Compound No. 3) of the formula:
[0083] 4-hydroxy-6-methyl-3-(2-ethylbutanoyl)-2-pyrone (hereinafter, referred to as Reference compound 2) described in Japanese Unexamined Patent Publication No. sho-51-19126 (Compound No. 5) of the formula:
[0084] and 4-hydroxy-6-methyl-3-(cyclopropanecarbonyl) -2-pyrone (hereinafter, referred to as Reference compound 3) described in Japanese Unexamined Patent Publication No. sho-51-19126 (Compound No. 11) of the formula:
[0085] were used as references.
Test Example 1
[0086] According to Production example 7, each of the 0.5% oil solutions of The Pyrone Compound and Reference compound 1 was prepared.
[0087] A square of paper (side: 20 cm) was covered on the iron net set on the bottom of the metallic chamber (46 cm×46 cm, 70 cm in height). A container (8.75 cm in diameter, 7.5 cm in height, having 16-mesh net at the bottom and spreading butter on the wall for preventing escape) was set on the paper. In the container, ten (5 males and 5 females) adult German cockroaches were released. By means of spray gun, 1.5 ml of the above oil solution was applied to the test insects at pressure of 4.1×10 4 Pa from the upper part of the chamber. The container was taken out of the chamber 30 seconds after spraying and the test insects were transferred to a plastic cup. Two minutes after spraying, the knocked-down cockroaches were counted.
[0088] The results are given in Table 1.
TABLE 1 Knock-down percentage (%) The Pyrone Compound 100 Reference compound 1 10
Test Example 2
[0089] According to Production example 7, each of the 0.25% oil solutions of The Pyrone Compound and Reference compounds 2 and 3 was prepared. The same procedures as Test Example 1 gave the knock-down percentages and KT 50 values (minutes for knocked-down 50% of cockroaches) in Table 2.
TABLE 2 Knock-down percentage (%) KT 50 (minutes) The Pyrone Compound *1 95 0.85 Reference compound 2 *2 0 more than 10 Reference compound 3 *2 6.7 more than 10
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4-Hydroxy-6-methyl-3-(3-methylbutanoyl)-2-pyrone has a rapid controlling effect against arthropods such as Dictyoptera insects (e.g. German cockroach, smokybrown cockroach).
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RIGHTS OF THE GOVERNMENT
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
BACKGROUND OF THE INVENTION
This invention relates a method for preparing aromatic heterocyclic block copolymers.
In general, aromatic heterocyclic extended chain polymers are well known for their outstanding thermal, physical, and chemical properties. Arnold et al, U.S. Pat. No. 4,108,835, disclose extended rod-like benzo-bis-oxazole and benzo-bis-thiazole polymers having superior mechanical properties as well as a high degree of thermal and hydrolytic stability. However, these materials presented special processing problems because of the extended-chain, rigid-rod, structural character of their molecules.
In accordance with the invention defined in U.S. Pat. No. 4,207,407, to Helminiak et al, it was found that the processing problem could be overcome by blending a coil-like, aromatic, heterocyclic polymer with a rod-like, aromatic, heterocyclic polymer. An improved method for blending coil-like and rod-like polymers is disclosed in U.S. Pat. No. 4,377,546, to Helminiak et al.
Wolfe et al, in application Ser. Nos. PCT/US82/01285 and PCT/US82/01286, both filed Sept. 17, 1982, disclose aromatic heterocyclic block copolymers made up of rigid and flexible segments. These copolymers are prepared by separately polymerizing the rigid segments and the flexible segments onto the rigid segments.
We have found that these block copolymers can be prepared by a simpler procedure.
Accordingly, it is an object of the present invention to provide a method for preparing aromatic heterocyclic block copolymers having rigid and flexible segments.
Other objects and advantages of the present invention will be apparent to those skilled in the art.
DESCRIPTION OF THE INVENTION
In accordance with the present invention, there is provided a method for preparing aromatic heterocyclic block copolymers having rigid and flexible segments of the general formulas: ##STR1## wherein Y and Z are the same or different and are selected from the group consisting of ═NH, ═S, ═O and ═NC 6 H 5 ; m is an integer equal to the number of repeating units and has a value such that the rigid segment has an intrinsic viscosity of about 8 to 31 dl/g as determined in methanesulfonic acid at RT; and n is an integer equal to the number of repeating units and has a value such that the polymer Ia or Ib has an intrinsic viscosity of about 4 to about 24 dl/g as measured in methane sulfonic acid at RT.
The method of this invention comprises the steps of preparing the rigid rod polymer block in polyphosphoric acid (PPA) followed by addition of a copolymerizable monomer and copolymerization of the same. The rigid rod segment is prepared according to the following general reactions: ##STR2## wherein n and Y are as described previously, and X is --NH 2 , --SH, --OH or --NHC 6 H 5 .
Following polymerization of the rigid rod segment IVa or IVb, a copolymerizable monomer of the general formula ##STR3## wherein X is as previously defined, is added to the reaction mixture containing the rigid rod segment, and polymerization of the flexible segments as well as grafting of these segments onto the rigid rod segments is carried out.
In carrying out the process, the diamino monomer IIa or IIb is initially dehydrochlorinated. This is accomplished by mixing the monomer IIa or IIb and terephthalic acid with polyphosphoric acid and heating the mixture under an inert gas atmosphere at a temperature ranging from about 40° to 100° C. for a period of about 6 to 24 hours. A slight excess of one of the monomers is employed.
Following dehydrochlorination, the reaction mixture is heated at a temperature in the approximate range of 100° to 200° C. for a period of about 18 to 36 hours. In a preferred procedure, the reaction temperature is increased gradually during the reaction period, e.g., 130° C. for 3 hours, 150° C. for 3 hours, 170° C. for hours, 185° C. for 3 hours, and 195°-200° C. for 16 hours, or 160° C. for 16 hours and 190° C. for 16 hours, or the like. At the end of the reaction period, a small aliquot of the polymer is precipitated from solution into water, washed with water until acid-free and air dried. If the intrinsic viscosity of the polymer in methanesulfonic acid is not within the desired range of about 8 to 31 dl/g, polymerization is continued until an aliquot sample has the desired viscosity.
Once the rigid-rod segment has a desired intrinsic viscosity, as determined by one or more aliquot samples, the reaction mixture, is cooled to about 30° to 60° C. and the monomer Va or Vb is added thereto. The resulting mixture is heated under an inert gas atmosphere at a temperature ranging from about 40° to about 100° C. for a period of about 6 to 24 hours to effect the dehydrochlorination of monomer Va or Vb. Following the dehydrochlorination, the reaction mixture is heated at a temperature in the approximate range of 100° to 250° C. for a period of about 12 to 36 hours. Aliquot samples may be collected, as described previously, to determine the intrinsic viscosity of the resulting polymer.
Intrinsic viscosity is determined by extrapolation of η rel/c and ln η rel/c to zero concentration in methanesulfonic acid at RT.
At the end of the reaction period the polymer is precipitated from solution by pouring the reaction mixture into a coagulation bath, such as water or methanol. If a bulk polymer is desired, the reaction mixture is poured directly into the coagulation bath, with or without stirring. The polymer may also be formed into fibers by extruding the polymer/PPA solution through a suitable spinnerette into the coagulation bath. The resulting fiber may be drawn and heat-treated following known procedures.
The relative proportions of the rigid-rod segment to the flexible segments can range from about 1:5 to 5:1, preferably 1:3 to 3:1.
The extended chain polymer compositions of the present invention are suitable for spinning into highly ordered and high strength fibers. Such fibers are suitable substitutes for other inorganic or organic products.
The following examples illustrate the invention.
EXAMPLE I
2,5-Diamino-1,4-benzenedithiol dihydrochloride (3.04 g, 12.4 mmol) and terephthalic acid (2.08 g, 12.5 mmol) were placed in a 50 ml resin flask equipped with mechanical stirrer and nitrogen inlet/outlet tubes. 76 g of polyphosphoric acid (84% P 2 O 5 ) was added to the flask. The resulting mixture was stirred and heated to 40° C. for 8 hours and 70° C. for 12 hours to effect dehydrochlorination of the diamino monomer. The reaction mixture was then heated to 160° C. for 16 hours followed by heating to 190° C. for an additional 16 hours. A small aliquot of the polymer was precipitated into water, washed with water until acid free, then air dried. This sample had an intrinsic viscosity of 12.9 dl/g in methanesulfonic acid at RT.
To 14.8 g of the above polyphosphoric acid solution containing 0.66 g of carboxy-terminated rigid rod, was added 3,4-diaminobenzoic acid monohydrochloride (3.23 g, 1.7 mmol). After the system was purged with nitrogen, 103 g of polyphosphoric acid (84% P 2 O 5 ) was added. The resulting mixture was slowly heated to 100° C. and maintained at that temperature for 10 hours to effect dehydrochlorination. The reaction mixture was then heated to 200° C. for 3 hours, then 230° C. for 16 hours. The viscous solution was cooled to 100° C., precipitated into water, washed with water, then dried at 140° C. under reduced pressure. Yield 2.16 g (82%).
Analysis for 75% C 7 H 4 N 2 .H 2 O-25% C 14 H 6 N 2 5 2 : Calculated: C, 62.7; H, 3.93; N, 18.28, Found: C, 60.96; H, 3.94; N, 18.42.
The polymer had an intrinsic viscosity of 10.7 dl/g in methanesulfonic acid at RT. Films of the above block copolymer cast from methanesulfonic acid exhibited the following mechanical properties: Tensile, 40,100 psi; Modulus, 350,000 psi.
EXAMPLE II
The procedure given in Example I was carried out to prepare a like copolymer containing 50% rigid rod/50% flexible. Films of this copolymer had the following mechanical properties: Tensile, 9,700 psi; Modulus, 1,520,000 psi.
EXAMPLE III
To 0.53 g of a carboxy-terminated poly-para-phenylenebenzbisthiazole (intrinsic viscosity, 17.75 dl/g) was added 88 g of polyphosphoric acid (84% P 2 O 5 ). The mixture was heated under nitrogen at 160° C. until a homogeneous solution was obtained. The solution was cooled to 50° C. and 1.92 g (0.0093 mol) of 4-amino-3-mercaptobenzoic acid hydrochloride was added thereto under reduced pressure. The temperature was maintained at 50° C. until dehydrochlorination was complete. The reaction mixture was slowly heated to 190° C. and maintained at that temperature for 24 hours. On cooling to room temperature the polymer was precipitated into water, washed and dried at 140° C. under reduced pressure.
Analysis for 30% C 14 J 6 N 2 S 2 -70% C 7 H 3 NS: Calculated: C, 63.13; H, 2.80; N, 10.51; S, 24.09 Found: C, 61.31; H, 2.48; N, 10.26; S, 21.90 Intrinsic viscosity 6.5 dl/g.
EXAMPLE IV
Fibers were made by extruding a solution containing 5.8 wt% of the block copolymer of Example I in methanesulfonic acid through a single hole 254 micron spinnerette into a quenching bath of deionized water at room temperature. The coagulated fiber was drawn between two rollers at a draw ratio of 3.4. The fibers were neutralized in ammonium hydroxide solution over night, washed with deionized water and air dried.
The block copolymer fibers were heat treated by passing them through an oven under constant tension in an air atmosphere. Residence time of the fiber was 30 sec. at 800° F.
The data presented in the following table demonstrate the excellent mechanical properties of these fibers. For comparison the mechanical properties of a polybenzimide (PBI) fiber are included.
TABLE______________________________________ w %w % rigid YoungsFlexible seg- Modulus Tensile ElongationSegment ment (psi) (psi) at break______________________________________As spun 70 30 4.83 × 10.sup.6 13.4 × 10.sup.4 6.5Heat 70 30 15.94 × 10.sup.6 20.34 × 10.sup.4 1.4Treated 100 0 2.09 × 10.sup.6 9.6 × 10.sup.4 28% (PBI)______________________________________
Various modifications may be made to the present invention without departing from the spirit or the scope of the following claims.
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Thermally stable aromatic heterocyclic block copolymers are prepared by reacting a diamino monomer and terephthalic acid to form a carboxy-terminated rigid rod segment and then polymerizing a carboxy-monoamine monomer therewith to form flexible segments grafted onto the rigid rod segments.
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[0001] This is a continuation-in-part of the patent application filed on Oct. 24, 2001 under attorney docket number USA.288 entitled “Scanning Techniques in Selective Deposition Modeling.”
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention.
[0003] The invention relates in general to solid freeform fabrication and, in particular, to a cooling technique for removing heat from the surface of a an object being formed by a solid freeform fabrication apparatus.
[0004] 2. Description of the Prior Art.
[0005] Recently, several new technologies have been developed for the rapid creation of models, prototypes, and parts for limited run manufacturing. These new technologies can generally be described as solid freeform fabrication, herein referred to as “SFF.” Some SFF techniques include stereolithography, selective deposition modeling, laminated object manufacturing, selective phase area deposition, multi-phase jet solidification, ballistic particle manufacturing, fused deposition modeling, particle deposition, laser sintering, and the like. In SFF, complex parts are produced from a modeling material in an additive fashion as opposed to conventional fabrication techniques, which are generally subtractive in nature. For example, in conventional fabrication techniques material is removed by machining operations or shaped in a die or mold to near net shape and then trimmed. In contrast, additive fabrication techniques incrementally add portions of a build material to selected locations, typically layer by layer, in order to build a complex part.
[0006] SFF technologies typically utilize a computer graphic representation of a part and a supply of a build material to fabricate the part in successive layers. SFF technologies have many advantages over the prior conventional manufacturing methods. For instance, SFF technologies dramatically shorten the time to develop prototype parts and can quickly produce limited numbers of parts in rapid manufacturing processes. They also eliminate the need for complex tooling and machining associated with the prior conventional manufacturing methods, particularly when creating molds for casting operations. In addition, SFF technologies are advantageous because customized objects can be produced quickly by processing computer graphic data.
[0007] One category of SFF that has emerged is selective deposition modeling, herein referred to as “SDM.” In SDM, a build material is dispensed in a layerwise fashion while in a flowable state and allowed to solidify to form an object. In one type of SDM technology the modeling material is extruded as a continuous filament through a resistively heated nozzle as described, for example, in U.S. Pat. No. 5,303,141 to Batchelder et al. In yet another type of SDM technology the modeling material is jetted or dropped in discrete droplets in order to build up a part. In one particular SDM apparatus, a thermoplastic material having a low-melting point is used as the build material, which is delivered through a jetting system such as those used in ink jet printers. One type of SDM process utilizing ink jet print heads is described, for example, in U.S. Pat. No. 5,555,176 to Menhennett, et al. Hence, there is a variety of dispensing devices available for dispensing build material in SDM applications.
[0008] Recently there has developed an interest in dispensing curable phase change materials in SDM. After dispensing the material, the material is cured by exposure to actinic radiation. This produces a substantial amount of heat that must be removed before dispensing the next layer of material so that the next layer will solidify. The amount of heat is significantly greater than that produced when dispensing non-curable materials. As disclosed in U.S. Pat. No. 6,136,252 to Bedal et al., an axial fan is used to direct a flow of cooling air over the layers formed from a non-curable phase change material. The flow is directed perpendicular to the layers and disperses in all directions along the layers. Undesirably, this configuration does not produce a uniform distribution of cooling air across the layers. Further, if flow is increased to remove the additional heat produced by curable materials, the temperature of the material dispensing device is affected. If the temperature of the dispensing device is reduced, so too is the drop mass of the material being dispensed which can result in build failure.
[0009] Thus, there is a need in the art to develop a cooling technique capable of uniformly removing a substantial amount of heat generated in the layers of the three-dimensional object formed by SFF. These and other difficulties have been overcome according to the present invention.
BRIEF SUMMARY OF THE INVENTION
[0010] The present invention provides its benefits across a broad spectrum of SFF processes by providing a method and apparatus for removing heat from the layers of a three-dimensional object formed in a layerwise manner from a build material. The cooling system comprises at least one fan for generating a flow of air, and at least one air duct in communication with the fan for receiving the flow of air. The air duct shapes the flow of air into a uniform sheet of air flow that is delivered from an exit end of the air duct across the layers of the three-dimensional object. The flow is uniform in that the velocity of the air flow is substantially the same when measured at any location along a transverse direction to the direction of flow at the midpoint of the thickness of the sheet of air flow. The air duct is provided with a protrusion on the exit end for diverting the uniform sheet of air flow away from the air duct and towards the layers of the three-dimensional object. In SDM applications, which dispense a build material from a dispensing device, the protrusion diverts the flow path of the uniform sheet of air flow and has been found to substantially eliminate transient air flows moving toward the dispensing device.
[0011] In some embodiments, the air duct comprises a single containment wall for shaping the flow of air into a uniform sheet of air flow. In most of these single containment wall air duct configurations, the flow of air from the fans are bent between the inlet and exit ends of the air duct to bias the air flow against the containment wall as the uniform sheet of air flow is shaped.
[0012] In other embodiments, the air duct comprises two containment walls for shaping the flow of air into a uniform sheet of air flow. In most of these dual containment wall configurations, two uniform sheets of air flow are delivered across the layers of the three-dimensional object to effectively double the cooling capacity, when needed.
[0013] In most of the embodiments a protrusion is provided upstream from the exit end of the air duct. The sizing of the upstream protrusion adjusts the thickness of the uniform sheet of air flow and the velocity profile of the thickness of the uniform sheet of air flow. The upstream protrusion may or may not be needed depending on the desired air velocity and cooling rate for a particular application.
[0014] A variety of fan configurations are provided for generating the flow of air that is delivered to the air duct. The fans can be axial fans, centrifugal fans, mixed flow fans, cross flow fans, and the like. In some embodiments, a plurality of fans are used to generate the air flow used to form the uniform sheet of air flow or multiple uniform sheets of air flow to cool the three-dimensional object being built.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The present invention method and apparatus will become apparent upon consideration of the following detailed disclosure of the invention, especially when it is taken in conjunction with the accompanying drawings wherein:
[0016] [0016]FIG. 1 is a diagrammatic side view of a prior art SDM scanning system producing an axial flow of cooling air;
[0017] [0017]FIG. 2 is a diagrammatic side view of a dispensing trolley of the present invention;
[0018] [0018]FIG. 3 is a diagrammatic side view of another dispensing trolley of the present invention;
[0019] [0019]FIG. 4 is a diagrammatic view of an apparatus for practicing the present invention;
[0020] [0020]FIG. 5 is an isometric diagrammatic view of a curved air duct of the present invention;
[0021] FIGS. 6 A- 6 I are cross-sectional views of alternative air duct profiles of the present invention;
[0022] [0022]FIG. 7 is a cross-sectional view of an embodiment of the present invention cooling system;
[0023] [0023]FIG. 8 is an isometric diagrammatic view of the embodiment of FIG. 7;
[0024] [0024]FIG. 9 is a cross-sectional view of another embodiment of the present invention cooling system;
[0025] [0025]FIG. 10 is a cross-sectional view of another embodiment of the present invention cooling system;
[0026] [0026]FIG. 11 is a cross-sectional view of another embodiment of the present invention cooling system;
[0027] [0027]FIG. 12 is a cross-sectional view of another embodiment of the present invention cooling system;
[0028] [0028]FIG. 13 is a cross-sectional view of another embodiment of the present invention cooling system;
[0029] [0029]FIG. 14 is a cross-sectional view of another embodiment of the present invention cooling system;
[0030] [0030]FIG. 15 is a cross-sectional view of another embodiment of the present invention cooling system;
[0031] [0031]FIG. 16A and 16B are cross-sectional views showing the change in thickness of the uniform sheet of air flow when a protrusion is provided upstream on the air duct;
[0032] [0032]FIG. 17A and FIG. 17B are respective air velocity profiles of the thickness of the uniform sheet of air flows shown in FIGS. 16A and 16B;
[0033] [0033]FIG. 18 is a cross-sectional view of another embodiment of the present invention cooling system;
[0034] [0034]FIG. 19 is an isometric diagrammatic view of another embodiment of the present is invention cooling system; and
[0035] [0035]FIG. 20 is an isometric diagrammatic view of an apparatus adapted for practicing the present invention.
[0036] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0037] The present invention provides its benefits across a broad spectrum of SFF processes. While the description which follows hereinafter is meant to be representative of a number of such applications, it is not exhaustive. As will be understood, the basic apparatus and methods taught herein can be readily adapted to many uses. It is intended that this specification and the claims appended hereto be accorded a breadth in keeping with the scope and spirit of the invention being disclosed despite what might appear to be limiting language imposed by the requirements of referring to the specific examples disclosed.
[0038] While the present invention is applicable to all SFF techniques and objects made therefrom, the invention will be described with respect to solid deposition modeling utilizing a curable phase change build material and phase change support material dispensed in a flowable state. It is to be appreciated that the present invention can be implemented with any SFF technique utilizing a wide variety of materials. For example, the build material can be a photocurable or sinterable material that is heated to a flowable state but when solidified may form a high viscosity liquid, a semi-solid, a gel, a paste, or a solid. In addition, the build material may be a composite mixture of components, such as a mixture of photocurable liquid resin and powder material such as metallic, ceramic, or mineral, if desired. In general, the present invention may be implemented with any SFF technique where a substantial amount of heat transfer is needed to cool the object being formed.
[0039] As used herein, the term “a flowable state” of a build material is a state wherein the material is unable to resist shear stresses that are induced by a dispensing device, such as those induced by an ink jet print head when dispensing the material, causing the material to move or flow. Preferably, the flowable state of the build material is a liquid state, however, the flowable state of the build material may also exhibit thixotropic properties. The term “solidified” and “solidifiable” as used herein refer to the phase change characteristics of a material where the material transitions from the flowable state to a non-flowable state. A “non-flowable state” of a build material, as used herein, is a state wherein the material is sufficiently self-supportive under its own weight so as to hold its own shape. A build material existing in a solid state, a gel state, a paste state, or a thixotropic state, are examples of a non-flowable state of a build material for the purposes of discussion herein. Further, the term “cured” or “curable” refers to any polymerization reaction. Preferably the polymerization reaction is triggered by exposure to radiation or thermal heat. Most preferably the polymerization reaction involves the cross-linking of monomers and oligomers initiated by exposure to actinic radiation in the ultraviolet or infrared wavelength band. Further, the term “cured state” refers to a material, or portion of a material, in which the polymerization reaction has substantially completed. It is to be appreciated that as a general matter the material can easily transition between the flowable and non-flowable state prior to being cured, however, once cured, the material cannot transition back to a flowable state and be dispensed by the apparatus.
[0040] Additionally, the term “support material” refers to any material that is intended to be dispensed to form a support structure for the three-dimensional objects as they are being formed, and the term “build material” refers to any material that is intended to be dispensed to form the three-dimensional objects. The build material and the support material may be similar materials having similar formulations but, for purposes herein, they are to be distinguished only by their intended use.
[0041] Furthermore, the term “main scanning direction” refers to the direction of the reciprocal back and forth motion necessary to dispense material to form three-dimensional objects. The three-dimensional objects are formed by dispensing the materials to specific drop locations on raster or scanning lines aligned in the main scanning direction within the build environment. Generally, each raster line is associated with a discharge orifice of the dispensing device. With reference to the figures, the main scanning direction is the direction of the X-axis of the Cartesian coordinate system shown. The term “secondary scanning direction” refers to the sideways motion necessary to offset the raster lines associated with the discharge orifices of the dispensing device relative to the object being formed so the discharge orifices do not dispense along just one path on the object. With reference to the figures, the secondary scanning direction is the direction along the Y-axis of the Cartesian coordinate system shown. The term “build direction” refers to a direction that is perpendicular to the layers being formed by an SDM apparatus. The apparatus must shift the dispensing device relative to the object staging structure in the build direction as the layers are formed during the build process. With reference to the figures the shift in the build direction is the direction along the Z-axis of the Cartesian coordinate system shown. Further, a “substantially stationary” dispensing device refers to a dispensing device in an apparatus that does not move relative to the apparatus when dispensing material in the mains scanning direction, but may move in the secondary scanning direction and build direction when not dispensing material. The term “object staging structure” refers to any structure capable of supporting a three-dimensional object as it is formed in a layerwise manner by an SDM apparatus. For example, a plate or build platform can be used as an object staging structure, as well as a mesh grating or container, if desired.
[0042] In addition, the term a “uniform sheet of air flow” refers to an elongated stream of air flowing in a one direction along a surface such as a layer of a three-dimensional object being formed by any SFF process. The flow is uniform in that the velocity of the air flow is substantially the same when measured at any location along a transverse direction to the direction of flow at the midpoint of the thickness of the sheet of air flow. The velocity of the air flow measured in a transverse direction to the direction of flow along the midpoint of the thickness of the sheet should not vary by more than about 35%, and more preferably by no more than about 10%. Most preferably the velocity of the air flow within the sheet does not vary at all. Since the velocity of the air flow is directly related to the cooling rate of the surface over which it passes, the uniform sheet of air flow provided over the layers of a three-dimensional object formed by SFF helps achieve more consistent cooling for the object.
[0043] A conventional SDM scanning methodology is shown in FIG. 1. Generally, the dispensing trolley 11 carries the dispensing device 13 , planarizer 15 , and cooling fans 17 , and is reciprocally driven in the main scanning direction 12 between opposed ends 14 in the build environment 25 . The cooling fans 17 direct a cooling stream of air in a direction perpendicular to the layers being formed. Upon contact with the layers the cooling stream spreads out in all directions across the layers. The build platform 19 is offset in the secondary scanning direction 16 for randomizing dispensing and for targeting all locations parallel to the main scanning direction. The secondary scanning direction 16 is represented as a circle and dot in FIG. 1 since it is coincident with the line of sight of that view. The build platform 19 is also shifted in the build direction after each layer is formed. The SDM computer controller or processor 21 coordinates these motions and provides the firing pulses to the dispensing orifices 23 to dispense the material on targeted drop locations on the scanning lines. This conventional scanning technique is discussed, for example, in U.S. Pat. No. 6,136,252 to Bedal et al.
[0044] Now, referring to FIG. 2, a preferred scanning methodology is shown. The build platform 19 is reciprocally driven in the main scanning direction 12 between opposed ends 14 in the build environment 25 , instead of the dispensing trolley 11 . The dispensing trolley 11 remains substantially stationary during motion in the main scanning direction. The dispensing trolley is offset in the secondary scanning direction 16 for randomization when the build platform is at the opposed ends 14 of the reciprocating motion in the main scanning direction, and is shifted upward in the build direction after each layer is formed. Alternatively, the build platform may be offset in the secondary scanning direction 16 and shifted downward in the build direction 18 , if desired.
[0045] Referring to FIG. 2 a flow of air 22 for cooling the object is provided on the dispensing trolley 11 . Since a preferred build material is curable by exposure to actinic radiation, a significant amount of heat is generated during the layer formation process. This heat, in addition to the latent heat generated from the material as it transitions into a non-flowable state, must be removed without affecting the temperature of the dispensing device. The conventional cooling fan configuration shown in FIG. 1 provides an air profile in the shape of an inverted “T” that moves vertically downward towards the object and then disperses in all directions over the surface of the object. The inverted “T” air profile is sufficient for cooling objects in the prior SDM systems dispensing non-curable materials. However, increasing the air velocity of the inverted “T” air profile to meet the cooling capacity needed for curable materials undesirably affects the dispensing temperature of dispensing devices such as ink jet print heads used in SDM. As the dispensing temperature drops, so to does the drop mass of the dispensed material. Thus, non-uniform temperature distributions around the print head create non-uniform drop mass of ejected material droplets across the print head array. In addition, prior scanning techniques that reciprocate the print head throughout the build environment also contribute to this problem.
[0046] In order to maintain a uniform dispensing temperature across the dispensing device 13 it is desirable to substantially eliminate the transient convection air flows occurring around the print head while also providing the necessary cooling air flow rates required for removing heat from the layers of the object being formed. Referring to FIG. 2, a flow of air 22 for cooling the object is provided on the dispensing trolley 11 . The flow of air 22 is directed away from the dispensing device 13 in the shape of a uniform sheet of air flow 94 over the surface of the object 20 being formed below. Cooling air enters a fan or blower 24 as indicated by arrow 26 . In the embodiment shown, the fan 24 is a centrifugal fan that is elongated and extends the entire length of the dispensing device 13 in the Y-direction, which is coincident with the line of sight of FIG. 2. Alternatively, the fan may be an axial fan, a mixed flow fan, a cross flow fan, or the like. The fan or blower 24 ejects the air outwardly in a horizontal manner as a sheet of air shown by numeral 92 towards a curved air duct 28 which re-directs the sheet of air vertically downward toward the object 20 being formed. The flow of air 92 is shaped into a substantially uniform sheet of air 94 so that uniform cooling can be provided by convection across the surface of the layers. A protrusion 30 is provided to initially trip the flow of air to thicken the width of the sheet as shown at 32 , which in turn thickens the width of the sheet in the area indicated by numeral 22 . At the exit end of the air duct 28 there is another protrusion 34 . The protrusions 34 and 30 establish high pressure zones 36 , which impart a sideways force on the stream of air that diverts the stream air flow away from the dispensing device 13 . The diverted flow path of the sheet of air is shown by numeral 22 . The point where the uniform sheet of air flow 94 traverses the surface of the object 20 is shown by numeral 38 . Heat is transferred by convection from the object 20 to the air flow, which travels away from the object and dispensing device in the direction noted by numeral 40 . The uniform sheet of air flow 94 is directed away from the dispensing device 13 to substantially prevent active cooling of the dispensing device 13 . This is true even when the air flow does not traverse the object 20 , such as when the build platform 15 is located at the left opposed end 22 in FIG. 8. However, as the build platform 15 moves from right to left, the uniform sheet of air flow 94 is directed across the surface 38 of the object 20 .
[0047] The protrusion 34 , which diverts the flow path of the uniform sheet of air flow, has been found to substantially eliminate transient air flow moving toward the dispensing device. Experiments were conducted wherein a flow of air from a flat air duct was provided at an inclined angle to the object surface in order to eliminate transient air flow moving backwards toward the dispensing device. The inclined angle was intended to direct the air flow away from the dispensing device. However, these experiments revealed that transient air flow still migrated backwards to the dispensing device, and could not be substantially eliminated. Thus, it is believed that the provision of the protrusion on the exit end of the air duct to divert the uniform sheet of air flow prevents transient air flow from migrating toward the dispensing device.
[0048] With the uniform sheet of air flow being directed away from the dispensing device 13 , the velocity of the air flow can be substantially increased in order to achieve the desired heat transfer rate necessary for removing the heat being released from the layers of three-dimensional object. In addition, with the print head positioned between the uniform sheet of air flow 94 and the planarizer 15 , a pocket of air 42 is established around the dispensing device 13 . This pocket or buffer zone of air 42 is substantially undisturbed within the apparatus and provides an insulating or shielding effect around the dispensing device 13 . This in turn allows for more uniform temperature control of the dispensing device.
[0049] The dispensing trolley 11 in FIG. 2 shows just one uniform sheet of air flow 94 for cooling the object 20 . In the embodiment shown in FIG. 3, a second uniform sheet of air flow 94 ′ for cooling the object is provided adjacent to the planarizer 15 on the left side of the dispensing trolley 11 . The second uniform sheet of air flow 94 ′ is the mirror image of the one shown in FIG. 2 and has its own fan 24 ′ for generating the air flow. The second uniform sheet of air flow 94 ′ is diverted outwardly to the left. Utilizing two uniform sheets of air flows effectively doubles the convention heat transfer capabilities of the system. This configuration is desirable when just one uniform sheet of air flow is insufficient to remove the heat from the layers of the object 20 formed within the SDM apparatus. Furthermore it is to be appreciated that the configuration of the uniform sheets of air flows may also be implemented on the dispensing device 11 of the prior art scanning methodology shown in FIG. 1, if desired.
[0050] Referring to FIG. 4 there is illustrated generally by the numeral 10 a solid freeform fabrication apparatus for practicing the present invention. The build platform 19 is reciprocally driven by the conventional drive means and motor 44 , instead of the dispensing trolley 11 shown in FIG. 1. A gear reduction means 46 is provided so that the motor 44 can be driven at a high speed under low torque conditions. This eliminates the control problems associated with accelerating and decelerating a varying mass. The dispensing trolley 11 is precisely positioned by actuation means 48 in the build direction to adjust for each layer of the object 20 as it is formed. The actuation means 48 comprises precision lead screw linear actuators driven by servomotors (both not shown). The ends of the linear actuators of the actuation means 48 reside on opposite ends of the build environment 25 and in a transverse direction to the direction of reciprocation of the build platform. In this transverse direction, which is in line with the secondary scanning direction 16 , the dispensing trolley 11 is shifted to execute randomization as discussed previously. However, for ease of illustration in FIG. 4, the linear actuators and dispensing trolley are shown in a two-dimensionally flat manner giving the appearance that the linear actuators are aligned in the direction of reciprocation of the build platform 19 . Although they may be aligned with the direction of reciprocation, the use of space within the apparatus is optimized by situating them in a transverse direction to the reciprocation in the main scanning direction.
[0051] In the build environment generally illustrated by numeral 25 , there is shown by numeral 20 a three-dimensional object being formed with integrally formed supports 50 . The object 20 and supports 50 both reside in a sufficiently fixed manner on the build platform 15 so as to withstand the acceleration and deceleration forces induced during reciprocation of the build platform while still being removable from the platform. This is achieved by dispensing at least one layer of support material on the build platform before dispensing the build material since the support material is designed to be removed at the end of the build process. The material identified by numeral 52 A is dispensed by the apparatus 10 to form the three-dimensional object 20 , and the material identified by numeral 52 B is dispensed to form the support 50 . Containers identified generally by numerals 54 A and 54 B respectively hold a discrete amount of these two materials 52 A and 52 B. Umbilicals 56 A and 56 B respectively deliver the material to the dispensing device 13 , which in the embodiment shown is an ink jet print head having a plurality of dispensing orifices 23 .
[0052] The dispensing trolley 11 shown in FIG. 4 comprises a heated planarizer 15 that removes excess material from the layers to normalize the layers being dispensed. The heated planarizer 15 contacts the material in a non-flowable state and because it is heated, locally transforms some of the material to a flowable state. Due to the forces of surface tension, this excess flowable material adheres to the surface of the planarizer, and as the planarizer rotates the material is brought up to the skive 58 which is in contact with the planarizer 15 . The skive 58 separates the material from the surface of the planarizer 15 and directs the flowable material into a waste reservoir identified generally by numeral 60 located on the trolley 11 . A heater 62 and thermistor 64 on the waste reservoir 60 operate to maintain the temperature of the waste reservoir at a sufficient level so that the waste material in the reservoir remains in the flowable state. The dispensing trolley 11 is configured to have two uniform sheets of air flows for cooling the object as shown in FIG. 3, however the air flows have been omitted in FIG. 4 for ease of illustration.
[0053] In the apparatus shown in FIG. 4, the build material 52 A is a phase change material that is cured by exposure to actinic radiation. After the curable phase change material 52 A is dispensed in a layer it transitions from the flowable state to a non-flowable state. After a layer has been normalized by the passage of the planarizer 15 over the layer, the layer is then exposed to actinic radiation by radiation source 66 . Preferably the actinic radiation is in the ultraviolet or infrared band of the spectrum. For this SDM apparatus, planarizing occurs prior to exposing a layer to the radiation source 66 . This is because the planarizer shown can only normalize the layers if the material in the layers can be changed from the non-flowable to the flowable state, which cannot occur if the material 52 A has been already cured by exposure to radiation. However, the planarizer may be replaced with a mill cutter or similar device that chips or grinds the layers smooth, which could normalize the layers even after they have been cured, if desired.
[0054] In conjunction with the curable build material 52 A, a non-curable phase change material 52 B is used for forming the support 50 . Since the support material cannot be cured, it can be removed from the object and build platform, for example, by being dissolved in a solvent or by being melted by application of heat. A preferred method for removing the support material is disclosed in U.S. patent application Ser. No. 09/970,727 filed Oct. 3, 2001 entitled “Post Processing Three-Dimensional Objects Formed by Selective Deposition Modeling.” A preferred method for dispensing a curable phase change material to form a three-dimensional object and for dispensing a non-curable phase change material to form supports for the object is disclosed in U.S. patent application Ser. No. 09/971,337 filed Oct. 3, 2001 entitled “Selective Deposition Modeling with Curable Phase Change Materials.” A preferred curable phase change material and non-curable phase change support material is disclosed in U.S. patent application Ser. No. 09/971,247 filed Oct. 3, 2001 entitled “Ultra-Violet Light Curable Hot Melt Composition.” A preferred material feed and waste is disclosed in U.S. patent application Ser. No. 09/970,956, filed Oct. 3, 2001 entitled “Quantized Feed System.” All of these related applications are incorporated by reference in their entirety herein.
[0055] The air duct 28 is shown in further detail in FIG. 5. The air duct 28 has an inlet end identified generally by numeral 68 and exit end identified generally by numeral 70 . The air duct has guide walls 72 extending between the inlet end and exit end which constrain the flow of air traveling through the air duct to prevent the flow of air from fanning out as the air exits from the air duct 28 . The air duct 28 shown in FIG. 5 forms a single containment wall that is curved so as to bend the air flow approximately 90 degrees as it travels from the inlet end to the exit end. Because the curvilinear motion of the air flow imparts a centrifugal force that acts against the air duct 28 , the air flow is biased against the air duct as it travels from the inlet end 68 to the exit end 70 . Hence, the air duct configuration shown in FIG. 5 does not need an additional containment wall to form the uniform sheet of air flow.
[0056] It is not necessary for the air duct comprising a single containment wall to bend the air 90 degrees as it travels from the inlet end to the exit end of the duct to establish the uniform sheet of air flow. Referring to FIG. 18, the bend angle of the air duct 28 , identified by numeral 108 , can be significantly less than 90 degrees, such as about 10 degrees or less, if desired. In addition, the bend angle can be greater than 90 degrees, such as up to 180 degrees, if desired. Whatever bend angle 108 is used, a large bend radius 110 along the containment wall will provide for a uniform sheet of air flow traveling along the surface of the air duct between the inlet and exit ends. The large bend radius further assists the shaping of the uniform sheet of air flow for cooling the layers of the object being formed. However, the air duct may also be substantially straight as long as the air duct is provided with a uniform sheet of air flow directly from the fan or fans that generate the air flow.
[0057] In FIG. 5 the protrusion 34 which establishes the high pressure zone 36 to divert the air flow is square in cross-section, however other configurations may be used as well. Referring to FIGS. 6A through 61 a number of alternative configurations for the shape of the protrusion 34 are shown. In FIG. 6A, the protrusion 34 is square in cross section as in FIG. 5. In FIG. 6B, a double step configuration is shown while in FIG. 6C the protrusion 34 is a tab extending generally perpendicular at the end of the air duct 28 . Still further, FIGS. 6D, 6E, and 61 show alternative configurations incorporating either a convex or concave radius on the protrusion 34 . In FIG. 6F a chamfered configuration is shown and in FIG. 6H a reverse chamfer configuration is shown. In FIG. 6G a double sided tab configuration is shown. Other configurations and combinations of shapes for the protrusion are possible as well, such as polygonal shapes, elliptical shapes, and the like.
[0058] Another embodiment of the present invention cooling system is shown in FIGS. 7 and 8. The air duct 28 in this embodiment is the same as the one shown in FIG. 5, however a plurality of fans 24 are used. The fans 24 are arrayed above a cowling 74 which directs the air 26 drawn through the fans 24 towards the air duct 28 through opening 76 . In this embodiment the fans 24 are axial fans used in conjunction with the cowling 74 to generate the flow of air delivered to the air duct 28 , instead of the elongated centrifugal fan configuration shown in FIGS. 2 and 3. The cowling may include guide vanes (not shown) to direct the flow of air in a single direction towards the air duct 28 . Further, guide vanes may also be provided on the air duct 28 , if needed. It may also be desirable to stagger the direction of rotation of the fans, for example, by rotating one fan clockwise and an adjacent fan counter clockwise so as to minimize spiraling effects in the air flow stream.
[0059] Another embodiment of the present invention cooling system is shown in FIG. 9. In this embodiment two arrays of axial fans 24 generate the flow of air that is delivered to the air duct 28 through a cowling 74 . Two separate openings draw in the air 26 to form the air flow. Another embodiment having a double array of axial fans 24 is shown in FIG. 10 where the cowling 74 positions the fans 24 at an angle as opposed to the parallel configuration shown in FIG. 9.
[0060] Another embodiment of the present invention cooling system is shown in FIG. 11 in conjunction with a dispensing trolley 11 carrying a dispensing device 13 and planarizer 15 . In this embodiment, the air duct comprises a first containment wall 78 and second containment wall 80 which function to form two uniform sheets of air flows similar to those shown in FIG. 3. However, in this embodiment an array of axial fans 24 is provided to generate a flow of air that is divided in two to form two uniform sheets of air flow. Further, the protrusion 30 that widens the thickness of the uniform sheets of air flow is located on the first guide wall and the protrusion 34 that diverts the sheets away from the dispensing device is located on the ends of the second guide wall 80 . Four embodiments similar to the one shown in FIG. 11 are shown in FIGS. 12, 13, 14 , and 15 . These embodiments possess a similar air duct structure, however, they employ different fan configurations for generating the air flow. In FIG. 12, a double stacked array of axial fans 24 are used to generate the air flow needed to form the uniforms sheets of air flows. In the embodiment shown in FIG. 13, two separate arrays of axial fans 24 are used to generate the air flow needed. In FIG. 14 a centrifugal fan 24 is used having an axial air inlet 26 that is coincident with the line of sight in the view. Further, the embodiment shown in FIG. 15 comprises two elongated centrifugal fans 24 for generating the air flow needed. When centrifugal fans are used, they can have straight radial blades, curved forward blades, curved backward blades, or straight backward blades. In addition, other fan types can be used as well, such as mixed flow fans and cross flow fans, if desired.
[0061] It is to be appreciated that when forming the air duct with two containment walls, the flow of air need not be bent as it travels from the inlet end to the exit end of the air duct when forming the uniform sheet of air flow. Hence, the containment walls may be substantially straight instead of being curved, as are shown in the air duct configurations in FIGS. 11, 12, 13 , 14 , and 15 .
[0062] Now referring to FIGS. 16A, 16B, and 17 A, 17 B the effect on the thickness of the uniform sheet of air flow by the provision of the protrusion 30 is shown. FIG. 16A shows air duct 28 without the protrusion upstream from the exit end of the air duct. Without the upstream protrusion, the thickness 82 for the uniform sheet of air flow adjacent protrusion 34 is established as shown. The velocity profile of the sheet of air flow taken at thickness 82 is shown in FIG. 17A by numeral 100 . The same air duct is shown including the protrusion 30 upstream from the exit end of the air duct 28 is shown in FIG. 16B. As discussed in conjunction with FIG. 2, the protrusion 30 triggers the air flow to widen just after the protrusion, as indicated by numeral 32 . The widening of the air flow caused by the protrusion 30 also widens the thickness 84 of the uniform sheet of air flow adjacent the protrusion 34 compared to the thickness 82 of the air flow without the protrusion. The velocity profile of the sheet of air flow taken along the thickness 84 is shown in FIG. 17A by numeral 102 . As shown in FIGS. 17A and 17B, the velocity profile is more uniform across the thickness of the sheet of air flow when the upstream protrusion is provided. Further, the peak air velocity of the profile, identified by numeral 104 in FIG. 17B and by numeral 106 in FIG. 17A, is less when the upstream protrusion is provided on the air duct. Normally the peak air velocity of the profile will reside generally at the midpoint of the thickness of the sheet of air flow. According to the present invention, the peak air velocity remains substantially the same when measured at any location along a transverse direction to the direction of flow. However, lowering the peak air velocity of the profile may be needed in order to prevent damage to the object being formed, and particularly when forming geometrically fragile objects under optimal cooling rates. Thus, the protrusion 30 can be used to optimally adjust the thickness of the uniform sheet of air flow and the velocity profile of the thickness of the uniform sheet of air flow as may be needed depending on the desired air velocity and cooling rate for a particular application. However, not all applications will need the upstream protrusion according to the present invention.
[0063] Referring to FIG. 19 another alternative embodiment of the present invention cooling system is shown. In this embodiment two separate uniform sheets of air flow are provided which are directed substantially parallel to the secondary scanning direction 16 . The two cooling systems represented by air ducts 28 and centrifugal fans 24 need not be mounted on the dispensing trolley with the dispensing device 13 and planarizer 15 as in the other embodiments.
[0064] Now referring to FIG. 20, an SDM apparatus is shown at 10 for practicing the present invention. To access the build environment, a slideable door 86 is provided at the front of the apparatus. The object can be easily removed when the build platform (not shown) is positioned at the opposed end of reciprocation adjacent slideable door 86 . The door 86 does not allow radiation within the machine to escape into the environment. The apparatus is configured such that it will not operate or turn on when the door 86 open. In addition, when the apparatus is in operation the door 86 will not open. A build material feed door 88 is provided so that the build material can be inserted into the apparatus 10 . A support material feed door 70 is also provided so that the support material can be inserted into the apparatus 10 . A waste drawer 90 is provided at the bottom end of the apparatus 10 so that the expelled waste containers can be removed from the apparatus. A user interface 98 is provided which is in communication with the external computer 35 previously discussed which tracks receipt of the print command data from an external computer.
[0065] What have been described are preferred embodiments in which modifications and changes may be made without departing from the spirit and scope of the accompanying claims.
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A cooling system for removing heat from the layers of a three-dimensional object built in a layerwise manner from a build material in a solid freeform fabrication apparatus. The cooling system provides an air duct that delivers a uniform sheet of air flow over the layers of the three-dimensional object while it is built. It is emphasized that this abstract is provided to comply with the rules requiring an abstract that will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. 37 CFR 1.72(b)
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BACKGROUND OF THE INVENTION
The present invention generally relates to an automatic safe disposable blood sampling device for medical use, more particularly, to a casing self-locking type of automatic safe blood sampling device, in which a press button of which is locked by engagement thereof with the casing of the blood sampling device after a lancet needle of the blood sampling device is launched so that the blood sample device is brought into a self-locking state and can not be reused.
Various types of medical blood sampling device are known, there is a tendency to develop a “mini” type automatic blood sampling device which is safe and disposable once the lancet needle is launched. In order to make it disposable, this kind of blood sampling device is provided with a disposable self-locking mechanism which achieves self-locking effect immediately after a lancet needle of the blood sampling device is launched, thus causing the catch-launching mechanism failure. Therefore, the potential safety hazards involved in the previous blood sampling device are thoroughly eliminated.
Presently, there are two types of self-locking mechanism. The first type of self-locking mechanism employs a structure in which the lancet needle is engaged with a casing, that is, the lancet needle and the casing each are provided with a special structure, the engagement of the lancet needle with the casing achieves a self-locking effect after the lancet needle of the blood sampling device is launched. For example, the Chinese Utility Model No. CN2486104Y filed on Jul. 30, 2001 and granted to the applicant of the present application on Apr. 17, 2002 discloses an automatic safe disposable blood sampling device having a new type catch-launching mechanism, in the blood sampling device of the above Chinese Utility Model No. CN2486104Y, an elastic arm C is slantwise provided on the lancet needle and a stopping notch is provided in the casing of the blood sampling device. After the lancet needle of blood sampling device is launched, the elastic arm C is retracted together with the lancet needle so as to fall into the stopping notch to be self-locked therewith.
The second type of self-locking mechanism is a lancet needle self-locking structure, that is, the self-locking mechanism is completely provided on the lancet needle, and achieves a self-locking effect after the lancet needle of the blood sampling device is launched. For example, the Chinese Patent Application No. 200420025752.5 filed on Mar. 25, 2004 by the same applicant as that of the present application discloses an automatic safe disposable blood sampling device of lancet needle self-locking type. In the blood sampling device, and an elastic arm is provided on a side portion of the lancet needle. A self-locking hook is provided on an end of the elastic arm, and the elastic arm is inwardly bent upon application of an external force when the lancet needle of the blood sampling device is launched by pressing. Consequently, and the end is forced across the hook so as to be caught by the self-locking hook, thus achieving the self-locking effect. The above two types of self-locking mechanisms have disadvantageous in their structures, features and effects respectively.
BRIEF SUMMARY OF THE INVENTION
An object of the present invention is to provide a novel casing self-locking type of automatic safe blood sampling device based on “one-off launching and not reusable” principle, in the casing self-locking type of automatic safe blood sampling device of the present invention, a self-locking mechanism is completely formed by structures on a casing. This self-locking mechanism is of the third type, that is, the casing self-locking type.
In order to achieve the above object, there is provided a casing self-locking type of automatic safe blood sampling device, comprising: a casing formed with a launching chamber therein, the launching chamber being provided with a lancet needle-exiting hole at a front end thereof; a lancet needle arranged inside the launching chamber; a spring; a launching mechanism composed of the spring and a catch-launching mechanism; a press-launching mechanism provided on the casing; and a self-locking mechanism composed of barbs provided on the press-launching mechanism and self-locking hooks or self-locking notches provided on the casing corresponding to the barbs, the self-locking hooks or self-locking notches being located on paths along which the barbs are advanced, respectively.
The related contents and variations of the above technical scheme are explained as follows:
1. In the above technical scheme, the self-locking mechanism has two types, i.e. the side-pressing type and the end-pressing type.
2. With regard to the side-pressing type of self-locking mechanism, the press-launching mechanism is embodied as press button for launching provided on a side of the blood sampling device, the press button is mounted on a side of a casing or formed by a first elastic arm extended integrally from the side of the casing, barbs are provided on the press button, and self-locking hooks or self-locking notches are provided on the casing corresponding to the barbs.
3. With regard to the end-pressing type of self-locking mechanism, the press-launching mechanism is embodied as a sliding sleeve provided at an end of the blood sampling device, the sliding sleeve as a part of the casing of the blood sampling device is slideably connected to another part of the casing, barbs are provided on the sliding sleeve, and self-locking hooks or self-locking notches are provided on provided on the another part of the casing corresponding to the barbs respectively.
The operation of the blood sampling device according to the present invention is described as follows.
When being pressed, the press-launching mechanism triggers the catch-launching mechanism, so that the lancet needle is disengaged from the casing, the spring pushes the lancet needle so as to launch the lancet needle. As the same time, because of movement of the press-launching mechanism, the barbs pass across the self-locking hooks or self-locking notches during the forward movement thereof. Therefore, during retraction, the barbs are locked with the self-locking hooks or self-locking notches and thereby can not return to their primed states, thereby the catch-launching mechanism is caused to be failure and can not be reused.
By comparison to the prior art, the blood sampling device has the following advantages.
1. The self-locking mechanism of the blood sampling device according to the present invention is novel, the self-locking function is achieved by changing structure of the casing, so that the blood sampling device is simple in structure and can be operated reliably.
2. The operation of the self-locking mechanism is performed in the following orders: the self-locking mechanism firstly enters into its self-locking state, and then enters into launching state. However, the conventional self-locking mechanism using engagement of the lancet needle with the casing is firstly launched, and then enters into its self-locking state. Therefore, the blood sampling device according to the present invention can reflect the design philosophy of one-off launching and not reusable.
3. In comparison to the conventional self-locking mechanism, the self-locking mechanism of the present invention is novel, simple in structure.
4. The blood sampling device according to the present invention is easy to use and simple to operate.
5. After use, the lancet needle is retracted into the casing automatically and will be not exposed to outside, thus ensuring safety of the used blood sampling device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a structural sectional view of the blood sampling device according to the first embodiment of the present invention, showing an assembled state before use;
FIG. 2 is a structural sectional view of the blood sampling device according to the first embodiment of the present invention, showing that the lancet needle is pushed into a self-locked state;
FIG. 3 is a structural sectional view of the blood sampling device according to the first embodiment of the present invention, showing that the blood sampling device is in a state to be launched with a lancet needle cap being removed;
FIG. 4 is a structural sectional view of the blood sampling device according to the first embodiment of the present invention, showing that the blood sampling device is in a launching state;
FIG. 5 is a structural sectional view of the blood sampling device according to the first embodiment of the present invention, showing a state after use;
FIG. 6 is a partial sectional view of a self-locking mechanism of the blood sampling device according to the first embodiment of the present invention, showing a state before the lancet needle is locked;
FIG. 7 is a sectional view taken along line B-B in FIG. 6 ;
FIG. 8 is a partial sectional view of a self-locking mechanism of the blood sampling device according to the first embodiment of the present invention, showing that the blood sampling device is in a state to be launched;
FIG. 9 is a sectional view taken along line A-A in FIG. 8 ; and
FIG. 10 is a structural schematic view of the blood sampling device according to the second embodiment of the present invention.
In the above drawings, the reference numerals denote the following members respectively: 1 : case; 2 : lancet needle; 2 - 1 : first locking section; 2 - 2 : second locking section; 3 : spring; 4 : launching chamber; 5 : lancet needle-exiting hole; 6 : elongated lancet needle cap; 7 : boss; 8 : lancet needle tip; 9 : catching plate; 10 : catching groove; 11 : protruding ring; 12 : second elastic arm; 13 : first elastic arm; 13 - 1 : intermediate section of the first elastic arm; 13 - 2 : extension section of the first elastic arm; 13 - 3 : leg; 14 : blocking notch; 15 : barb; 16 : self-locking hook; 17 : sliding sleeve; 18 : bevel; 19 : elastic catching member; 20 : outer sleeve.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described in detail with reference to the accompanying drawings.
THE FIRST EMBODIMENT
As shown in FIG. 1 to FIG. 5 , there is illustrated a side-pressing and casing self-locking type of automatic safe disposable blood sampling device, comprising a casing 1 , a lancet needle 2 , an elongated lancet needle cap 6 and a spring 3 .
The casing 1 comprises an upper part and a lower part which are connected into an integral structure by using holes and pins provided on contacting surfaces thereof respectively. A launching chamber 4 is formed inside the casing 1 , and the lancet needle 2 and the spring 3 are arranged in the launching chamber 4 . The spring 3 is located behind the lancet needle 2 wherein the head of the spring 3 is caught in a catching groove 10 , and the tail of the spring 3 is caught on the catching plate 9 , thus forming an elastic sliding structure in a launching direction. A lancet needle-exiting hole 5 is provided at one end of the casing 1 in a direction consistent with the launching chamber direction. A cylindrical boss 7 is provided at the head of the lancet needle 2 , and a lancet needle tip 8 is extended centrally out of the boss 7 . Further, a protruding ring 11 is provided circumferentially on the boss 7 . An elongated lancet needle cap 6 has a rod structure and is provided with a deep hole in a front portion thereof and a tail wing at a rear end thereof. The front portion of the elongated lancet needle cap 6 passes through the lancet needle-exiting hole 5 so as to fit over the boss 7 , and the elongated lancet needle cap 6 can be prevented from retracting accidentally from the boss 7 through engagement of the protruding ring 11 with the deep hole.
A catch-launching mechanism and a self-locking mechanism are provided between the lancet needle 2 and a side of the casing 1 along a compression path of the spring 3 .
As shown FIGS. 6 to 9 , the catch-launching mechanism comprises a second elastic arm 12 extended from a side of the casing 1 , a first elastic arm 13 extended from another side of the casing 1 , and a blocking notch 14 provided in the lancet needle 2 . The second elastic arm 12 and the blocking notch 14 are located at a bottom side of the casing 1 in FIGS. 1 to 5 , and the second elastic arm 12 is inclined towards to the inside of the launching chamber 4 . A cantilever end of the second elastic arm 12 is engaged with the blocking notch 14 so as to form a locking structure. The first elastic arm 13 serving as a press button is located at an upper side of the casing 1 in FIG. 1 , and an intermediate section 13 - 1 of the first elastic arm 13 serving as a pressing portion protrudes from the upper side of the casing 1 in FIG. 1 . An extension section 13 - 2 of the first elastic arm 13 has an inversed U-shape, and the lancet needle 12 is located between two legs 13 - 3 of the inversed U-shape extension section 13 - 2 while two legs 13 - 3 extend into holes provided on the casing 1 and pass across the launching chamber 4 respectively. Distal ends of the two legs 13 - 3 contact or are close to the cantilever end of the second elastic arm 12 .
The self-locking mechanism comprises barbs 15 provided respectively on two outer sides of the inversed U-shape extension section 13 - 2 , and self-locking hooks 16 provided at positions corresponding to the barbs 15 on the inner wall of the casing 1 . The self-locking hooks 16 are located on paths along which the barbs 15 are advanced. In order to protect the self-locking mechanism in a state in which the lancet needle 2 of the blood sampling device is not launched, the lancet needle 2 is provided with a first locking section 2 - 1 and a second locking section 2 - 2 . Prior to being locked, the position of the second locking section 2 - 2 corresponds to that of the inversed U-shape extension section 13 - 2 as shown in FIG. 1 , and the bottom side of the second locking section 2 - 2 has the same inclination and inclined direction as that of the second elastic arm 12 . The cross section of the second locking section 2 - 2 has substantially the same width from top to bottom, and widths of gaps formed between the two sides of the second locking section 2 - 2 and the inner walls of the casing 1 are smaller than that of the two legs 13 - 3 of the inversed U-shape extension section 13 - 2 . Therefore, at this time, the inversed U-shape extension section 13 - 2 of the first elastic arm 13 can not move downwards. As a result, the barbs 15 on the inversed U-shape extension section 13 - 2 can not engage with the self-locking hooks 16 on the casing 1 so as to lock with each other respectively, as shown in FIG. 7 . When the lancet needle 2 is pushed towards to the rear side (right side in FIG. 1 ) of the casing 1 , the first locking section 2 - 1 of the lancet needle 2 is moved rearwards so that the position of the first locking section 2 - 1 is brought to gradually come close to the position of the inversed U-shape extension section 13 - 2 of the first elastic arm 13 . The width of the cross-section of the first locking section 2 - 1 is decreased gradually from top to bottom, and the widths of gaps formed between two sides of the first locking section 2 - 1 and the inner walls of the casing 1 are equal to or larger than that of the two legs 13 - 3 of the inversed U-shape extension section 13 - 2 respectively. Therefore, the inversed U-shape extension section 13 - 2 can be moved downwards so that the barbs 15 can be moved downwards along with the inversed U-shape extension section 13 - 2 so as to be engaged and locked with the self-locking hooks 16 on the casing 1 . Before the cantilever end of the second elastic arm 12 is caught by the blocking notch, since the second locking section 2 - 2 has a larger width in the transverse direction of the cross-section thereof (the cross-section of the second locking section 2 - 2 has a rectangle shape in the embodiment, as shown in FIG. 7 ), the inversed U-shape extension section 13 - 2 of the first elastic arm 13 can not pass through the gaps formed between the inversed U-shape extension section 13 - 2 and inner walls of the casing 1 even if pressing the inversed U-shape extension section 13 - 2 , thus achieving the self-locking mechanism. The lancet needle 2 is brought into a locking state by pushing the elongated lancet needle cap 6 , at this time, the first locking section 2 - 1 of the lancet needle 2 corresponds to the inversed U-shape extension section 13 - 2 , since the transverse width of the cross-section of the first locking section 2 - 1 is decreased from top to bottom (the cross-section of the first locking section 2 - 1 has a tapered shape in this embodiment, as shown in FIG. 9 ), the widths of the gaps increase, so that two legs 13 - 3 of the inversed U-shape extension section 13 - 2 of the first elastic arm 13 can be inserted into the gaps formed between the inversed U-shape extension section 13 - 2 and inner walls of the casing 1 by pressing the inversed U-shape extension section 13 - 2 , contact with and act on the cantilever end of the second elastic arm 12 at last, thus causing the cantilever end of the second elastic arm 12 to disengage from the blocking notch 14 .
THE SECOND EMBODIMENT
As shown in FIG. 10 , there is illustrated an end-pressing and casing self-locking type of automatic safe disposable blood sampling device, comprising a casing, a lancet needle 2 , an elongated lancet needle cap 6 and a spring 3 . The casing comprises a sliding sleeve 17 and an outer sleeve 20 , and an elastic catching member 19 is provided at a side of the lancet needle 2 . When the elongated lancet needle cap 6 is pushed, the lancet needle 2 presses the spring 3 . While the elastic catching member 19 is caught at an end of the sliding sleeve 17 , thus achieving locking. The self-locking mechanism comprises a barb 15 and a self-locking hook 16 , and the barb 15 is provided on the sliding sleeve 17 while the self-locking hook 16 is provided on the outer sleeve 20 .
In operation, the elongated lancet needle cap 6 is first pulled out, then the outer sleeve 20 is held by hand of a user. Thereafter, the lancet needle-exiting hole in the casing is directed at a region of a human body to be blood-sampled and the blood sampling device is pressed. At the same time, the sliding sleeve 17 is moved by an external force towards a closed end (right end in FIG. 10 ) of the outer sleeve 20 (rightward in the FIG. 10 ) inside an inner chamber formed inside the outer sleeve 20 . The bevel 18 forces the elastic catching member 19 to disengage from the sliding sleeve 17 , and the spring 3 pushes the lancet needle 2 along a guide groove (not shown) to launch the lancet needle 2 . Then a lancet needle tip of the lancet needle 2 is ejected out of the lancet needle-exiting hole so as to puncture the region of a human body to be blood-sampled. At the same time, since the sliding sleeve 17 is slid towards the closed end of the outer sleeve 20 inside inner chamber of the outer sleeve 20 , the barb 15 is engaged and locked with the self-locking hook 16 . Therefore, the sliding sleeve 17 can not further slide inside the inner chamber of the outer sleeve 20 , thus causing the blood sampling device to fail.
While the present invention has been described with reference to the specific embodiments thereof, it should be understood by those ordinary skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt to a particular situation, material, composition of matter, process, process step or steps, to the objective, spirit and scope of the present invention. All such modifications are intended to be within the scope of the claims appended hereto.
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An automatic safe disposable blood sampling device includes a casing with a launching chamber formed therein. The launching chamber has a lancet needle-exiting hole at a front end thereof; a lancet needle arranged inside the launching chamber; a spring; a launching mechanism composed of the spring and a catch-launching mechanism; a press-launching mechanism provided on the casing; and a self-locking mechanism composed of barbs provided on the press-launching mechanism and self-locking hooks or notches provided on the casing which engage corresponding barbs. When pressed, the press-launching mechanism triggers the catch-launching mechanism, to disengage the lancet needle from the casing. The spring pushes the lancet needle so as to launch the lancet needle. During forward movement of the press-launching mechanism, the barbs pass across the self-locking hooks or notches. In the process of retraction, the barbs are locked with the self-locking hooks or notches and cannot return to their initial states.
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RELATED APPLICATION
This application is a national stage application based on PCT/LT2004/000002 filed on Mar. 31, 2004, which claims priority from Lithuania application 2003 081 filed Sep. 11, 2003.
FIELD OF THE INVENTION
The invention relates to man-powered flying devices.
BACKGROUND OF THE INVENTION
A sailplane-ornithopter, which has two pairs of flapping wings, links, cables, interconnected rods, and loops is known (USSR patent no. 1205, 64 C 33/02). A man-powered flying device with two flapping wings, and two different variants of stands and arms pedals, and links is known (M. K. Tichonov Moscow. 1949, pp. 168).
A motorised ornithopter with flapping wings with feather-shaped panels, where a mechanism automatically controls the rotation of its rods to the necessary angle, is known (USSR, certificate of authorship no. 187 533). A flying apparatus with inclined horizontal wing axes, two flapping wings consisting of a wing panel with a solid part and a second part consisting of panels-flaps mounted on rotatable rods, is known (French patent no. 2 171 946). A serious deficiency of the flapping wings of these flying devices is their imperfect aerodynamic profiles: the movement of the rods during the wings' rising-upbeat cycle creates a negative aerodynamic force directed downward. Thus these apparatuses cannot fly at slow speeds.
SUMMARY OF THE INVENTION
The purpose of this invention is to increase in every way the possibilities of a human pilot to make the most effective use of the power from all the strongest muscle groups: thighs, torso, shoulders, and arms, which would allow him to selectively fly in turns by flapping his wings or gliding, smoothly descend, manoeuvre easily, and steer it during such a flight with effective propulsion and guiding mechanisms adapted for this.
The specified aim is achieved by using two muscular propulsion engines: a femoral propulsion engine and a humeral propulsion engine in accordance with USSR invention certificate of authorship no. 945 491 of R. Dainys, the creator of this invention, and in accordance with international publication WO 03/035186 of an invention of R. Dainys. The invention of a muscular propulsion ornithopter-sailplane is intended to create an opportunity for a human pilot to use only the power of his own muscles to take off, fly by flapping his wings or gliding, manoeuvre freely, make various turns, and gradually or abruptly descend by reducing the speed of the descent and the flying speed and by reducing them to practically zero at the moment of landing. Such flying and gliding possibilities can be created by using both the first and the second variant of the muscular propulsion ornithopter-sailplane characterised by fundamental new features so that thanks to femoral and humeral propulsion engines the principal parts of the person's body which are joined and securely attached to them: the torso, thighs, shoulders, upper arms, and arms become a single integrated propelled-steered mechanism for flight. According to the first variant, the ornithopter-sailplane has one pair of flapping wings and a hang glider wing. According to the second variant, the ornithopter-sailplane has two pairs of flapping wings and a hang glider wing. The delta shaped-hang glider wing is used in this invention only as a well-mastered flying apparatus, although any other construction having markedly better aerodynamic profile parameters than a delta-shaped wing, could be much more effectively used in its place.
The fundamental originality Consists of the use a femoral propulsion engine in the flapping mechanism. To the femoral engine's torso base is attached a frame, to which is attached the posterior ball joints of inclined horizontal wing axles. The mobile anterior ball joints of the flapping wing axles are connected through intermediate links and intermediate ball joints to the humeral engine's humeral arms, which are attached by straps to one another, to the upper arms, and the shoulder base, which is joined to the torso base by a sliding ball joint. The kinematic chain of the flapping mechanism consists of femoral arms attached to the torso base, which arms are connected to the flapping wings through intermediate joints, intermediate links, and the wing arms.
The fundamentally original flapping wings have wing panels with rotatable stiff rods, to which are attached, asymmetrically to the rods' axes, stiff feather-like panels, which narrow at the ends and create a broken aerodynamic profile at the end of the wing with intervals between the adjacent feather-like panels and a solid aerodynamic profile in the middle of the wing when gliding or during the downward flapping movement of the wing. This profile creates increased lift and propulsion aerodynamic forces, which are created by the strong air whirls and flows created in the intervals between these panels due to the lengthwise and rotated deformations of the rods and due to bending deformations of the posterior edges of the feather-like panels. This wing construction during the period of its movement upwards and backwards forces the feather-like panels to rotate and changes them into a broken wing consisting of a row of rotated feather-like panels creating not only lifting but also forward propulsion forces. This effective action of the flapping wings is very important in the initial period of the ornithopter's ascent, which can create possibilities for the pilot to rise vertically or by flapping the wings to briefly hover by staying at one height.
The construction of the first variant of the ornithopter-sailpiane creates essentially new possibilities to perform such guiding-steering movements. The direct kinematic connection between the femoral arms and the wings allows the pilot to set one or both wings in positions with different angles by fixing the thighs in corresponding positions, by the thighs moving at different speeds, or by letting them lag according to the phases of the flapping cycle when each change in the angle of the declination of the flapping wings simultaneously changes the balance of the aerodynamic forces of these wings and creates possibilities for the pilot to make turns with just the uneven movements of the thighs.
Very diverse, essentially new guiding-steering movements can be performed by using the humeral engine by leaning the torso forward, backwards, and/or to the sides, rotating the shoulders about the lengthwise axis of the spine in different directions, or by making all the same movements while moving just the shoulders and upper arms. All of these steering movements are transmitted from the humeral arms to the mobile anterior joints of the wing axles through a direct kinematic chain of intermediate links and joints. By rotating the humeral arms backwards, the wings are rotated backwards, their angle of attack is increased, and the wings rise upwards and vice versa, by rotating the arms forward, the aerodynamic forces of the wings are reduced and the wings descend. By rotating one shoulder forwards or backwards or by rotating the shoulders in different directions, the wings move in opposite directions and therefore the ornithopter's tail end makes turns and banks. All of these ascending, descending, and banking steering-guiding movements can be made synchronically in co-ordination with the femoral steering-guiding movements. Furthermore, all of the guiding movements of the flapping wings that are described here can be made simultaneously in co-ordination with various steering movements of the hang glider wing and made during any ascent, active flapping flight, gliding, and descent. Therefore these great possibilities for a variety of guiding movements and their derivatives allow a pilot to perform completely analogous guiding movements such as agile flying birds make. Furthermore, by descending vertically like a parachute, otherwise called a ‘parachuting’ regime, it is even possible to descend in a backwards direction or descend while rotating about a vertical axis like a whirligig.
According to the second variant, an omithopter-sailpiane characterised by other essentially novel features can be created with a hang glider wing and two pairs, anterior and posterior, of flapping wings. Likewise in this variant, the femoral engine is used to perform various propulsion-flapping movements. In this case, the posterior ball joints of the axles for the anterior flapping wings and the anterior ball joints of the axles for the posterior flapping wings are attached in an immobile manner to the frame attached to the femoral engine's torso base. In this case, it is novel that in the direct kinematic chain the left femoral arm is joined to the anterior pair of flapping wings and the right femoral arm to the posterior pair of flapping wings. The guiding kinematic chain consists of intermediate links, arms, and joints that join the humeral arms to the anterior mobile ball joints of the anterior pair of wings and through additional arms and joints, to the posterior mobile ball joints of the posterior pair of wings. A pilot can perform flapping propulsion movements by moving his thighs simultaneously and also performing simultaneous upwards-backwards and downwards-forwards movements of both pairs of wings. But the essential difference in this case is that the pilot can simultaneously move his thighs in opposite directions just like a person running on the ground does. The essential novelty in this case is that the anterior and posterior pairs of wings move in opposite directions, one downwards, the other upwards, and can therefore create very uniform aerodynamic forces. In this variant the guiding movements are performed by fixing the flapping wings in various positions and creating different aerodynamic forces with them. The guiding-steering movements with the humeral engine are made in the same way as in the first variant by moving the humeral arms in a great diversity of ways and by alternating the angle of attack of the flapping wings. The essentially new difference and new possibilities in this case arise in the parachuting-descending regime where the parachuting-descending regime is created by using only the hang glider wing and posterior pair of flapping wings. In this case a possibility arises to regulate or reduce the speed of descent by slow flapping movements of the anterior pair of wings. In the second variant there are more favourable possibilities to perform vertical ascents or to maintain a longer hovering regime at one height by moving the thighs in opposite directions during a ‘running’ regime since during this period the aerodynamic forces created by both pairs of flapping wings even out.
BRIEF DESCRIPTION OF THE DRAWINGS
The essence of the invention is explained in the drawings, in which:
FIG. 1 depicts a side view of the first variant of the man-powered ornithopter-sailplane with one pair of flapping wings and a hang glider wing;
FIG. 2 depicts a top view of the same first variant in FIG. 1 ;
FIG. 3 depicts an axonometric view of the central part of the same first variant;
FIG. 4 depicts a rear view of the same first variant in FIG. 1 ;
FIG. 5 depicts part of a flapping wing;
FIG. 6 depicts cross section BB of the flapping wing from FIG. 5 ;
FIG. 7 depicts cross section CC of the flapping wing from FIG. 5 ;
FIG. 8 depicts cross section BB from FIG. 5 with rotatable feather-like panels when the horizontal flying speed V H equals 0 ;
FIG. 9 depicts cross section BB from FIG. 5 with rotatable feather-like panels when the horizontal flying speed is V H ;
FIG. 10 depicts the aerodynamic forces and the speeds of the feather-like panels of a wing moving upwards and backwards in the case depicted in FIG. 8 where the flying speed is zero;
FIG. 11 depicts the aerodynamic forces and the speeds of the feather-like panels of a wing moving upwards and backwards in the case depicted in FIG. 9 ;
FIG. 12 depicts a side view of the second variant of the man-powered ornithopter-sailplane with two pairs of flapping wings and a hang glider wing and depicts the feather-like panels of the posterior pair of flapping wings in a rotated position like in FIG. 8 and FIG. 9 ;
FIG. 13 depicts a top view of the second variant of the man-powered ornithopter-sailplane in FIG. 12 ;
FIG. 14 depicts the construction of the immobile attachment of the frame to the ball joints of the posterior pair of flapping wings that partially replaces part of the second variant of the ornithopter-sailplane in FIG. 12 ;
DETAILED DESCRIPTION OF THE INVENTION
A man-powered ornithopter-sailplane according to the first variant with femoral and humeral propulsion engines in accordance with USSR certificate of authorship no. 945 941 and in accordance with international invention publication WO 03/035 186 having torso base 1 , torso strap 2 , two femoral arms 3 with thigh straps 4 , two axles 5 joining torso base 1 to femoral arms 3 . Torso base I is connected in the front by sliding ball or cardan joint 6 to shoulder base 7 in front of it. To the edges of torso base 1 are attached the frame's left and right framework, which consists of strip pairs 8 , 9 , 10 . The strip pairs 9 , 10 converge in the front, are joined together, and are attached to ball or cardan joint 11 . Created from strip pairs 8 , 10 , the frame's posterior corners are connected by strip 12 . The left 15 and right 16 ball joints of the left 13 and right 14 wing axles of the flapping wings are rigidly attached respectively to the left and right corners created by strips 8 , 10 . Wing axles 13 , 14 are rotated horizontally and the angle of that rotation can be variously and easily changed by guiding-steering movements. The mobile anterior left 17 and right 18 ball joints of wing axles 13 , 14 are joined respectively through intermediate left 19 and right 20 links to the left 21 and right 22 ball joints, which are attached to the left 23 and right 24 humeral arms respectively. Humeral arms 23 , 24 are attached in front to each other by strap 25 , in back to shoulder base 7 by left and right straps 26 and 27 , and to the upper arms by left 28 and right 29 upper arm straps respectively. Wing axles 13 , 14 have rigidly attached left 30 and right 31 brackets creating an extension of axles 13 , 14 beyond immobile ball joints 15 , 16 . The ends of brackets 30 , 31 are joined to one another by tightly stretched posterior cord 32 , which acts like a counterbalance to tightly stretched anterior cord 33 between mobile anterior ball joints 17 , 18 . This counterbalance between stretched cords 32 , 33 guarantees the maintenance of a uniform distance between mobile anterior ball joints 17 , 18 when performing all the guiding movements of the flapping wings with humeral arms 23 , 24 . To femoral arms 3 are attached respectively the left 34 and right 35 ball joints, which are joined through left and right intermediate links 36 , 37 to left and right ball joints 38 , 39 , which are attached to left and right moving wing arms 40 , 41 , which are rigidly attached to wing axles 13 , 14 .
Wing arms 40 , 41 are rigidly attached respectively to the left 42 and right 43 flapping wing panels. In the variant depicted in FIG. 5 , in the middle of wing panels 42 , 43 are mounted four stiff rotatable rods 44 , to the external ends of which are attached, asymmetrically to their axes, four stiff feather-like panel 45 with an aerodynamic profile. The axes of the bend in rods 44 are mounted so that in the middle part of the wing, in a cross section according to BB ( FIG. 6 ) the feather-like panel 45 lie snug against one another and form the wing's general aerodynamic profile and in the end part of the wing, in a cross section according to CC ( FIG. 7 ), they form an analogous aerodynamic profile but have narrowing intervals between the adjacent feather-like panel 45 . In the middle of wing panels 42 , 43 is a mechanism for uniformly rotating the rods, which is made from cranks 46 , which are mounted on rotatable rods 44 and interconnected by parallel links 47 , 48 , 49 . To link 48 is attached support 50 , which limits the angle of rotation of rods 44 by resting on support 51 , which is attached to the immobile construction of the wing panels and to which is also attached spring 52 , the other end of which is attached to link 48 . Spring 52 returns links 47 , 48 , 49 and rods 44 to their initial position after their rotation and at the same time ensures the rotation of feather-like panels 45 to the shut position.
In both the first and the second variant of the ornithopter-sailplane with one or two pairs of flapping wings, hang glider wing 53 and guiding trapezium 54 are attached to a ball joint 11 at the front of the frame.
A man-powered ornithopter-sailplane according to the second variant with a hang glider wing and two pairs of flapping wings and with femoral and humeral propulsion engines in accordance with USSR certificate of authorship no. 945 941 and international invention publication WO 03/035 186, has torso base 1 , torso strap 2 , two femoral arms 3 with thigh straps 4 , and two axles 5 joining the torso base to femoral arms 3 . Torso base 1 is connected in front by sliding ball or cardan joint 6 to shoulder base 7 . To the sides of the torso base are attached the frame's left and right framework, which consists of strip pairs 8 , 9 , 10 . Strip pairs 9 , 10 converge in front, are joined together, and are attached to ball or cardan joint 11 . Created from strip pairs 8 , 10 , the frame's posterior corners have an extension consisting of strip 8 and are attached to one another by strip 12 . According to the first design of the second variant, to strips 10 are rigidly attached left and right posterior ball joints 57 , 58 of left and right axles 55 , 56 of the anterior left and right wings and to the frame's posterior corners are rigidly attached anterior left and right ball joints 61 , 62 of axles 59 , 60 of the posterior left and right flapping wings. To strips 10 are attached in a sliding manner left and right ball joints 63 , 64 , which are connected to left and right links 65 , 66 , in front of which are left and right joints 67 , 68 , which are joined respectively to left and right links 69 , 70 , which are connected on top to anterior mobile left and right ball joints 71 , 72 of axles 55 , 56 of the anterior pair of wings. The inferior ends of links 69 , 70 are connected to left and right ball joints 21 , 22 , which are connected to left and right humeral arms 23 , 24 , which are attached to themselves in front by strong strap 25 , in back by straps 26 , 27 to shoulder base 7 , and at the other end to the upper arm by upper arm straps 28 , 29 . Left and right links 65 , 66 at the posterior end are connected to left and right ball joints 73 , 74 , which are connected through left and right intermediate links 75 , 76 respectively to left and right mobile joints 77 , 78 of axles 59 , 60 respectively of the posterior pair of wings. Femoral arms 3 through left and right ball joints 34 , 35 are connected to left and right links 79 , 80 . Left link 79 through intermediate joints 81 , 82 is connected to left and right intermediate links 83 , 84 , which through ball joints 85 , 86 are connected to left and right anterior wing arms 87 , 88 , which are rigidly attached to axles 55 , 56 of the anterior wings. Wing arms 87 , 88 are rigidly attached to anterior left and right flapping wing panels 89 , 90 , in which, like in the first omthopter variant, are mounted rotatable rods 44 and to these are attached feather-like panels 45 and mounted an analogous mechanism for the uniform rotation of the rods. Right link 80 through intermediate joints 91 , 92 is connected to left and right intermediate links 93 , 94 , which through ball joints 95 , 96 are connected to posterior flapping wing arms 97 , 98 , which are rigidly attached to posterior wing axles 59 , 60 . Wing arms 97 , 98 are rigidly attached to posterior flapping wing panels 99 , 100 , which, like the anterior wings, have rotatable rods 44 , feather-like panels 45 , and a mechanism to uniformly rotate the rods. Left and right axles 55 , 56 for the anterior wings have extensions: left and right brackets 101 , 102 , the ends of which are joined by stretched cord 103 and the stretched counterbalance to it consists of cord 104 stretched between axles 55 , 56 at anterior mobile joints 71 , 72 . Similarly axles 59 , 60 of the posterior wings have extensions in front: left and right brackets 105 , 106 , the ends of which are joined by stretched cord 107 and the stretched counterbalance to it consists of cord 108 stretched between axles 59 , 60 at posterior mobile joints 77 , 78 . According to the second design of the second variant of the ornithopter-sailplane with two pairs of flapping wings, posterior ball joints 77 , 78 of posterior wing axles 59 , 60 are rigidly attached to strip 109 , which is rigidly attached to extension 110 of strip 10 of the frame.
In the case of the first variant of the ornithopter-sailplane, when flying the pilot makes the propulsion-flapping movements gradually and simultaneously by moving his thighs-femoral arms 3 and makes propulsion steering movements by moving his shoulders and humeral arms 23 , 24 . The pilot can also make guiding steering movements by-diversely and unevenly moving femoral arms 3 , moving one femoral arm, or slowing or completely stopping one or the other femoral arm 3 . In this case the different position of the wings' declination angles directs the joint aerodynamic force of the wings to the side with the wing that is less tilted.
The movements of femoral arms 3 are transmitted to wing panels 42 , 43 through ball joints 34 , 35 , intermediate links 36 , 37 , ball joints 38 , 39 , and wing arms 40 , 41 . By bringing up the thighs, the wing rises upwards and backwards and by stretching them out, the wings descend downwards and forwards.
The pilot can make guiding-steering movements with flapping wings by moving just his upper arms and shoulders, bending or twisting the upper part of his torso, or by making all these movements simultaneously, for example, those of the upper arm and torso. All of these movements are transmitted from humeral arms 23 , 24 to wing panels 42 , 43 through joints 21 , 22 , intermediate links 19 , 20 , mobile joints 17 , 18 , and wing axles 13 , 14 . Humeral arms 23 , 24 can be moved forwards and backwards simultaneously or in opposite directions, i.e. one forwards, the other backwards, or only one of them moved with the other remaining in a fixed position. The backwards movements of humeral arms 23 , 24 increase a flapping wing's angle of attack α (See FIG. 6 , 7 .) and at the same time the increased vertical lifting aerodynamic force of each wing lifts the wing upwards. The downwards movements of humeral arms 23 , 24 reduce the wings' angle of attack a and the aerodynamic force and the wings descends.
The pilot can make additional and very varied movements for guiding the flight with guiding trapezium 54 and by changing the declination angles of hang glider wing 53 . All the very diverse hang glider wing guiding movements, which are now used, hang glider pilots can very broadly use in guiding the ornithopter-sailplane.
In the second variant of the ornithopter-sailplane, the movements of left femoral arm 3 are transmitted to wing panels 89 , 90 through joint 34 , intermediate link 79 , intermediate joints 81 , 82 , intermediate links 83 , 84 , ball joints 85 , 86 , and anterior wing arms 87 , 88 . Similarly the movements of right femoral arm 3 are transmitted to wing panels 99 , 100 through joint 35 , intermediate link 20 , intermediate joints 91 , 92 , intermediate links 93 , 94 , ball joints 95 , 96 , and posterior wing arms 97 , 98 . By drawing up both thighs, both pairs of wings rise upwards and backwards and by extending the thighs, descend downwards and forwards. The pilot can make guiding movements by just using the thighs to fix a different angled position of the thighs and both pairs of flapping wings or by moving the thighs and pairs of wings at different speeds, or when the movements of one thigh and pair of wings lag behind the others during the periods of their movement cycle.
In the second variant of the ornithopter-sailplane, the guiding-steering movements are transmitted from humeral arms 23 , 24 to anterior wing panels 89 , 90 through joints 25 , 26 , intermediate links 69 , 70 , mobile joints 71 , 72 , and wing axles 55 , 56 and are transmitted to posterior wing panels 99 , 100 through intermediate links 69 , 70 , joints 67 , 68 , links 65 , 66 , joints 73 , 74 , intermediate links 75 , 76 , posterior mobile joints 77 , 78 , and posterior wing axles 59 , 60 . Movements by the upper arms and humeral arms 23 , 24 are made in various ways directly for mobile anterior joints 71 , 72 of the anterior wings and for the mobile posterior joints 77 , 78 of the posterior wings. Backwards movements of humeral arms 23 , 24 raise mobile joints 71 , 72 and simultaneously lower mobile joints 77 , 78 of the posterior wings. In this way they simultaneously increase the angle of attack α of the anterior wings and the posterior wings (See FIGS. 6 , 7 .) and at the same time increase the aerodynamic lifting forces of both pairs of wings, both pairs of wings lifting the ornithopter upwards. On the contrary, forward movements of humeral arms 23 , 24 reduce the posterior wings' angle of attack a and after thus reducing the aerodynamic forces, the ornithopter descends. If backwards or forwards movements are made with only left or right humeral arm 23 or 24 , they correspondingly increase or decrease the angle of attack a of the left or right wings being controlled and thus the joint effect of the aerodynamic forces of both pairs of wings causes the ornithopter to make turns and banks.
According to the second design of the second variant, of the ornithopter-sailplane (See this variant of the frame's left framework in FIG. 14 .), it is possible to control only the anterior pair of flapping wings with humeral arms 23 , 24 .
In the second variant, a pilot can steer hang glider wing 53 by rotating trapezium 54 . A pilot can use the steering trapezium as an arm brace to push or pull himself to it while using the muscle power of both arms when making steering movements with humeral arms 23 , 24 .
Flapping the wings when moving downwards and forwards meets increased air resistance and then rods 44 additionally bend and rotate about their axes to create a flatter side for feather-like panels 45 . At the same time the edges of the feather-like panels 45 elastically bend and deform in the air intervals as depicted in FIG. 7 , cross-section CC. As a consequence of these deformations, the aerodynamic lifting and propulsion forces, additionally increase. During this movement, the feather-like panels 45 in cross-section BB form the solid aerodynamic profile depicted in FIG. 6 . The greater aerodynamic forties generated when a wing moves upwards and backwards push harder on the flatter side of asymmetrical panels 45 . These forces, by rotating panels 45 and rods 44 , at the same time rotate cranks 46 attached to them, the uniform and equal rotation of which is ensured by parallel links 47 , 48 , 49 moving together with them. In moving, parallel link 48 stretches spring 52 and stops when support 50 , which is attached to it, comes to rest on immobile support 51 . The movements up to support 51 occur when the ornithopter's horizontal speed is small or zero at the beginning of an ascent. At that moment rotatable panels 45 occupy the position depicted in FIG. 8 and create the aerodynamic forces P and T depicted in FIG. 10 . After the ornithopter reaches horizontal speed V H , the feather-like panels 45 rotate to the acuter angle depicted in FIG. 9 and then create smaller aerodynamic forces ( FIG. 11 ). It also depicts vector V H for the ornithopter-sailplane's speed, vector V S for the speed of a flapping wing's movement in the space, and vector V HS for its horizontal projection. It is evident that when the ornithopter reaches horizontal flying speed V H ≧V S , feather-like panels 45 can no longer rotate in moving the wing upwards and backwards. After the ordinary upwards and backwards movement of the flapping wing ends, the aerodynamic forces that affected panels 45 fall to zero and then spring 52 returns the entire mechanism and feather-like panels 45 to the initial closed position depicted in FIG. 6 .
When a pilot begin to fly, by using sharp movements of femoral arms 3 he can develop aerodynamic forces increased by the flapping wings (see FIG. 10 ) by synchronically bending his torso and humeral arms 23 , 24 forward.
An ornithopter-sailplane can be used in flying sports, recreation, and leisure time.
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A man-powered ornithopter-sailplane, which has one or two pair of flapping wings and a hang-glider wing wherein substantially novel femoral and humeral muscular propulsion engines with the aid of which the body members connected thereto form integrated moving-flying and controlling-guiding mechanisms. Femoral arms are fixed to the torso base from which the movements for the wings flapping with respect to axles inclined to a horizontal direction are transmitted through the intermediate links of a kinematic chain. The wings comprise a row of rotational rods arranged therein and provided with elastic feather-like panels which produced during flapping, in a closed or turned position thereof, aerodynamic profiles and corresponding lifting and propulsion aerodynamic forces. The controlling-guiding movements are transmitted from the humeral arms to the flapping wings using movable ball joints. The diversity of movements of the femoral arms, humeral arms, hang-glider wing make it possible to control the flight.
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BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The invention relates generally to the field of marine aquaculture. More specifically, the invention is directed to an improved method and apparatus for processing sea cucumbers.
[0003] 2. Description of Prior Art
[0004] Sea cucumbers are any of the more than one thousand species of marine invertebrates belonging to a group of echinoderms called holothurians. They have soft, cylindrical bodies, ranging in length from less than an inch to several feet, and in thickness from half an inch to almost a foot. They are usually a dull, dark color and their outer skin is often warty, thus resembling a cucumber. They are sluggish, bottom dwelling animals that are found worldwide. Sea cucumbers have a tough, leathery outer skin, a mouth located at one end having a circle of branching tentacles, and an anal opening at the other end. The internal organs (viscera) of the sea cucumber lay within the tube-like body chamber surrounded by the skin and a layer of longitudinal muscle bands.
[0005] There are several species of edible holothurians, including Cucumaria frondosa , which is found off the northeast coast of the United States. Sea cucumber meat, which includes the body wall and longitudinal muscle bands, is highly prized in many Asian markets. Sea cucumbers traditionally have been processed by cutting the outer skin with a knife and removing the longitudinal muscle bands by hand. This is a labor-intensive, time consuming method. Moreover, Cucumaria frondosa has a particularly tough outer skin, making it especially difficult to prepare.
[0006] Recently, there has been disclosed a method of improved sea cucumber processing utilizing a vacuum system for removing the viscera from a sea cucumber. However, this method still relies on an initial step of cutting open the sea cucumber by hand to expose the internal organs and fluids. It also does not separate the layer of longitudinal muscle bands from the outer skin. Moreover, it is complicated and costly and is not amenable to use by small sea cucumber processors. There is therefore a need for an improved method of separating the desirable portions of a sea cucumber during processing which is effective and simple to use while reducing the amount of labor needed to perform the task.
[0007] The present invention overcomes the problem of separating the components of a sea cucumber to more readily obtain the desired portions. As more fully described below, the disclosed methods and apparatus utilize the application of pressure to a sea cucumber to force apart the various components of a sea cucumber quickly and easily, greatly facilitating further processing.
[0008] It is therefore an objective of the present invention to provide one or more useful methods for separating the components of a sea cucumber.
[0009] It is a further objective of the present invention to provide one or more useful methods for separating the components of the species Cucumaria frondosa.
[0010] It is yet a further objective of the present invention to provide one or more useful methods for separating the components of a sea cucumber by the application of pressure thereto.
[0011] It is yet a further objective of the present invention to provide one or more useful methods for separating the components of a sea cucumber which are simple in application.
[0012] It is yet a further objective of the present invention to provide a useful apparatus for separating the components of a sea cucumber.
[0013] It is yet a further objective of the present invention to provide a useful apparatus for separating the components of the species Cucumaria frondosa.
[0014] It is yet a further objective of the present invention to provide a useful apparatus for separating the components of a sea cucumber by the application of pressure thereto.
[0015] It is yet a further objective of the present invention to provide a useful apparatus for separating the components of a sea cucumber which is simple in application.
[0016] Other objectives of the present invention will be readily apparent from the description that follows.
SUMMARY OF THE INVENTION
[0017] The present invention discloses various methods for processing sea cucumbers and apparatuses for practicing those methods. The methods utilize an application of mechanical pressure to a decapitated sea cucumber. The pressure on the outer portions of the sea cucumber forces the layer of longitudinal muscle bands and the viscera out of the sea cucumber through the opening created by the removal of the anterior portion (“head”) of the sea cucumber.
[0018] The basic method involves the steps of obtaining a sea cucumber; removing a portion of the anterior end of the sea cucumber to expose the layer of longitudinal muscle bands and viscera; applying pressure to the sea cucumber such that the application of pressure squeezes the longitudinal muscle bands and viscera out of the sea cucumber through the first end; and separating the longitudinal muscle bands from the remainder of the sea cucumber. Variations of the basic method include using either a knife or other hand-held cutting implement to remove the anterior end of the sea cucumber or using an automated cutting device, such as a guillotine blade, a circular slicing blade, or the like. Other variations include using one or more cylindrical rollers to apply the pressure to the sea cucumber, or substantially planar pressing surfaces to apply the pressure to the sea cucumber, or a combination. Yet other variations employ conveyor belts to move the sea cucumbers into contact with the pressing mechanism.
[0019] The apparatuses disclosed by the present invention are suitable for implementing the above described methods. These apparatuses may use one or more cylindrical rollers, or substantially planar pressing surfaces, or a combination. The apparatuses may be hand powered, electrically powered, hydraulically powered, or some combination thereof. Variations may also employ conveyor belts to move the sea cucumbers into contact with the pressing mechanism.
[0020] Other features and advantages of the invention are described below.
DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1A is a perspective view of one embodiment of the device in which the method of applying pressure to the sea cucumber utilizes a cylindrical roller and a substantially planar pressing surface.
[0022] FIG. 1B is a plan view of the embodiment of the device and method depicted in FIG. 1A .
[0023] FIG. 2 is a perspective view of another embodiment of the device in which the method of applying pressure to the sea cucumber utilizes two cylindrical rollers.
[0024] FIG. 3 is a perspective view of yet another embodiment of the device in which the method of applying pressure to the sea cucumber utilizes two cylindrical rollers and a conveyor belt.
[0025] FIG. 4 is a plan view of yet another embodiment of the device in which the method of applying pressure to the sea cucumber utilizes multiple cylindrical rollers and the pressing surface is a conveyor belt.
[0026] FIG. 5 is a perspective view of an embodiment of the device in which the method of applying pressure to the sea cucumber utilizes two substantially parallel pressing surfaces.
[0027] FIG. 6 is a perspective view of an embodiment of the device in which the method of applying pressure to the sea cucumber utilizes two pressing surfaces at an angle to each other.
[0028] FIG. 7 is a perspective view of an alternative embodiment of the device in which the method of applying pressure to the sea cucumber utilizes two pressing surfaces at an angle to each other, whereby the two pressing surfaces are hingedly connected to each other.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present invention discloses an improved method for processing a sea cucumber 10 . The method is applicable to any of the edible species of sea cucumbers 10 , but especially to the species Cucumaria frondosa . In all cases, the sea cucumber 10 to be processed is substantially elongate, has a first end 12 and a second end 14 located opposite the first end 12 , and has an outer portion 16 , a layer of longitudinal muscle bands 18 , and internal viscera 19 .
[0030] In the most general embodiment, the improved method comprises the steps of:
[0031] A: obtaining a sea cucumber 10 ;
[0032] B: removing a portion of the first end 12 of the sea cucumber 10 , thereby creating an opening 13 and exposing the layer of longitudinal muscle bands 18 and viscera 19 ;
[0033] C: applying pressure to the sea cucumber 10 such that the application of pressure squeezes the longitudinal muscle bands 18 and viscera 19 out of the sea cucumber 10 through the opening 13 at the first end 12 ; and
[0034] D: separating the longitudinal muscle bands 18 from the outer portion 16 and viscera 19 .
[0035] In one embodiment the removal of the portion of the first end 12 of the sea cucumber 10 to create an opening 13 in step B is performed by use of a knife. The knife may be held by a human hand in a manual operation. A circumferential cut is made about the first end 12 of the sea cucumber 10 through the outer portion 16 . Alternatively, the knife may be used to make a through cut through the outer portion 16 of the sea cucumber 10 at the first end 12 generally perpendicular to the longitudinal axis of the sea cucumber 10 . In other embodiments the knife may be attached to a mechanical device.
[0036] In yet other embodiments the removal of the portion of the first end 12 of the sea cucumber 10 is step B is performed by use of an automated cutting device. The automated device may incorporate a guillotine blade for decapitating the sea cucumber 10 to create an opening 13 at the first end 12 . Alternately, a circular slicing blade may be used. Any other appropriate method for removing the first end 12 of the sea cucumber 10 known in the art, whether manual or by use of an automatic device, is also contemplated by this invention.
[0037] Step C of the method involves applying pressure to the sea cucumber 10 to force the longitudinal muscle bands 18 and viscera 19 out of the opening 13 at the first end 12 . In the preferred embodiment the pressure is applied asymmetrically to the sea cucumber 10 , first beginning at its second end 14 and thereafter in a continuous manner being applied substantially along the longitudinal axis of the sea cucumber 10 towards its first end 12 . This action mimics, for example, the application of pressure to an open tube of tooth paste to cause the paste to be most efficiently squeezed therefrom. Alternatively, the pressure may be applied uniformly to the outer body 16 of the sea cucumber 10 . Because the outer portion 16 of the body is entirely intact except for the opening 13 at the first end 12 , the application of uniform pressure will tend to squeeze the longitudinal muscle bands 18 and viscera 19 out of the sea cucumber 10 through the opening 13 at the first end 12 .
[0038] In one embodiment, the application of pressure to the sea cucumber 10 in step C of the method is accomplished by the use of a cylindrical roller 20 in near proximity to a substantially planar pressing surface 30 . See FIG. 1 . The cylindrical roller 20 is spaced apart from the pressing surface 30 forming a gap 40 that is somewhat smaller than the cross-section of the sea cucumber 10 . Step C is performed by placing the second end 14 of the sea cucumber 10 into the gap 40 between the cylindrical roller 20 and the pressing surface 30 , with the longitudinal axis of the sea cucumber 10 oriented substantially perpendicular to the longitudinal axis of the cylindrical roller 20 . The sea cucumber 10 is then moved through the gap 40 . The pressure exerted on the sea cucumber 10 by the cylindrical roller 20 and the pressing surface 30 squeezes the longitudinal muscle bands 18 and viscera 19 out of the sea cucumber 10 .
[0039] In another embodiment of the method, the application of pressure to the sea cucumber 10 in step C is accomplished by the use of a plurality of cylindrical rollers 20 in near proximity to a substantially planar pressing surface 30 . See FIG. 4 . Each of the cylindrical rollers 20 is oriented parallel to and in close proximity to the other cylindrical rollers 20 . The plurality of cylindrical rollers 20 work in conjunction with the pressing surface 30 in the same manner as in the embodiment utilizing just one cylindrical roller 20 , and the sea cucumber 10 is moved between the cylindrical rollers 20 and the pressing surface 30 in the same manner. In an alternative embodiment, each of the cylindrical rollers 20 forms a different sized gap 40 with the pressing surface 30 , with the largest gap 40 being formed between the pressing surface 30 and the cylindrical roller 20 which first contacts the second end 14 of the sea cucumber 10 , and the gaps 40 for each successive cylindrical roller 20 being slightly smaller, with the final cylindrical roller 20 forming the smallest gap 40 with the pressing surface 30 . This configuration allows for pressure to be exerted in an ever increasing manner along the length of the sea cucumber 10 , thereby more efficiently extracting the longitudinal muscle bands 18 and viscera 19 while minimizing the risk of rupturing the outer body 16 .
[0040] In yet another embodiment, the pressing surface 30 is a cylindrical roller 32 oriented substantially parallel to each of the other of the one or more cylindrical rollers 20 . See FIG. 2 .
[0041] In each embodiment of the method utilizing cylindrical rollers 20 , an alternate configuration provides that at least one of the one or more cylindrical rollers 20 has a circumferential band 22 having gripping members 24 . The gripping members 24 may be projections depending outward from the surface of the cylindrical roller 20 , such as teeth or small flanges, or depressions formed into the surface of the cylindrical roller 20 , or a combination of both, or simply a roughening of the surface. Ideally the circumferential band 22 is of substantially uniform width, though it need not be in all circumstances. The use of gripping members 24 improves movement of the sea cucumber 10 past the cylindrical roller 20 , as fluids extracted from the sea cucumber 10 during the application of pressure thereto may otherwise reduce the friction between the cylindrical roller 20 and the sea cucumber 10 .
[0042] In the embodiments utilizing one or more cylindrical rollers 20 , the method may further comprise the steps of:
[0043] B 1 : causing the one or more cylindrical rollers 20 to rotate, with each such roller 20 rotating in the same direction as each other roller 20 ; and
[0044] B 2 : placing the second end 14 of the sea cucumber 10 into the gap 40 between one of the cylindrical rollers 20 and the pressing surface 30 such that said roller 20 and said pressing surface 30 simultaneously contact the second end 14 of the sea cucumber 10 .
[0045] In these embodiments, step B 1 is begun before step C and continues until step C is completed. Step B 2 is performed after step B and before step C. Where the pressing surface 30 is also a cylindrical roller 32 , step B 1 is modified such that the pressing surface roller 32 rotates in a direction opposite the rotation of the other cylindrical rollers 20 . The rotation of the one or more cylindrical rollers 20 in step B 1 may be performed by use of a hand crank or other manual device. In the preferred embodiment the rotation is accomplished by use of one or more powered devices, such as an electric motor 70 .
[0046] In an alternative embodiment of the method using one or more rotating cylindrical rollers 20 , step B 2 is performed by use of a conveyor belt 50 . See FIGS. 3 and 4 . The conveyor belt 50 may be located adjacent to the gap 40 between the cylindrical roller 20 and the pressing surface 30 , such that a sea cucumber 10 placed on the conveyor belt 50 will be carried towards the gap 40 . In such a configuration when the sea cucumber 10 is placed on the conveyor belt 50 its second end 14 is oriented towards the gap 40 , and as the sea cucumber 10 reaches the end of the conveyor belt 50 its second end 14 extends beyond the end of the conveyor belt 50 and is placed into the gap 40 . In the preferred embodiment the conveyor belt 50 runs between the one or more cylindrical rollers 20 and the pressing surface 30 . In yet another embodiment the conveyor belt 50 itself serves as the pressing surface 30 . In all embodiments using a conveyor belt 50 and one or more rotating cylindrical rollers 20 the sea cucumber 10 should be placed on the conveyor belt 50 with its second end 14 oriented towards the one or more cylindrical rollers 20 . The conveyor belt 50 moreover may be a flexible, continuous belt that runs in a single direction, or a substantially rigid member which runs in two opposing directions.
[0047] In yet another alternative embodiment of the method, the application of pressure to the sea cucumber 10 in step C is accomplished by the use of a first pressing surface 34 and a second pressing surface 36 . See FIGS. 5-7 . The first and second pressing surfaces 34 , 36 are substantially planar and are suitably adapted to move towards each other and away from each other. In one embodiment step C comprises the substeps of:
[0048] C 1 : placing the sea cucumber 10 onto the first pressing surface 34 between the first and second pressing surfaces 34 , 36 ; and
[0049] C 2 : moving the first and second pressing surfaces 34 , 36 towards each other such that the first and second pressing surfaces 34 , 36 simultaneously contact the sea cucumber 10 .
[0050] In one alternative of this embodiment the first and second pressing surfaces 34 , 36 are substantially parallel to each other. See FIG. 5 . In another alternative the first pressing surface 34 is oriented substantially horizontal and the second pressing surface 36 is located above the first pressing surface 34 at an angle to the first pressing surface 34 . See FIG. 6 . In this embodiment the sea cucumber 10 is placed onto the first pressing surface 34 in substep C 1 whereby the sea cucumber 10 is oriented with its first end 12 towards the greater separation between the first and second pressing surfaces 34 , 36 and its second end 14 towards the lesser separation between the first and second pressing surfaces 34 , 36 . Thus, in substep C 2 , when the first and second pressing surfaces 34 , 36 move towards each other the first and second pressing surfaces 34 , 36 simultaneously contact the sea cucumber 10 beginning at its second end 14 . In this embodiment the first and second pressing surfaces 34 , 36 may be connected to each other by a hinge 60 . See FIG. 7 . In all embodiments using first and second pressing surfaces 34 , 36 hydraulics may be used to move the first and second pressing surfaces 34 , 36 toward and away from each other. Other methods of moving the pressing surfaces 34 , 36 are also contemplated by the present invention.
[0051] The present invention also discloses devices for accomplishing the method of the present invention. In one embodiment the device 100 comprises a cylindrical roller 20 in near proximity to a pressing surface 30 , with the pressing surface 30 being substantially planar, and with the cylindrical roller 20 forming a gap 40 between it and the pressing surface 30 , and with 12 the gap 40 being smaller than the cross-section of the sea cucumber 10 , as described above. See FIG. 1 . The device 100 is suitably adapted to apply pressure to a decapitated sea cucumber 10 when the second end 14 of the sea cucumber 10 is placed into the gap 40 between the cylindrical roller 20 and the pressing surface 30 and the cylindrical roller 20 is rotated such that the sea cucumber 10 is drawn between the cylindrical roller 20 and the pressing surface 30 . As such, the pressure applied to the sea cucumber 10 begins at the second end 14 of the sea cucumber 10 and thereafter in a continuous manner progresses substantially along the longitudinal axis of the sea cucumber 10 towards its first end 12 , squeezing the longitudinal muscle bands t 8 and viscera 19 out of the sea cucumber 10 through the opening 13 at the first end 12 . As described above, the pressing surface 30 may also be a cylindrical roller 32 oriented substantially parallel to the rotating cylindrical roller 20 . See FIG. 2 .
[0052] In another embodiment the device 100 may comprise a plurality of cylindrical rollers 20 located in near proximity to a substantially planar pressing surface 30 . See FIG. 4 . Each of the cylindrical rollers 20 is oriented parallel to and in close proximity to the other cylindrical rollers 20 . The plurality of cylindrical rollers 20 work in conjunction with the pressing surface 30 as described above. In an alternative embodiment, each of the cylindrical rollers 20 forms a different sized gap 40 with the pressing surface 30 , as described above. See FIG. 4 .
[0053] In each embodiment utilizing cylindrical rollers 20 , an alternate configuration provides that at least one of the one or more cylindrical rollers 20 has a circumferential band 22 having gripping members 24 , as described above.
[0054] In the embodiments of the device 100 , 110 utilizing one or more cylindrical rollers 20 , the cylindrical rollers 20 may be powered to rotate in the same direction. Power may t 3 be provided by one or more electric motors 70 . Alternatively, the one or more cylindrical rollers 20 may be rotated by hand, as by a crank. Where the pressing surface 30 is also a cylindrical roller 32 , it will be rotated in the opposite direction as the other rollers 20 .
[0055] In an alternative embodiment, the cylindrical roller 20 may be moved across the pressing surface 30 by a movable armature. In this embodiment the roller 20 is adapted to move in opposite directions, first rolling over the sea cucumber 10 to apply pressure and then rolling back, readying itself for the next sea cucumber 10 .
[0056] In a preferred embodiment of the device 100 , the pressing surface 30 is a conveyor belt 50 . See FIGS. 3 and 4 . In an alternative embodiment, the device 100 may utilize a conveyor belt 50 in conjunction with the one or more cylindrical rollers 20 and the pressing surface 30 . In such a configuration the conveyor belt 50 is suitably adapted to place the second end 14 of the sea cucumber 10 into the gap 40 between one of the cylindrical rollers 20 and the pressing surface 30 such that said roller 20 and said pressing surface 30 simultaneously contact the second end 14 of the sea cucumber 10 . As described above, the conveyor belt 50 may be a flexible, continuous belt that runs in a single direction, or a substantially rigid member which runs in two opposing directions. In the latter embodiment, the conveyor belt 50 first moves in a direction towards the one or more cylindrical rollers 20 , and after pressure is applied to the sea cucumber 10 the conveyor belt 50 moves away from the one or more cylindrical rollers 20 .
[0057] In another embodiment the device 200 , 210 comprises a first pressing surface 34 and a second pressing surface 36 . See FIGS. 5-7 . The first and second pressing surfaces 34 , 36 are substantially planar, the first pressing surface 34 is oriented substantially horizontal, and the second pressing surface 36 is located above the first pressing surface 34 . The first and second t 4 pressing surfaces 34 , 36 are further suitably adapted to move towards each other and away from each other. This may be accomplished by hydraulics, or any other method known in the art.
[0058] In this embodiment a decapitated sea cucumber 10 is placed onto the first pressing surface 34 between the first and second pressing surfaces 34 , 36 , and the first and second pressing surfaces 34 , 36 are moved towards each other, causing the first and second pressing surfaces 34 , 36 to simultaneously contact the sea cucumber 10 . This application of pressure squeezes the muscles bands 18 and viscera 19 of the sea cucumber 10 out through the opening 13 at the first end 12 .
[0059] In one embodiment of the device 200 the second pressing surface 36 is oriented substantially parallel to the first pressing surface 34 . See FIG. 5 . In this embodiment pressure is applied substantially uniformly to all portions of the sea cucumber 10 simultaneously. In an alternative embodiment of the device 210 the second pressing surface 36 is oriented at an angle to the first pressing surface 34 . See FIG. 6 . In this embodiment the sea cucumber 10 is placed onto the first pressing surface 34 between the first and second pressing surfaces 34 , 36 oriented with its first end 12 towards the greater separation between the first and second pressing surfaces 34 , 36 and its second end 14 oriented towards the lesser separation between the first and second pressing surfaces 34 , 36 . When the first and second pressing surfaces 34 , 36 are moved towards each other the first and second pressing surfaces 34 , 36 simultaneously contact the sea cucumber JO beginning at its second end 14 , with the pressure applied to the sea cucumber 10 beginning first at its second end 14 and thereafter in a continuous manner substantially along its longitudinal axis towards its first end 12 , squeezing the longitudinal muscle bands 18 and viscera 19 of the sea cucumber 10 through the opening 13 at the first end 12 . In yet another embodiment, the first pressing surface 34 may be hingedly connected to the second pressing surface 36 . See FIG. 7 .
[0060] In all embodiments of the device 200 , 210 utilizing first and second pressing surfaces 34 , 36 , the sea cucumbers 10 may be delivered to the first pressing surface 34 by a conveyor belt 50 . Alternatively they may be placed thereupon by hand.
[0061] Those skilled in the art will perceive improvements, changes and modifications in the invention. Such improvements, changes and modifications within the skill of the art are intended to be covered by the claims set forth herein, and that all matter contained in the accompanying specification shall be interpreted as illustrative only and not in a limiting sense.
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An improved method for processing sea cucumbers by applying pressure to the outer body of a decapitated sea cucumber, thereby forcing the layer of longitudinal muscle bands and internal viscera out of the outer body allowing for ready separation of the components for further processing, and an apparatus for implementing said improved method.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
Various devices have been developed and patented throughout the years to aid to the mobility of the fisherman. The device of this invention is in the category which might well be defined as a sailing trotline. A sail mounted on a float is utilized to propel a trotline carrying numerous hooks to a distance from the shore line or a boat or pier.
2. Description of Prior Art
Various fishing devices designed to utilize the force of the wind have been developed and patented. Among these are: U.S. Pat. No. 3,314,632, to Lewis, describing a fishing kite; U.S. Pat. No. 3,462,870 to Terilli employs a kite with a series of hooks suspended from the kite line with the nearest reference, to the best of the knowledge of your applicant, being U.S. Pat. No. 3,747,248, to Baer, which employs a miniature barge-like structure having a sail member attached thereto which extends a line from a point and is capable of moving the extended line from side to side. The device of this invention differs from the prior art in the components and method of construction. The device of this invention employs a PVC frame to which is attached floats. A sail frame projects upward from the PVC frame. The sail frame is controlled by guy lines secured to the frame at the top of the sail and an adjustable chain harness at the bottom extremity of the sail which facilitates a maneuvering or mobility of the float sail structure as desired by various adjustments to the guy lines or the chain harness.
SUMMARY OF THE INVENTION
The device of this invention is constructed from light, PVC pipe utilizing jam fits or sleeve-like connections. To assemble the various components prior to use, T connectors, cross connectors, elbows, and cap-like structures are employed in PVC frame. The sail may be constructed of any desired fabric or sheet of plastic. The guy lines extending to the top of the sail could be constructed from a nylon line or stainless steel. The floats adding buoyancy to the PVC frame are preferably of cylindrical Styrofoam closed-cell material. The forward end of the PVC frame is provided with a stanchion to which is secured the guy lines, the chain harness, and the trotline. The trotline extends from the float sail structure to a shore windlass, which may be either hand cranked or powered by an electric motor and gear train. A series of drop lines and hooks are spaced along the trotline. Preferably, the trotline would also include a series of bobbers attached to help trotline to stay afloat. These bobbers may well be brightly colored to warn boats or water skiers. The device of this invention lends itself to extending the trotline a substantial distance from a pier, boat, or a shore line if the prevailing wind is in the desired direction. The adjustable guy lines and chain harness of this invention permit a projection of the sail float structure in various desired directions other than directly downwind. The prototype of this invention has been tested and utilized with amazingly successful results. The poundage of fish caught in the use obtained enviable results.
BRIEF DESCRIPTION OF THE DRAWINGS
For an illustration of this invention and the following detailed description illustrating the method of construction of the device in two embodiments and the operation or utilization of the invention, reference is made to the attached several views wherein identical reference characters will be utilized to refer to identical or equivalent components throughout the various view and the later detailed description.
FIG. 1 is a perspective view illustrating the device anchored to a shore line and the sail float structure extending offshore.
FIG. 2 is a fragmented view indicating some of the details of the float sail structure together with the guy lines and the chain harness.
FIG. 3 is a perspective view of the shore windlass suggesting either a hand crank for the windlass or an electrical powered drive for the windlass.
FIG. 4 is a side view partially fragmented of the shore windlass indicating some of the detail of the electric power drive.
FIG. 5 is an exploded view of the PVC frame and sail indicating the details of construction and suggested assembly procedures of Species One of the invention.
FIG. 6 is a perspective view of Species Two of the invention which is an alternative embodiment utilizing a modified chain harness means employing an upper swivel and a lower swivel from which is supported rotatably a sail frame.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
For the detailed description of the construction and operation of the device of this invention, reference is made to the various drawings. FIG. 5 illustrates Species One of the invention. Numerous adjustable positions are provided for positioning the sail in Species Two of the invention. FIG. 6 illustrates a more flexible maneuvering of the sail float combination.
The trotline 10 of FIG. 1 is of conventional construction consisting of a heavy trotline 10, hook line 11, hooks 12, and a series of bobbers 13. To propel the line 10 from the shore, boat, or pier, a float sail structure 14 is utilized. Float sail 14 is constructed utilizing a PVC frame 15. Plastic pipe employed is preferably lightweight and waterproof, having a diameter of approximately one inch; however, the size of the pipe employed and the lengths of the various components are relatively optional. In the preferred embodiment, an extension member 16 was utilized in both Species One and Species Two as illustrated in FIGS. 5 and 6. An elongated, cross frame 17 is also employed in both species. In Species One of the invention, as illustrated in FIGS. 1, 2 and 5, two T joints 18 are positioned in the cross frame 17. Projecting outward from these T joints 18 at each end of cross frame 17 are float extensions 19 to which are secured Styrofoam floats 20. Any buoyant material might be used for constructing these floats 20; however, it is visualized that a closed-cell, expanded plastic having high buoyancy qualities, such as Styrofoam, would be the preferable method of construction. A sail frame 22 is attached to cross frame 17 in the T joints 18. Side members of sail frame 22 are elongated, tubular sections of PVC, illustrated as upright extensions 23. Completing sail frame 22 is a top cross member 24 which is attached to the upright extensions 23 by means of two elbow joints 25. In view of the fact the device of this invention is to be utilized frequently in salt water and in areas of sandy beach, it is preferable that all joint connections be unthreaded telescopic slip fit joints retained by wedge or friction contact only. It is visualized that the device of this invention may be disassembled and reassembled at the point of next use. Secured to sail frame 22 is a fabric sail 28. This fabric may be of any desired construction; however, a plastic or a nylon-coated plastic fabric would be preferable. The sail 28 is constructed with sail sleeves 29 at each extremity. The sail sleeves 29 slide over the upright extensions 23 and retain the sail 28 in position. In the embodiment of the invention of Species One of FIGS. 1, 2 and 5, the first guy line 31 and the second guy line 32 project from the top edge of the sail frame 22. These guy lines 31 and 32 extend from cross member 24 to the forward end of extension member 16. In the preferred embodiment, these guy lines were slidably or movably attached to stanchion 33. Connecting the lower extremity of sail frame 22 to stanchion 33 is a chain harness 34. This structure varies somewhat in its configuration in Species One, FIG. 5, and Species Two, FIG. 6. In each embodiment, however, there is utilized a first chain 35 and a second chain 36 which are adjustably attached to stanchion 33. The guy lines 31 and 32 are movably or slidably attached to stanchion 33 by means of a sliding contact through stanchion 33 or some type of block or pulley. Regardless of the detail of the construction attaching guy lines 31 and 32 to the stanchion 33, this structure functions as a guy runner 37. Chain harness 34 is attached to sail frame 22 by means of a chain anchor 38. This structure may comprise a ring attached to the end of the chain which is of sufficient size to fit around the upright extension 43 adjacent T joint 18. Unlike the guy runner 37 connection for the guy lines 31 and 32, chain harness 34 must be fixedly secured to stanchion 33 in a selected position. This may be accomplished by a chain adjusting clip 39, as illustrated in FIGS. 5 and 6, or some other suitable attaching means. The floats 20 could be securely attached to segments of the extension member 16 or cross frame 17 or they might be slidably affixed to these members and retained in position by float retainers 43, which might be cap covers. At the center of cross frame 17 is positioned cross joint 45 which connects extension member 16 and cross frame into an integral structure.
Species One of the invention is illustrated in FIG. 5. In Species One of the invention, the positioning of the sail 28 at an angle to the wind is accomplished by the releasing of the chain harness 34 from one of the upright extensions 23. When this is accomplished, the force of the wind will cause a shift of the guy lines 31 and 32 through the guy runner 37 which places the entire float sail structure 14 at an angle to the wind on the extension of trotline 10. This would cause the float sail structure 14 to move at an angle slightly into the wind in a similar manner to a sailboat beating into the wind.
In Species Two of the invention, as illustrated in FIG. 6, this result is accomplished by tilting of the sail frame 22 at an angle to the float sail structure 14. To permit this, as illustrated in FIG. 6, an upper swivel 47 and a lower swivel 48 are provided. This swivel structure utilizes a large, flat lower disk 49 and a smaller upper cap 50. This, in effect, secures sail frame 22 to the structure in a pivoting position. To stabilize the sail frame structure 22 of this species of the invention, some auxiliary bracing is required. This structure is illustrated in FIG. 6, and may be constructed of PVC pipe utilizing elbow joints 25 as employed in the remainder of the structure. This configuration, however, would desirably employ two 45° angle connectors 51 in its construction. The remainder of this construction is illustrated in detail in FIG. 6. It is apparent that in this embodiment a second cross joint 45 would be positioned in the extension member 16 adjacent the rear float 20.
For an illustration of a possible shore windlass 52 to be utilized in conjunction with the float sail structure 14 of this invention, reference is particularly made to FIGS. 1, 3, and 4. The shore windlass 52 may be hand driven or electrically driven. One method of operation would be the attaching to the windlass 53 of FIG. 3 a hand crank 54. The electric powered version of this structure is suggested in FIGS. 1, 3, and 4. This structure might employ a windlass sprocket 55 and a drive sprocket 56. Drive sprocket 56 could be mounted on an axle together with a spur gear 57 which interconnects to a worm gear 58 which is rotated by motor 59. In the preferred embodiment, as illustrated in FIG. 1, extension cord 60 is attached to motor 59. The extension cord 60 should be equipped with battery clips 61 which might be attached to battery of a car, boat, or an electric troll motor. The shore windlass 52 would preferably be a composite structure having a windlass base 62 to which is secured motor 59 and windlass 53 with interconnecting structures. As illustrated in FIG. 1, anchor stakes 63 would connect the windlass base 62 to the shore. If the device were utilized on a boat or pier, some other means of connection, such as a "C" clamp or other attaching means, might be employed. As previously mentioned, the device of this invention may be either hand powered or electric powered. To activate or deactivate the electric motor 59, the circuit should be provided with an on-off switch 64 and a 30-amp fuse 65, as illustrated in FIGS. 1 and 3.
OPERATION OF THE DEVICE
In fishing from a shore installation with the prevailing wind blowing offshore, an example of the operation of this device is as illustrated in FIG. 1. The prevailing wind would carry the float sail structure 14 offshore carrying with it the trotline 10 and the series of baited hooks 12. When trotline 10 is at an extended distance, the operator can detect the presence of fish on the line by observing the position of various bobbers 13. With no fish on the line 10, the bobbers 13 would be substantially in a straight line. With the presence of one or more fish attached to the hooks 12, the bobbers 13 form an arched or curved line. It would be permissible to leave the trotline 10 extended in position for a substantial period of time. When it is desired to reel in the line 10 with the fish, hand crank 54 may be utilized or the on-off switch 64 activated reeling the trotline 10 in onto the windlass 53. As desired, the switch 54 might be de-energized to remove fish from hooks 12. To avoid continuous fishing in the same position or to endeavor to reach more productive areas, either the first chain 35 or second chain 36 might be disconnected from one of the upright structures 23 and connected to the opposite structure 23. This shift of the chain harness 34 would cause the float sail structure 14 to move to the left in the configuration illustrated in FIG. 2. If an opposite connection of the chain harness 34 were utilized, the float sail structure 14 would move to the right.
After a desired adjustment is applied to the sail to move the device windward away from a shore to a desired position, should the wind change direction, the sail will not have to be taken in to apply new adjustment for direction. The sail is light and will turn as a wind vane. The fisherman can slack the trotline followed by a tightening and cause the trotline to arc back and move forward with the wind.
In operating the species of the device as illustrated in FIG. 6, corresponding adjustment would cause the device to proceed to the right or the left as desired. In summary, the species of the device in FIG. 6 would move in the direction of that point of the sail 28 nearest the shore, pier, or boat. When the right-hand corner of the sail 28 is retracted toward the trotline 10, the float sail structure 14 proceeds to the right. If the left hand corner is retracted, the float sail structure 14 proceeds to the left.
Having described the construction and operation of the device of this invention in two species, what is desired to be claimed is all embodiments of modification of this invention not departing from the scope of equivalents of the invention as defined in the appended claims.
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A sailing trotling consisting of a buoyant frame member to which is adjustably secured a sail. The buoyant frame member is designed to project a trotline from an operator to a remote position. A hand-operated or electric-motor-operated windlass is provided for reeling out or reeling in the trotline. The said adjustable means permits a projecting of the trotline selectively, either downward or into a selected partial cross-wind position.
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[0001] The applicant claims the benefit of U.S. Application No. 62,000,882 that was filed on May 20, 2014. The present invention relates to an improvement for a rotary line trimmer. Trimmers that use line, such as nylon line or other heavy gauges thermoplastic material are attached to a rapidly spinning head and are used to trim grass, weeds and other non-woody materials. In some embodiment rather than using line, a resin blade or even a metal chain is attached to the rotating head of the trimmer. The motor is typically provided on the opposite end of a pole and may be powered by a small gas engine or an electric motor. The control of motor is provided by a switch that is accessible to the user.
[0002] While the prior art embodiments satisfactory will cut grass, they are generally not effective nor are they designed for cutting heavy brush or small saplings that have woody stems. The plant cell wall surrounds the cell membrane. It is made up of multiple layers of cellulose which are arranged into primary and secondary walls. The cellulose content of cotton is 90% and wood is 50% cellulose. The cell walls of all vascular plants also contain a polymer called lignin. Lignin is water-resistant. It reinforces cell walls, keeping them from collapsing. This is particularly important in the xylem, because the column of water in the hollow xylem cells is under tension (negative pressure) and without the lignin reinforcement the cells would collapse. Lignin provides the mechanical support for stems and leaves and supplies the strength and rigidity of plant walls.
[0003] The present invention is therefore directed to an improvement for conventional rotary line trimmers by providing a blade that will allow the tool to cut woody plants or saplings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 is a top view of the blade according to an embodiment of the invention.
[0005] FIG. 2 is a view in elevation of the blade according to the embodiment of the invention depicted in FIG. 1 that includes a view of the top surface.
[0006] FIG. 3 is a view in elevation of the blade according to the embodiment of the invention depicted in FIG. 1 that includes a view of the bottom surface of the blade.
[0007] FIG. 4 a is an end view of the blade in elevation.
[0008] FIG. 4 b is an end view of the opposite end of the blade depicted in FIG. 1 .
[0009] FIG. 5 is a side view in elevation of the blade of FIG. 1 .
[0010] FIG. 6 is a side view in elevation taken from the opposite side from that of FIG. 5 .
[0011] FIG. 7 depicts the blade assembled on the head of a rotary trimmer.
[0012] FIG. 8 is an exploded view of a head assembly including the blade of FIGS. 1-6 and cartridge in elevation.
[0013] FIG. 9 is an exploded view of a head assembly including the blade of FIGS. 1-6 and cartridge in perspective.
[0014] FIG. 10 is a perspective exploded view of a head assembly including a blade and clutch elements in perspective
[0015] FIG. 11 is a front perspective view of a further embodiment of a blade.
[0016] FIG. 12 is a rear perspective view of the embodiment of FIG. 11 .
[0017] FIG. 13 is a side view in elevation of the blade of FIG. 11 .
[0018] FIG. 14 is an opposite side view in elevation of the blade of FIG. 11 .
[0019] FIG. 15 is a bottom view of a clutch plate assembly used in an embodiment of the invention.
[0020] FIG. 16 is a top view of the clutch plate of FIG. 15 .
[0021] FIG. 17 is a front view in elevation of the clutch plate of FIG. 15 .
[0022] FIG. 18 is end view in elevation of the clutch plate of FIG. 15 .
[0023] FIG. 19 is rear view in elevation of the clutch plate of FIG. 15 .
[0024] FIG. 20 is an opposite end view in elevation of the clutch plate of FIG. 18 .
[0025] FIG. 21 is a further embodiment of a clutch plate in engagement with a blade and the head member of a rotating tool.
[0026] FIG. 22 is a front view in elevation of the clutch member depicted in FIG. 21 .
DETAILED DESCRIPTION
[0027] Now referring to FIG. 1 , an embodiment of a blade 101 according to the present invention is shown which is designed to be attached to a conventional rotary trimmer. These trimmers have a rapidly rotating head that is provided on the end of a pole. A control switch and motor are provide on the opposite end. In the embodiment depicted in FIG. 1 the blade 101 includes an engagement region or leading edge 103 on a first lateral side that includes a serrated edge. The lateral ends also include a serrated surface as well as a transitional region 105 that is angled to the end surface 107 . Surface 107 also includes a series of teeth designed to engage woody plants. The opposite side of the blade also has a leading edge 113 , a transitional region 111 and an end edge 111 .
[0028] As best seen in FIG. 2 the blade has a center region 117 from which two opposite lateral extension parts 115 and 119 are angled downwardly. In a preferred embodiment the blade is comprised of steel. While the embodiment depicted in the FIGS. 1-7 includes a blade that defines three separate and distinct planes it is completed that the blade may take other shapes such as a polygonal blade like that disclosed in FIG. 1 wherein the blade curves away on opposite sides from the central region. In yet further contemplated arrangement the blade may take the form of cross wherein four opposite blade extension are provide at 90 degree locations. In yet a further embodiment the blade may take the form of a conical section shape, or in the shape of a bell, wherein there is a flat center section for engagement to the head or line cartridge of the trimmer. The outer flared section of the bell or conical section can be provided with a continuous serrated edge or other saw teeth arrangements. The edge of the flared section of the bell may define a single plane or may have portions that do not extend to the planar location.
[0029] FIG. 3 depicts the rear surface of the blade. It includes a hook and look fastener elements 125 and 126 that have been affixed to the blade surface. FIG. 4 a depicts and end view of the blade and includes a depiction of cutting teeth 11 on the end of the surface. FIG. 4 b depicts the opposite end. FIGS. 5 and 6 depicts side views of the blade, both front and rear.
[0030] Now referring to FIG. 7 , blade 202 according to an embodiment of the invention, is depicted in engagement with the head of a rotary trimmer. The blade 202 is positioned and attached to provide for rotational movement between element 714 and the cartridge 706 . The head is posited on the end of pole 719 . A guard 750 is also attached to the end of pole 719 . Line 705 extends from cartridge 706 which can be spooled out as new line may be needed. As seen in FIG. 8 , the rotational movement of the blade and cartridge is effected by axel 785 which extends through a central aperture on the blade and into the top of the cartridge 706 .
[0031] As best seen in FIG. 9 , the top of cartridge 706 is provided with hook and loop element such as strip 925 that is positioned to engage opposite strips on the rear surface of blade 202 . The presence of these strips allows the blade to rotate with the cartridge. However, if the blade impacts a stationary object and sufficient force is translated through the blade, the engaged strips can be displaced and the axel 785 is able to turn independent from the blade.
[0032] While a hook and loop fastener is depicted in the embodiment shown, it is contemplated that other releasable fasteners can be advantageously used such as break away pins that engage both the blade and the cartridge or releasable adhesive.
[0033] FIG. 10 depicts a further embodiment wherein the assembly further includes a clutch plate 1104 and blade 2100 that is positioned between the head 1108 and the drive 1107 elements of a rotary tool. The head includes a portal 1125 from which cutting line 1161 extends. In this embodiment 2100 the blade has a ridges 2101 and 2102 that extend from the bottom surface 2107 of the blade. In this embodiment the clutch plate 1104 is attached to head 1108 by double sided adhesive tape 1110 and 1118 . While adhesive tape is used in this embodiment depicted in FIG. 10 , other forms of adhesives may be advantageously used to attach the clutch plate to the head 1108 including hook and loop device and fasteners. The clutch plate engaged the bottom surface of the blade by frictional engagement and can be displaced when a heavy loads is encountered by the blade such as a large woody plant, fence or rock. As best seen in FIG. 13 , an opposite groove 3102 and 3101 extends into the top surface as the ridge and groove structure is formed by press fitting the metal blade 2100 . This groove and ridge feature provides improved strength of the blade and increases the coefficient of friction between clutch plate 1104 and blade 2100 along the interface of the bottom surface 2107 .
[0034] In this embodiment of FIG. 10 that includes both a blade and string cutting implements, preferable the blade is oriented at a position approximately ninety degrees to the location where the string exits the head. In the event that the blade is not optimally positioned, it can interfere and cut the string.
[0035] Referring no to FIG. 1 , the opposite end of the blade extend from the middle section to define and angel that is 115 degrees. However angle anywhere from 110 degrees to 140 degrees may be useful depending on the application. As the angle approaches of the cutting section to the middle section approaches 180 degrees, the tool is harder to control and can become more dangerous to use. In preferred embodiments, the opposite cutting portions of the blade form angles between 115 to 120 degrees with the middle section. In an embodiment both the blade and the clutch member will flex in response to pressure exerted on the blade.
[0036] Referring to FIGS. 15-20 , a clutch member 3101 as a length that is slightly less than the middle section of the blade for which it is used. It has a central aperture 1305 allow the drive member 1352 to pass through the member. The member 3103 is affixed to the clutch and is used for attachment to the head. Fig, 21 depicts an alternative arrangement 4201 that includes a clutch member 3202 . This member has a profile with a middle section 3214 that not in the same plane as the outer section 3216 and 3218 . Section 3216 and 3218 engage the blade member. This embodiment provides some flexibility between the clutch and blade 4250 . As head 3280 is attached to the opposite member 3281 on the tool the clutch 3202 is comprised and put into tension and therefore will flex to provide an improved grip on the blade.
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A rotary tool for cutting woody brush, that includes an engine, a transmission for transferring rotational movement to a head, an elongate pole, and the head is positioned at the end of the pole, and connected to the head is a cutting blade that has a flat middle section that is adapted to engage and opposite cutting sections that extend downwardly from the middle section, and the cutting sections have cutting surfaces and, in embodiments, the tool includes cutting line.
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CROSS-REFERENCE TO RELATED APPLICATION
This is a continuing application, under 35 U.S.C. §120, of copending International Application PCT/EP 2004/008560, filed Jul. 30, 2004, which designated the United States; this application also claims the priority, under 35 U.S.C. §119, of German Patent Application 103 37 265.2, filed Aug. 13, 2003; the prior applications are herewith incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a process for producing a body for exhaust gas treatment, which has a plurality of metallic layers forming passages through which a gas stream can flow. Bodies of that type are used in particular for purifying the exhaust gases from mobile internal combustion engines, such as spark ignition or diesel engines. Primary application areas in this context are passenger automobiles as well as trucks and motorcycles. It is also known for such bodies to be used in exhaust systems of portable hand-held appliances such as, for example, power saws, lawnmowers, etc. Bodies of that type have a number of different functions. For example, they are used as catalyst carrier bodies, as adsorbers, as filters, as flow mixers or as mufflers. The body is usually distinguished by a favorable ratio of surface area to volume, i.e. it has a relatively large surface area and therefore ensures intensive contact with the gas stream flowing through it.
With regard to catalyst carrier bodies, the surface or body is provided with a catalytically active coating, which preferably includes a washcoat. The washcoat has a particularly fissured surface, so that the ratio of surface area to volume can be improved even further. The washcoat is impregnated with various catalysts, for example platinum, rhodium or the like.
Adsorbers substantially have a similar basic structure to that selected for bodies used as catalyst carrier bodies. However, a different objective is pursued with regard to the coating, so that consequently different coatings are used. The purpose of the adsorbers is, for example, to retain nitrogen oxides until suitable reaction partners and/or temperatures are present to allow those constituents of the exhaust gas to be converted as fully as possible.
Flow mixers are distinguished by the fact that their bodies have a multiplicity of passages which are flow-connected to one another. At the same time, guide surfaces, which allow the partial gas streams to be diverted, are provided in the interior of the body or of the passages. In that way, the gas stream is made more uniform in terms of its pollutant concentration, its flow properties, its temperature, etc.
A wide range of different structural forms are known for the above-mentioned bodies as catalyst carrier bodies, adsorbers, mufflers and flow mixers. Those forms include, for example, honeycomb bodies having at least partially structured sheet-metal foils. As compared to known bodies made from ceramic material, the metallic honeycomb bodies have a considerably greater flexibility in terms of their intended use and also allow a greater degree of design freedom. It should also be borne in mind that particularly effective conversion processes with regard to the pollutant concentration are ensured due to good heat conduction and extremely low area-specific heat capacity.
A distinction is drawn in particular between two typical structures of metallic honeycomb bodies. An early structure, of which German Published, Non-Prosecuted Patent Application DE 29 02 779 A1, corresponding to U.S. Pat. No. 4,273,681 shows typical examples, is the helical structure, in which substantially one smooth and one corrugated sheet-metal layer are placed on top of one another and wound helically. In another structure, the honeycomb body is constructed from a multiplicity of alternately disposed smooth and corrugated or differently corrugated sheet-metal layers, the sheet-metal layers initially forming one or more stacks which are then intertwined. In that case, the ends of all of the sheet-metal layers come to lay on the outside and can be connected to a housing or tubular casing, producing numerous connections, which increase the durability of the honeycomb body. Typical examples of those structures are described in European Patent EP 0 245 737 B1, corresponding to U.S. Pat. Nos. 4,946,822; 4,923,109; 4,832,998 and 4,803,189, or International Publication No. WO 90/03220, corresponding to U.S. Pat. Nos. 5,139,844; 5,135,794 and 5,105,539. It has also long been known to equip the sheet-metal layers with additional structures in order to influence the flow and/or bring about cross-mixing between the individual flow passages. Typical examples of those configurations include International Publication No. WO 91/01178, corresponding to U.S. Pat. No. 5,403,559, International Publication No. WO 91/01807, corresponding to U.S. Pat. Nos. 5,130,208 and 5,045,403, and International Publication No. WO 90/08249, corresponding to U.S. Pat. No. 5,157,010. Finally, there are also conical honeycomb bodies, optionally also with further additional structures for influencing the flow. A honeycomb body of that type is described, for example, in International Publication No. WO 97/49905, corresponding to U.S. Pat. No. 6,190,784. Furthermore, it is also known to leave free a cutout in a honeycomb body for a sensor, in particular for accommodating a lambda sensor. One such example is described in German Utility Model DE 88 16 154 U1.
Of course, the structures described above are also suitable for forming filter bodies. Basically, two different principles are known for those or other filter bodies. One principle relates to what is known as the “closed particulate filter”, in which the passages formed by the body are closed on alternate sides, therefore forcing the gas stream to pass through passage walls including filter material. That leads to the accumulation of particulates or solids contained in the gas stream, which are burnt and/or oxidized continuously or at predeterminable intervals. An alternative known structure is that of the “open particulate filter”, which is not closed on alternate sides, but rather has flow diversion points in the interior of the passages, which cause the partial gas streams to be swirled up in such a way that at least 80% of the partial gas streams pass through the filter wall, preferably a number of times. The major advantage of the “open particulate filter” is that blockage of the filter material caused by an excessive accumulation of particulates is avoided. A particulate filter is described as “open” if particulates can fundamentally flow completely through it, specifically including particulates which are considerably larger than the particulates that are actually to be filtered out. As a result, a filter of that type cannot become blocked even in the event of an agglomeration of particulates during operation. A suitable method for measuring the openness of a particulate filter is, for example, to test the diameter up to which spherical particles can still trickle through a filter of that type. In present applications, a filter is open in particular if spheres with a diameter of greater than or equal to 0.1 mm can still trickle through it, preferably spheres with a diameter of over 0.2 mm. One such example is given in German Utility Model DE 201 17 873 U1, to which reference is made in full for the purposes of explanation.
In addition to those bodies with wound or intertwined layers, it is also known to use what are known as plate filters, which include a plurality of in particular sheet-like or substantially planar filter plates that are disposed spaced apart from one another. Plate filters of that type are usually also constructed in accordance with the principle of passages that are closed on alternate sides, but it is in principle also possible to realize an “open particulate filter”.
Whereas wound structures and plate structures of that type have the gas stream flowing through them substantially axially, bodies or filter bodies which the gas stream flows through radially are also known. Such bodies usually have an inner flow passage and an outer flow passage which is annular in form and is generally disposed coaxially with respect to the inner flow passage. The inner flow passage is generally delimited by an inner tube, which is provided with openings through which the gas stream to be purified is passed. Layers of a filter material are disposed around the inner tube. Substantially two different concepts are known in that respect. The first concept can be described on the basis of a “star shape”, which is realized when the filter plates are viewed in the direction of the inner tube or a cross section perpendicular to the inner tube. That means in other words that the filter plates form folds which extend substantially parallel to the axial extent of the inner tube. Another known concept involves the formation of folds in the circumferential direction, in which case a plurality of the folds are positioned on the inner tube, spaced apart from one another in the axial direction. According to the routing of the flow, the gas stream that is to be purified is fed to the filter material from the inside (or from the outside), penetrates through the filter material and is discharged again on the opposite side.
The bodies described above generally include a plurality or multiplicity of different components made from in some cases different materials. Considering the high thermal and dynamic stresses in the exhaust system of mobile internal combustion engines, those individual components have to be permanently connected to one another. Numerous different connection techniques are known for that purpose, for example brazing and/or welding. With regard to those connection techniques, it should be noted that they have to be suitable for at least medium-sized series production. In that respect, cost aspects also play an important role, such as cycle rates, connection quality, process reliability, etc. Known processes used to form connections by technical joining (in particular in the structure including the filter surfaces and/or the layers) require an additional material such as, for example, brazing material or weld filler. It is particularly difficult in that case for the filler to be applied at precisely the location at which a join is subsequently to be produced. Moreover, it should be noted that increasingly thin-walled materials need to be used, since such materials very quickly adapt to the temperature of the exhaust gas and accordingly have highly dynamic reaction properties. In order to ensure the long-term functionality of those bodies, however, a spatially tightly delimited introduction of heat is required to form the connections by technical joining. Heretofore, that has not been achievable to a satisfactory extent, and indeed brazing generally requires heating of the entire body in a high-temperature vacuum furnace, and welding has heretofore usually also been carried out through the outer housing, and consequently in that case too considerable temperature gradients have been realized across a large part of the body.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a roller seam welded body for exhaust gas treatment and a process for producing the body, which overcome the hereinafore-mentioned disadvantages and technical problems of the heretofore-known devices and processes of this general type, in which the process for producing metallic bodies of this type for exhaust gas purification is inexpensive, simple, effective and reliable and is suitable for automation as far as possible, producing connections by joining which are distinguished by a particularly long service life, and in which the corresponding body for exhaust gas treatment can be configured variably and is versatile in use.
With the foregoing and other objects in view there is provided, in accordance with the invention, a process for producing a body for exhaust gas treatment. The process comprises bringing a plurality of metallic layers into contact with one another in a connection region. A connection of the layers is produced by a continuous resistance welding process, causing the layers to form passages or channels through which a gas stream can at least partially flow. In other words, this means in particular that the connection between layers disposed adjacent one another is effected by the continuous resistant welding process.
In this context, it should be noted that the term “continuous” may mean that the welding takes place along one welding track, in which case the weld seam that is generated is made uninterrupted. However, this need not necessarily be the case. For example, it is also possible for a plurality of weld seams which are spaced apart to be provided along the welding track, in which case the proportion in which the weld seams are present along the welding track is advantageously significantly greater than the proportion formed by the interruptions. It is particularly preferable for the proportion formed by the weld seam, based on the welding track, to amount to at least 80%, in particular even more than 90%.
With regard to the “passages”, it should also be noted that these passages need not necessarily have a tube-like structure. Rather, this term is to be understood as meaning a limited flow path which has a spatial boundary. In this case, the boundary is generally configured in such a way that it encloses the flow path over at least 60% (in particular 80%) of the circumference, with the length of the flow path advantageously being greater than the circumference.
In view of the fact that the above-mentioned body may also be constructed as a filter, it will be clear that the passages do not necessarily need to have a gastight passage wall, i.e. it is also eminently possible for the layers to be configured so as to be at least partially gas-permeable. In particular in this case, the gas stream does not flow completely through the passage, in which case although the passage does have a suitable cross section, the gas stream nevertheless uses a different route. Therefore, it is considered sufficient for the passage to offer the option of at least partially allowing a gas stream to flow through it, in particular with open end sides.
In accordance with another mode of the invention, the continuous resistance welding process includes roller seam welding and/or projection seam welding.
Roller seam welding and projection seam welding processes belong to pressure-joining welding processes, in particular resistance pressure welding or conductive pressure welding. In the resistance pressure welding process, the heating at the welding location takes place as a result of Joule resistance heating when current flows and through the use of an electrical conductor. The current is supplied through electrodes with a convex or planar working surface. Two roller-like (driven) electrodes are used for the roller seam welding. The metal sheets to be welded are disposed predominantly overlapping in this case. In practice, roller seam welding is a continuous spot welding, but using roller-like electrodes. Unlike the case when using resistance spot welding, the electrodes remain in contact after the first weld spot has been produced and are then rolled continuously onward. Further current flows at the locations where a weld spot is to be formed. Spot seams or sealed seams with overlapping weld nuggets or weld spots are produced, depending on the feed rate of the electrodes and the frequency of the welding current. Permanent direct current likewise produces a sealed seam.
The use of this production process to connect the layers has proven particularly advantageous in particular with a view toward series production of these bodies. The process in which the two layers adjacent or lying on top of one another are passed through the rotating electrodes is surprisingly well able to withstand the high thermal and dynamic stresses, for example in the exhaust system of automobiles. It has also been established that even in the case of very thin metal foils which are connected to one another in this way, sealed weld seams can be produced in very short working cycles. As a result, it is possible to achieve in particular a cost benefit, which was unexpected in view of the additional material that is required for the overlap between the two layers. Roller seam welding is suitable in particular for connection regions which have a certain length, i.e. extend over a predetermined portion. This should generally amount to at least 5 cm, in particular at least 15 cm, and the work can be carried out at particularly low cost beyond a length of 25 cm. The roller seam welding makes do without filler. Furthermore, in many cases it is also possible to do without a step of cleaning the layers, since the introduction of the electrode force ensures that contact between the electrodes and/or the layers which is sufficient for the flow of current and the formation of the weld spot is already ensured to a considerable extent. Moreover, only an insignificant change in the microstructure of the layer adjacent the weld nugget can be established. Accordingly, the use of this manufacturing process offers numerous advantages and at the same time overcomes all of the technical problems listed in the introduction hereto at once. Moreover, the process can also be applied to each of the types of bodies mentioned in the introduction hereto.
In accordance with a further mode of the invention, a weld seam in which there are at least overlapping weld spots is formed, at least in part. This applies in particular to the case in which the ends or edge regions of the layers are to be fixed to one another. These edge regions or edges, for example, close up flow paths, so that the exhaust gas to be purified is forced to pass through a filter material. In order to ensure the principle of a “closed particulate filter”, a sealed seam should be at least partially present. This is to be understood as meaning that the welding current pulses take place in succession at such short time intervals that the respectively adjacent weld spots or weld nuggets merge into one another, i.e. there are no unconnected locations on the layers between adjacent weld spots. As has already been stated above, a sealed seam of this type is achieved by virtue of the frequency of the current pulses being selected to be relatively short, the feed rate being relatively low or by the presence of direct current, i.e. current flows continuously between the electrodes during the feeding.
In accordance with an added mode of the invention, a feed rate during roller seam welding in a range of from 0.5 cm/s to 30 m/s, in particular in a range of from 0.5 m/min to 30 m/min, is used.
This feed rate is used in particular when connecting metallic foil material which has a thickness of from 0.03 to 0.1 mm. In this case, the material to be connected preferably includes the following constituents: from 0.1 to 7.5% by weight of aluminum, and from 17 to 25% by weight of chromium. Another preferred material includes from 12 to 32% by weight of nickel.
In accordance with an additional mode of the invention, during the welding operation, the electrodes exert a force of from 10 N to 20 kN, in particular from 200 N to 6 kN, on the layers. This ensures that, for example, any rolling oil or similar impurities adhering to the layers are forced out of the welding location. The result is both intensive contact between the components which are to be connected to one another and between the components and the electrodes. At the same time, this ensures that when the material is heated, the heated or molten materials are intimately mixed, so as to achieve a permanent connection.
In accordance with yet another mode of the invention, the layers, at least in an edge region, are laid on top of one another, are welded at least over a portion in this edge region and are then deformed, so as to form the passages. In other words, this also means that the weld seam at least partially delimits the passage through which the exhaust gas can flow. With regard to the preferred magnitudes of the length of the portion, reference should be made to the statements given above. In principle, however, it should also be noted that it is customary for the complete edge regions to be connected to one another, i.e. accordingly the portion corresponds to the longest extent of the edge region.
In accordance with yet a further mode of the invention, the layers are formed with at least one metallic foil which is made from a high-temperature-resistant and corrosion-resistant material and is preferably at least partially structured and/or allows a fluid to flow through it at least in regions. With regard to the material of the metallic foil, reference should be made at this point to the composition listed above. Furthermore, however, a person skilled in the art will be aware of a large number of further materials which are suitable for use in mobile exhaust gas systems. In this case, reference should be made to the large number of different materials which are given in the known prior art. When making a choice, it should also be borne in mind that this material must in general terms be suitable for resistance welding, i.e. in particular must also conduct current.
The preferred configuration of the metallic foil with structures or apertures, pores, holes or the like in this case is predominantly located outside the edge regions which are used for connection by roller seam welding. Examples of suitable structures include corrugations, guide vanes, stamped formations or other structures. They are usually used to guide or swirl up the exhaust gas flowing along the metallic foil, in order to ensure intimate contact with the surface of the body in this way. Furthermore, these structures can also be used to make sure that the layers are at a predeterminable distance from one another. In this case, the structure represents a type of spacer. The effect of the foil being configured such that medium can flow through it at least in regions is that gas exchange can take place through the metallic foil. This usually depends on a forced flow, for example imposed by diverting vanes, sealing materials, etc. or by pressure differences in adjacent passages, which are in each case partially delimited by the metallic foil.
In accordance with yet an added mode of the invention, the layers are formed with a filter fabric which may be a nonwoven or fleece filter fabric or a supporting structure including a filter material. The filter fabric includes in particular knitted fabrics, woven fabrics or similar configurations of chips, fibers or other particles which are bonded to one another. They are held together, for example, by sintered connections, brazed connections, welding connections or combinations thereof. The filter fabrics may be composed of metallic or ceramic material. Furthermore, it is also possible to provide a supporting structure on or in which a filter material is provided. Suitable supporting structures are once again woven fabrics, knitted fabrics, expanded metals or the like, in particular coarse-mesh formations, in the cavities of which the filter material is provided. It is in this context particularly advantageous for the supporting structure to be metallic in form, in which case both ceramic and metallic materials can be used as filter material. The filter material is connected to the supporting structure through the use of sintered connections, diffusion bonds, if appropriate also using filler materials, or combinations of these connection techniques. The connection according to the invention between the layers using a continuous resistance weld seam can also be carried out so as to incorporate this supporting structure, in particular by the layers being welded to one another exclusively through the supporting structures.
The filter material itself forms an extremely high surface area with a multiplicity of pores, openings, flow passages and cavities. As the gas stream flows through the filter material, the undesired particulates stick to the surface and are converted into gaseous constituents when heat and/or reaction partners contained in the exhaust gas are supplied.
In accordance with yet an additional mode of the invention, the layers have a multi-part structure, and the layers are provided with a metallic foil in the connecting region, so that the metallic foils of layers disposed adjacent one another are connected through the use of roller seam welding. This means in particular that the foils are provided only in the edge region of the layers. In this case, for a filter material or a supporting structure, they preferably form a construction which is suitable for roller seam welding. It is in this way possible to adapt components of the body which cannot normally be connected by such a process, to the requirements of roller seam welding.
In accordance with again another mode of the invention, the layer includes a filter fabric. The filter fabric, in the edge region which subsequently forms the connecting region, is surrounded, and preferably also flanged, by in each case one metallic foil. Finally, a plurality of layers produced in this way are welded to one another. In this case, the layers are configured in particular as a filter composite or filter layer as proposed by German Published, Non-Prosecuted Patent Application 101 53 284 A1, corresponding to U.S. patent application Ser. No. 10/823,996, filed Apr. 13, 2004 and U.S. Patent Application Publication No. US2004/0187456 A1 and German Published, Non-Prosecuted Patent Application 101 53 283 A1 corresponding U.S. patent application Ser. No. 10/828,813, filed Apr. 20, 2004 and to U.S. Patent Application Publication No. US2004/0194440 A1. With regard to the construction of filter layers or filter composites of this type, reference is made to the above-referenced publications in full, and consequently the descriptions given therein are used to explain the present situation and they are incorporated herein fully by reference.
In accordance with again a further mode of the invention, with regard to the above process variant for production of the body, it is particularly advantageous if the flanging and the roller seam welding are carried out simultaneously. By way of example, structured rolled electrodes are used for this purpose, which on one hand allows the metallic foil to be hooked to the filter fabric and at the same time, due to the flow of current, allows a material or cohesive connection by technical joining. In this case, the welding process can also be carried out in such a way that flanged connections and welded connections alternate in the welding direction. In the present context, the term flanging is to be understood in particular as meaning manual or mechanical bending-over of the edges of sheet-metal parts to remove the sharpness of the edge and/or to reinforce the workpiece.
In accordance with again an added mode of the invention, the layers are welded together in such a way that they are connected in the edge regions on alternate sides to an adjacent layer in each case, so as to form a fold in each case. The procedure described herein for the production of a body is suitable in particular for producing filter bodies. In this case, the layers, which preferably also include filter fabric or a filter material, are connected to one another at their edge regions, in order to realize the principle of the “closed particulate filter”. After two adjacent layers have been welded together, the layers can be folded open so that they form an angle relative to one another in an edge region. The intermediate space which has formed between the layers is referred to as a fold. This represents a passage or flow passage, in particular in the case of radial-flow particulate filters.
In accordance with again an additional mode of the invention, the layers are constructed with supports, which are preferably disposed in a passage and/or in a fold. The term support is to be understood in particular as meaning spacers, reinforcing structures, spacer pieces or similar devices which ensure that the predetermined position of the layers with respect to one another is retained even during subsequent use in the exhaust system of mobile internal combustion engines.
In accordance with still another mode of the invention, the supports are connected to the layer by the roller seam welding manufacturing process, preferably at the same time as a connection of the layers to one another is being executed. By way of example, the supports may be formed as a structure of the metallic foil, which therefore bear against regions of the adjacent layer and ensure the aperture angle or the spacing of the layers that are spaced apart from one another. The connection of the layers according to the invention by using a continuous resistance weld seam can also be carried out by incorporating these supports. Under certain circumstances, the layers are even welded to one another exclusively through the supports.
In accordance with still a further mode of the invention, the welded layers are connected to at least one housing, preferably by welding or brazing. In the case of axial-flow bodies, direct connection of the layers to the housing located on the outer side is preferred. Known brazing or welding techniques can be used for this purpose. If the body realizes a radial-flow structure, a connection to an outer housing is generally realized only indirectly, i.e. through additional elements. In structures of this type, a housing which is directly connected to the layers and is disposed on the outer periphery of the body is usually avoided, since this annular space is usually required for the incoming and/or outgoing flow of the gas stream. The outer housing is then fixed through any additional components, such as spacers, cover plates, collars or the like.
In accordance with still an added mode of the invention, in particular in the context of the radial-flow concept, it is proposed that the housing be an inner tube with a central axis, to the outer lateral surface of which inner tube the layers are secured. For this purpose, the inner tube is provided with holes or flow passages which allow the exhaust gas to flow through the inner tube without generating a high flow resistance. This makes is easy to connect the cavity disposed in the interior of the tubular casing toward the folds, which have been formed by the layers disposed on the outside. The connection of the layers toward the inner tube can be realized by mechanical connections or by thermal joining. In particular with a view toward securing by using mechanical securing measures, it is to be assumed that the inner tube preferably has a multi-part construction. The inner tube is usually equipped with a closed end, in order to divert the gas stream toward the filter surfaces.
In accordance with still an additional mode of the invention, the layers are to be disposed in such a way that the connecting regions or the folds or passages formed by the layers run in the direction of the central axis. With regard to the words “in the direction of the central axis”, it should be pointed out for clarification that this does not require any particular accuracy, but rather relatively large tolerances are possible under certain circumstances. In this case, therefore, there are a plurality of folds which are disposed adjacent one another in the circumferential direction and preferably extend over a large portion of the inner tube. The connection regions between the individual layers and between the layers and the inner tube in this case run in the axial direction parallel to the central axis.
In accordance with a concomitant mode of the invention, in an alternative configuration, the layers are disposed in such a way that the connecting regions and/or the folds or passages formed by the layers run perpendicular to the central axis. With regard to the words “perpendicular to the central axis”, it should be pointed out for clarification that this does not require any particular accuracy, but rather relatively large tolerances are possible under certain circumstances. The feature means in particular that the fold is constructed as an annular passage extending in the circumferential direction. A plurality of these annular folds are disposed spaced apart from one another (as seen in the direction of the central axis). The connection regions between the individual layers and between the layers and the inner tube run in the circumferential direction.
With the objects of the invention in view, there is also provided a body for treating exhaust gases from mobile internal combustion engines, in particular produced by one of the processes described above. The body comprises a plurality of metallic layers in contact with one another in a connecting region. At least some of the layers have a roller seam welded joint therebetween. The layers form passages through which a fluid can flow. A body of this type is suitable for use as a catalyst carrier body, an adsorber, a filter body or a flow mixer. It is also possible for the body to be configured in such a way as to form zones with different functions, for example by having different coatings in different zones. It is also possible for the layers to be constructed differently with regard to the gas permeability and/or the structuring in these zones, so that different exhaust-gas purification steps are passed through sequentially in the direction of flow.
The invention and the technical background will now be explained in more detail with reference to the figures. The figures show particularly preferred exemplary embodiments, although the invention is not restricted to these embodiments. Rather, the production process of roller seam welding can be used for numerous different structures of bodies for exhaust-gas purification, with in particular the connection between the layers forming the flow passages being produced by using these manufacturing processes.
Other features and further advantageous configurations which are considered as characteristic for the invention and are set forth in the appended claims, can be combined with one another in any desired way.
Although the invention is illustrated and described herein as embodied in a roller seam welded body for exhaust gas treatment and a process for producing the body, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic and schematic view illustrating a sequence of an implementation of a process for producing a body for exhaust-gas treatment;
FIG. 2 is a fragmentary, sectional view of a variant embodiment of a body for exhaust-gas treatment;
FIG. 3 is a further fragmentary, sectional view of an exemplary embodiment of the body;
FIG. 4 is a partly broken-away, perspective view of an exemplary embodiment of a body with longitudinal folds;
FIG. 5 is a perspective view of a further configuration of a body with coaxial folds;
FIG. 5A is an enlarged view of a portion VA of FIG. 5 ; and
FIG. 6 is a further sectional view of a body with folds in the circumferential direction.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the figures of the drawings in detail and first, particularly, to FIG. 1 thereof, there is seen a diagrammatic and schematic illustration of a sequence involved in the production process of roller seam welding, which is used in this case to produce a body for exhaust gas treatment. FIG. 1 illustrates two metallic foils 12 which are brought into contact with one another. The foils 12 , while resting on top of one another, are passed at a feed rate 7 through two rotating electrodes 8 . In the process, the two electrodes 8 press on the surface of the foils 12 with a force 9 . The two electrodes 8 are connected to one another through a current source 26 , with current flowing between the electrodes 8 and therefore also locally through the foils 12 with a predetermined frequency. The current leads to heating of the foils 12 , so that they become at least partially molten. The foils 12 in this case have a thickness 22 which is, for example, in the range from 0.02 to 0.1 mm. As a result of Joule resistance heating, a multiplicity of weld spots 6 , which preferably merge into one another so as to form a sealed seam 5 , are formed in a contact region between the two foils 12 .
FIG. 2 diagrammatically illustrates a fragmentary view of a connecting region 3 , which is formed between two adjacent layers 2 . The layers 2 are formed with a filter fabric 13 which may be a nonwoven or fleece filter fabric, and which is provided near an edge region 10 with a foil 12 that has been flanged. The foils 12 project beyond the filter fabric 13 and form the edge region 10 , which is finally pushed through the rotating electrodes 8 , so that a roller seam welded connection is produced between the two foils 12 . Whereas the filter fabric 13 has a gas-permeable structure, as is indicated by dashed arrows, the foil 12 itself in this case is impermeable to gases. The foil 12 in this case serves simultaneously to fix a support 17 , ensuring a defined position of the layers 2 with respect to one another, so that folds 16 are always of a desired shape.
FIG. 3 shows a body 1 with a plate construction, having the layers 2 disposed substantially parallel to one another. The plate-like layers 2 in the illustrated embodiment include a supporting structure 14 in which a filter material 15 has been integrated. A connecting region 3 is formed in each case in the edge regions on alternate sides of the layers 2 . The connecting regions 3 again include roller seam welded connections. The connection regions 3 bear directly against a housing 18 and are connected to it by technical joining. A support 17 disposed between the layers 2 is formed, for example, of structured metal foils or structures of the layers 2 themselves, which prevent the layers 2 from bearing directly flat against one another. It can also be seen that through the use of the illustrated body 1 , the principle of a “closed particulate filter” has been implemented, in which adjacent passages 4 are provided with a closure 24 , so that the gas stream has to pass through the layers 2 in a direction of flow 23 .
FIG. 4 shows another variant embodiment of a body 1 for exhaust gas treatment, which is used in particular as a filter. This figure shows a radial-flow concept, in which the gas stream that is to be purified first of all enters an inner region in the direction of a central axis 21 through a cover plate 25 . A rear-side cover plate 25 closes off the inner flow passage and therefore forces the exhaust gas to pass through the layers 2 which form the folds 16 . The illustrated body 1 again has a support 17 , which ensures the position of the layers 2 with respect to one another even in the event of pressure fluctuations occurring in the gas flow. In the illustrated exemplary embodiment, the layers 2 are disposed in such a way that the connection regions 3 and the folds 16 formed by the layers 2 run in the direction of the central axis 21 . The connection regions 3 are in each case formed over a portion 11 .
FIG. 5 shows a further variant embodiment of a body 1 , in particular a filter body. In this case, the folds 16 run substantially coaxially with respect to the central axis 21 . The layers 2 are mounted on end sides of a cover plate 25 which at least partially allows the exhaust gas to flow through it. The connection regions 3 of the layers 2 which are disposed adjacent one another are disposed substantially coaxially to the central axis 21 , once again realizing the principle of a “closed particulate filter”. The layers 2 in this case include a supporting structure 14 in which the filter material 15 is additionally provided, as is seen in FIG. 5A .
FIG. 6 shows a body 1 in which the layers 2 are disposed in such a way that the connection regions 3 and the folds 16 formed by the layers 2 run substantially perpendicular to the central axis 21 . The layers 2 are secured to an outer lateral surface 20 of an inner tube 19 . The inner tube 19 has openings through which the gas stream can enter radially inwardly, as is shown by arrows indicating a direction of flow 23 . Additional supports 17 are disposed between the layers 2 outside the folds 16 which are illustrated by dots. In this case, these supports 17 are connected on one side to the inner tube 19 and on the other side to the layers 2 . Moreover, the entire configuration is enclosed by a housing 18 spaced apart from the layers 2 . The connection regions 3 , which have been generated by using the roller seam welding process, are formed on the outer periphery and the inner periphery of the layers 2 . They produce a connection in each case between the layers 2 which are disposed adjacent one another. The preferred manner of producing the technical joining connection is by brazing. However, a sintering process or even welding may be used as well.
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A process for producing a body for exhaust gas treatment having a plurality of metallic layers, includes bringing the layers into contact with each other in a connection region. A connection is made by a roller seam welding process in such a way that the layers form passages through which a gas stream can flow. A corresponding body for exhaust gas treatment can especially be used as a filter or catalyst carrier body in the automobile industry.
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RELATED APPLICATIONS
The subject matter of this application is related to U.S. Design patent application Ser. No. 29/557,254 filed Mar. 7, 2016 and titled CASE FOR AUTHENTICATED COMIC BOOK, and U.S. Design patent application Ser. No. 29/557,255 filed Mar. 7, 2016 and titled CASE FOR AUTHENTICATED COMIC BOOK, both of which applications are hereby incorporated by reference in their entireties.
BACKGROUND
Comic books and other collectible items such as books and magazines are bought and sold at trade shows and collectible item dealer stores. In addition, collectible items are increasingly being transacted over the Internet. In these types of transactions, purchasers are concerned that the item purchased is not authentic and/or not accurately described or graded. There exist commercial services that authenticate, grade, and encapsulate comic books submitted by owners. Once a comic book is graded, the service encapsulates the book within a tamper-evident transparent plastic case with a certificate indicating the description and grade of the book. The graded and encapsulated book, which is then returned by the service to its owner, becomes a more marketable item than one that is not graded and encapsulated.
In addition to establishing authenticity and grade, comic book cases also protect books from wear and tear. Damage can occur, for example, during shipping of a book that is otherwise not protected by a case. U.S. Pat. No. 5,415,290 describes a comic book protection cover system including an open ended bag formed of thin flexible transparent polypropylene and a rectangular rigid transparent insert. Space remains in the bag for receipt of the comic book adjacent the insert. U.S. Pat. No. 5,353,925 describes a preservation device for a collectible article in which a front and back panel define a cavity for receiving the collectible article. A spacing sheet positioned between the front and back panels creates a channel around the article. A gaseous substance is circulated around the channel. The gaseous substance is exposed to a desiccant for removing moisture. Screws are used to secure the back panel to the front panel. The article can be removed from the preservation device by unscrewing the screws.
U.S. Pat. No. 6,102,207 describes a collectible article holder providing readily observable positive evidence if tampering of the holder has occurred, thereby indicating that the item contained in the holder is authentic. The collectible article, such as a comic book, is placed in a core. Means for authenticating the collectible article is coupled to the core. The core is received in a cavity formed between a top and a bottom of a case. The top and bottom are ultrasonically bonded together. The case is designed to include means for positively indicating sealing of the top to the bottom which means form a visible irreparable condition of the case indicative of tampering. Key slots are formed in the side of the case to allow a purchaser after purchasing the collectible article to insert a tool, such as a screwdriver, in order to open the case. After the case is opened, the core layers can be peeled apart for allowing the purchaser to handle the collectible article. It will be appreciated that after the case has been opened, the collectible article is no longer certified as authentic.
SUMMARY
A comic book case includes a base and a cover configured to compress and secure a comic book in place under frictional pressure such that the book cannot easily shift or slip within the case. Prior art cases that included walls surrounding the top, bottom and side edges of a book typically allowed some free movement or slippage of the book between the walls. This movement or slippage could result in damage such as curling or crinkling of the edges of the book if the case were exposed to a physical shock, such as by being dropped. The base includes a raised base platform and the cover includes a depressed cover platform, which extends towards the base platform to create a space within which the book is securely held. Appropriately configured and sized bases and/or covers can be used to account for the necessary space to provide adequate frictional pressure for different thicknesses of books. In addition to comic books, the case can be configured in different shapes and sizes to hold other types of books, magazines, pamphlets, documents, or other types of articles. In accordance with different embodiments, the case can be configured with an appropriate size and shape to encapsulate substantially any flat article.
To assemble the case, a book, optionally enclosed in a clear plastic envelope bag, is placed on the base platform, and a certificate is placed on a certificate platform. The cover is placed over the base such that a set of posts extending up from the base are received in a corresponding set of receptacles in the cover. The engagement of the posts and receptacles, such as by friction or deformation of the posts and/or receptacles upon engagement, can provide tension to at least temporarily hold the cover to the base. The temporarily assembled case can then be permanently or semi-permanently assembled using ultrasonic bonding around part of all of mating surfaces on the base and cover which extend around the perimeter of the case. Ultrasonic bonding can also or alternatively be used to bond the posts to the receptacles, which can provide a visual indication of tampering if the bond between the posts and receptacles is broken or if the posts and/or receptacles themselves are broken.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an exploded view of a comic book case from a lower right side perspective in accordance with one embodiment.
FIG. 2 illustrates a second exploded perspective view of the case from an upper left side perspective.
FIG. 3 illustrates a front elevation view of the assembled case.
FIG. 4A illustrates a high perspective view of the assembled case from a lower right side.
FIG. 4B illustrates a low perspective view of the assembled case from the lower right side.
FIG. 4C illustrates a low perspective view of the assembled case from the bottom side.
FIG. 5 illustrates a close perspective view showing detail of the upper left portion of the cover.
FIG. 6 illustrates a close perspective view showing detail of the lower left portion of the cover.
FIG. 7 illustrates a low perspective view of the assembled case from the right side.
FIG. 8 illustrates a low perspective view of the assembled case from the top side.
FIG. 9 illustrates a rear elevation view of the assembled case.
FIG. 10 illustrates a high side perspective view of the assembled case showing the base.
FIG. 11 illustrates a low perspective view of the assembled case showing the base from the bottom side.
FIG. 12 illustrates a low perspective view of the assembled case showing the base from the side.
FIG. 13 illustrates a low perspective view of the assembled case showing the base from the top side.
FIG. 14A illustrates an embodiment of a case configured with an approximately 1 mm gap between the upper surface of the base platform and the lower surface of the cover platform.
FIG. 14B illustrates an embodiment of a case configured with an approximately 3 mm gap between the upper surface of the base platform and the lower surface of the cover platform (this embodiment is also shown in all other figures).
FIG. 14C illustrates an embodiment of a case configured with an approximately 5 mm gap between the upper surface of the base platform and the lower surface of the cover platform.
FIG. 15 illustrates an elevation view of the inside of the base.
FIG. 16A illustrates a perspective view of the inside of the base from the lower right side.
FIG. 16B illustrates a perspective view of the inside of the base from the upper left side.
FIG. 17 illustrates a close up perspective view of the upper left hand section of the inside of the base.
FIG. 18 illustrates a close up plan view of the upper right portion of the base.
FIG. 19 illustrates a close up perspective view of a lower corner portion of the inside of the base.
FIG. 20 illustrates an elevation view of the inside of the cover.
FIG. 21A illustrates a perspective view of the inside of the cover from the lower right side.
FIG. 21B illustrates a perspective view of the inside of the cover from the upper right side.
FIG. 22 illustrates a close up perspective view of the upper right hand section of the inside of the base.
FIG. 23 illustrates the same elevational view of the assembled case as FIG. 3 , but with sight lines added that indicate the locations of cross section and cut-away views shown in FIG. 24A-G .
FIG. 24A illustrates a perspective view of a cut away through the case along sight line A.
FIG. 24B illustrates a sectional elevation view through the case along sight line B.
FIG. 24C illustrates a perspective view of a cut away through the case along sight line C.
FIG. 24D illustrates a perspective view of a cut away through the case along sight line D.
FIG. 24E illustrates a sectional elevation view through the case along sight line E.
FIG. 24F illustrates a sectional elevation view through the case along sight line F.
FIG. 24G illustrates a sectional elevation view through the case along sight line G.
DETAILED DESCRIPTION
In the following description, reference is made to the accompanying drawings, which form a part hereof, and which show, by way of illustration, specific embodiments or processes in which the invention may be practiced. Where possible, the same reference numbers are used throughout the drawings to refer to the same or like components. In some instances, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention, however, may be practiced without the specific details or with certain alternative equivalent devices, components, and methods to those described herein. In other instances, well-known devices, components, and methods have not been described in detail so as not to unnecessarily obscure aspects of the present invention.
FIG. 1 illustrates an exploded view of a comic book case from a lower right side perspective in accordance with one embodiment. The case includes a base 102 and a cover 104 , which are preferably each constructed of clear transparent rigid plastic. The base 102 and cover 104 can each be created, for example, using known injection molding processes.
FIG. 2 illustrates a second exploded perspective view of the case from an upper left side perspective. The exploded view of FIG. 2 further shows a comic book 202 and a certificate 204 in relative position above where they would rest within the base 102 . The comic book 202 will typically include bound printed material with a thickness between 1 mm and 5 mm, and different thickness books can be accommodated by varying the depth and configuration of the base 102 and/or cover 104 in accordance with different embodiments. As will be noted from the drawings, the book 202 and the certificate 204 are only shown in FIG. 2 and have been omitted from the remaining figures to more clearly illustrate the features of the base 102 and the cover 104 .
Referring to FIG. 1 , when the case is assembled, the book 202 is compressed and held in place between an upper surface of a base platform 112 of the base 102 and a lower surface of a cover platform 114 of the cover 104 . The base platform 112 can be raised by way of steps 130 on 2 or more sides relative to surrounding portions of the base 102 . The cover platform 114 can be depressed by way of steps 130 on 2 or more sides relative to a surrounding upper portion 2020 ( FIG. 20 ) of the cover 104 . The raised base platform 112 and depressed cover platform 114 are shown more clearly in subsequent figures such as the cut-away perspective view of FIG. 24C . The steps 130 that partially or completely circumscribe the base platform 112 and the cover platform 114 can function to counter deflection or bowing of the platforms by pressure exerted by the book on the platforms when the case is assembled. In accordance with one embodiment, the base 102 and the cover 104 are permanently assembled using ultrasonic bonding that surrounds part or all of the perimeters of the components.
Referring to FIG. 2 , the case also includes a certificate 204 marked with a description of the book. In one embodiment, the certificate is made of heavy stock paper that is scored, by cutting partially through the paper's thickness, and folded along the score at a right angle. The fold creates a larger face portion 204 A and smaller tab portion 204 B of the certificate 204 .
When the case is assembled, the face portion 204 A of the certificate 204 rests on an upper surface of a certificate platform 122 of the base 102 . The face portion 204 A can be viewed through a certificate window 124 of the cover 104 . The certificate platform 122 can be optionally integrated into or made a part of the base platform 112 , such that the top surface of the certificate platform 122 and the base platform 112 lie in the same plane. The certificate platform 122 can be substantially separate from the base platform 112 , with one or more steps up and/or down between the platforms, such that the top surface of the certificate platform 122 and the base platform 112 lie in different planes.
When the case is assembled, the tab portion 204 B is fitted in a slot 230 (shown more clearly in FIG. 18 ) formed between a top wall 210 of the base 102 and a number of vertically aligned fins 212 that extend outward from the certificate platform 122 . Both the face portion 204 A and the tab portion 204 B can include information identifying the book, such as a title, series and version. The face portion 204 A has additional space on which to include certification indicia and a grading indicating the condition of the book. When the tab portion 204 B is inserted into the slot 230 within the assembled case, the information on the tab portion can be viewed through the top wall 210 of the base 102 . In one embodiment, a separate label or certificate can be used instead of the tab portion 204 B. In one embodiment, one or more additional slots 230 can be formed on additional sides of the case, such as on the bottom, to accommodate additional labels.
In additional embodiments, one or more of the base platform 112 , the cover platform 114 , and the certificate platform 122 can be omitted in favor of a flat non-platform window panel that is not raised or depressed relative to the surrounding portions of the base 102 or cover 104 .
FIG. 3 illustrates a front elevation view of the assembled case. The base 102 and cover 104 are assembled such that the case has a top wall 210 , two side walls 310 , and a bottom wall 320 .
FIG. 4A illustrates a high perspective view of the assembled case from a lower right side. FIG. 4B illustrates a low perspective view of the assembled case from the lower right side. FIG. 4C illustrates a low perspective view of the assembled case from the bottom side.
FIG. 4B also shows an outer wall 410 , which bounds the perimeter of the case and which includes the top wall 210 , two side walls 310 , and bottom wall 320 . The outer wall 410 can be formed in part by each of the base 102 and the cover 104 , depending on how high the joint or break between the base 102 and cover 104 is positioned. In the illustrated embodiments, most of the outer wall 410 is formed by the base 102 . In additional embodiments, most of the outer wall 410 can be formed by the cover 104 , with the joint between the base 102 and the cover being located closer to the bottom of the base 102 .
FIG. 5 illustrates a close perspective view showing detail of the upper left portion of the cover 104 . Two steps 130 A and 130 B that form the upper and left side portions of the depressed cover platform 114 are visible. FIG. 5 also illustrates how the both the depressed cover platform 114 and the certificate window 124 can are positioned lower relative to an outer ridge 510 of the cover 104 in one embodiment.
In one embodiment, the outer ridge 510 defines four corner features 520 , where the ridge takes turns around the perimeter of the case. The four corner features 520 facilitate stacking of multiple cases as will be discussed below with reference to FIG. 9 .
FIG. 6 illustrates a close perspective view showing detail of the lower left portion of the cover 104 . Two steps 130 B and 130 C that form the left and lower side portions of the depressed cover platform 114 are visible.
FIG. 7 illustrates a low perspective view of the assembled case from the right side.
FIG. 8 illustrates a low perspective view of the assembled case from the top side. In one embodiment, the case can include a window area 810 on the top side of the case through which the tab portion 204 B of the certificate 204 can be viewed. The window area 810 , as shown, can extend along outside of the top wall 210 between near the left and right sides of the case, and between near the bottom of the base 102 , across the joint between the base 102 and the cover 104 , to near the top of the cover 104 . In certain embodiments, the window area 810 may not be visible or distinguishable from other areas of the case, for example, if the case is formed completely of clear transparent plastic and all of the outside portions of the case are polished.
FIG. 9 illustrates a rear elevation view of the assembled case. The underside of the base platform 112 and the certificate platform 122 are shown. In one embodiment, the base 102 includes a foot 902 near each the corner to stabilize the case when it is placed on a surface. Four feet 902 , one at each corner of the base 102 , can be configured to be receivable within the four corner features 520 of the outer ridge 510 of a cover 104 of another case. The matching between the feet 902 and the corner features 520 facilitates stacking of multiple cases atop one another such that the cases are prevented from sliding relative to one another by the interlocking of the feet 902 and corner features 520 .
FIG. 10 illustrates a high side perspective view of the assembled case showing the base 102 . FIG. 11 illustrates a low perspective view of the assembled case showing the base 102 from the bottom side. FIG. 12 illustrates a low perspective view of the assembled case showing the base 102 from the side. FIG. 13 illustrates a low perspective view of the assembled case showing the base 102 from the top side.
FIG. 14A-C illustrate three different embodiments of the case configured to accommodate different size comic books. The FIG. 14A-C each show a cut-away elevation taken along the top-bottom centerline of the assembled case. FIG. 14A illustrates an embodiment of a case configured with an approximately 1 mm gap between the upper surface of the base platform 112 and the lower surface of the cover platform 114 . FIG. 14B illustrates an embodiment of a case configured with an approximately 3 mm gap between the upper surface of the base platform 112 and the lower surface of the cover platform 114 (this embodiment is also shown in all other figures). FIG. 14C illustrates an embodiment of a case configured with an approximately 5 mm gap between the upper surface of the base platform 112 and the lower surface of the cover platform 114 . The same cover 104 can be used in each of the 1 mm, 3 mm, and 5 mm embodiments in conjunction with different bases 104 .
FIG. 14A-C also show steps 130 that define the base platform 112 relative to a bottom portion 1410 of the base 104 . The bases 104 of the 1 mm and 3 mm embodiments can be configured with the same outer dimensions to produce assembled cases with the same outer dimensions. In the case of the 1 mm case, the base platform 112 is raised higher above the surrounding portions of the base 102 by using a larger step 130 to form the base platform 112 . The base 104 of the 5 mm case of FIG. 14C has a thicker overall dimension resulting in a thicker case overall relative to the assembled 1 mm and 3 mm cases to accommodate a larger book while still incorporating a step 130 to form the base platform 112 . Different embodiments can be configured to accommodate still different thickness books. Additional embodiments of the case can also be configured to accommodate books of different heights and widths in addition to different thicknesses.
FIG. 15 illustrates an elevation view of the inside of the base 102 . FIG. 16A illustrates a perspective view of the inside of the base 102 from the lower right side. FIG. 16B illustrates a perspective view of the inside of the base 102 from the upper left side. FIGS. 15, 16A and 16B show the base platform 112 as well as the certificate platform 122 . FIGS. 15 and 16B also show four vertically aligned fins 212 that extend outward from the certificate platform 122 leaving the slot 230 between the top wall 210 into which the tab portion 204 B of the certificate 204 fits. The slot 230 is more clearly shown in FIG. 18 , discussed below. FIG. 15 also shows the two side walls 310 and the bottom wall 320 .
FIGS. 15, 16A and 16B also show a post 1510 in each corner of the base 102 . The four posts 1510 , which will be described in greater detail below with reference to FIG. 19 , are configured to be received in receptacles 2010 (shown and discussed below with reference to FIGS. 20-22 ) in the cover 104 to temporarily hold the assembled case together before the case is permanently closed using ultrasonic bonding. FIG. 15 also shows the base portion of the outer wall 410 that includes the top wall 210 , the side walls 310 and the bottom wall 320 .
FIG. 17 illustrates a close up perspective view of the upper left hand section of the inside of the base 102 . One of the posts 1510 is shown extending upward from a bottom portion 1410 of the base 102 . The certificate platform 122 includes a ridge 1710 that extends around three sides and upward from the upper surface of the certificate platform 122 . The ridge 1710 serves to fix the certificate 204 in place so that it does not become dislodged laterally. The ridge 1710 can optionally be configured to extend along two, three, or all sides of the perimeter of the certificate platform 122 in different embodiments.
FIG. 18 illustrates a close up plan view of the upper right portion of the base. The close up more clearly shows the thickness of the outer wall 410 of the case as well as a step 1810 that runs roughly along the center of the outer wall 410 . The step 1810 mirrors a matching inverse step in the perimeter of the cover such that the two steps fit together to align the base 102 and cover 104 upon assembly. The step 1810 is shown more clearly in FIG. 19 and the cross sections of FIG. 14A-C and FIG. 24A-G . The close up of FIG. 18 also more clearly shows the slot 230 between the inner surface 1820 of the top wall 210 and the fins 212 .
FIG. 19 illustrates a close up perspective view of a lower corner portion of the inside of the base 102 . This perspective view more clearly shows the geometry of one of the posts 1510 as well as the step 1810 . The post 1510 extends upwards from a bottom portion 1410 of the base. In one embodiment, each post has a hexagonally shaped top section that is configured for a snug fit into a boss or receptacle 2010 (shown and discussed below with reference to FIGS. 20-22 ). The post 1510 is preferably tapered such that as it is inserted into the receptacle 2010 , the edges of the hexagonal shape impinge upon the walls of the receptacle so as to hold the base 102 and cover 104 together. Although a hexagonal shape is shown, other shapes can be used, such as a cylinder or other polygonal shapes.
FIG. 20 illustrates an elevation view of the inside of the cover 104 . FIG. 21A illustrates a perspective view of the inside of the cover 104 from the lower right side. FIG. 21B illustrates a perspective view of the inside of the cover 104 from the upper right side. FIGS. 20, 21A and 21B show the depressed cover platform 114 as well as the certificate window 124 . FIGS. 20, 21A and 21B also show a receptacle 2010 for each post 1510 in each corner of the cover 104 .
FIG. 20 also shows an upper portion 2020 of the cover 104 relative to which the cover platform 114 is depressed (from the perspective of an assembled case) by way of steps 130 .
FIG. 22 illustrates a close up perspective view of the upper right hand section of the inside of the cover 104 . One of the receptacles 2010 is shown extending upward from a bottom (relative to the view) of the cover 104 . The certificate window 124 includes a ridge 2220 that protrudes from the inner surface of the certificate window 124 to match the ridge 1710 of the certificate platform 122 . The ridge 1710 of the certificate platform 122 and the ridge 2220 of the certificate window 124 preferably meet or interlock when the case is assembled to fix the certificate 204 in place so that it does not become dislodged laterally. The ridge 2220 can optionally be configured to extend along two, three, or all sides of the perimeter of the certificate window 124 in different embodiments. FIG. 22 also shows a portion of the outer wall 410 of the cover 104 that interlocks with a portion of the outer wall 410 of the base 102 .
FIG. 23 illustrates the same elevational view of the assembled case as FIG. 3 , but with sight lines added that indicate the locations of cross section and cut-away views shown in FIG. 24A-G . Each sight line A-G in FIG. 23 corresponds to an associated FIG. 24A-G .
FIG. 24A illustrates a perspective view of a cut away through the case along sight line A. A post 1510 is shown interlocking with a receptacle 2010 . The feet 902 and the outer ridge 510 of the cover 104 are also shown.
FIG. 24B illustrates a sectional elevation view through the case along sight line B. The sectional view is taken through the bottom step 130 of the cover platform 114 . The base platform 112 and cover platform 114 are shown.
FIG. 24C illustrates a perspective view of a cut away through the case along sight line C. The base platform 112 and cover platform 114 are shown bounding a space within which a book is held by the case.
FIG. 24D illustrates a perspective view of a cut away through the case along sight line D. The sectional view is taken through a step 130 of the cover platform 114 between the cover platform and the certificate window 124 . The base platform 112 and cover platform 114 are shown.
FIG. 24E illustrates a sectional elevation view through the case along sight line E. The sectional view is taken through a step 130 of the cover platform 114 between the cover platform and the certificate window 124 . The certificate platform 122 is shown.
FIG. 24F illustrates a sectional elevation view through the case along sight line F. A post 1510 is shown interlocking with a receptacle 2010 . The fins 212 that hold the tab portion 204 B of the certificate 204 in place are also shown. The certificate platform 122 is shown.
FIG. 24G illustrates a sectional elevation view through the case along sight line G. A post 1510 is shown interlocking with a receptacle 2010 . The fins 212 that hold the tab portion 204 B of the certificate 204 in place are also shown.
Referring again to FIG. 2 , before being encapsulated in the case, a book 202 is optionally first placed in a clear plastic envelope or bag. The envelope can be, for example, a clear archival film envelope made of polyethylene terephthalate or Mylar. The envelope can be sealed on three sides and left open on one end, or a fourth side can be closed using a fold over tab on the envelope.
In order to assemble the case, the optionally enveloped book is placed on the base platform 112 and a scored and folded certificate 204 is placed on the certificate platform 122 with the tab portion 204 B extending down between the fins 212 and the top wall 210 of the base 102 . The cover 104 of the case is then fitted over the book 202 and certificate 204 and depressed such that the posts 1510 and receptacles 2010 engage to provide a temporary fixing of the assembly. The temporarily assembled case is then placed in an ultrasonic bonding machine, which is then activated to bond the base 102 to the cover 104 . The base and cover can be designed using known techniques such that ultrasonic bonding occurs along parts or all of the perimeters of the base and cover. In one embodiment, the bonding occurs along the sides of the perimeter of the case but not along the top and bottom of the perimeter of the case.
In addition or in the alternative to ultrasonic bonding around the perimeter, ultrasonic bonding can be configured to occur within or on the mating junctions of the posts and receptacles. By using ultrasonic bonding on the posts and receptacles, the posts and receptacles can be used as a visual indication of tampering with the assembled case. In some embodiments the number of posts and receptacles can be increased or decreased and any appropriate number of posts/receptacles can be spaced around the perimeter of the case to provide a semi-permanent bond between the base 102 and the cover 104 . The ultrasonic bond around the perimeter can be omitted so as to allow the case to be more easily disassembled in case a user wants access to the book inside. The breaking of the bonds between the posts and receptacles or the breaking of the posts/receptacles themselves, however, will provide a visual indication that the case has been opened.
Although the invention has been described in terms of certain embodiments, other embodiments that will be apparent to those of ordinary skill in the art, including embodiments which do not provide all of the features and advantages set forth herein, are also within the scope of this invention. Accordingly, the scope of the invention is defined by the claims that follow. It should be understood that the subject matter defined in the appended claims is not necessarily limited to the specific implementations described above. The specific implementations described above are disclosed as examples only.
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A comic book case includes a base and a cover configured to compress and secure a comic book in place under frictional pressure such that the book cannot easily shift or slip within the case. Prior art cases that included walls surrounding the top, bottom and side edges of a book typically allowed some free movement or slippage of the book between the walls. This movement or slippage could result in damage such as curling or crinkling of the edges of the book if the case were exposed to a physical shock, such as by being dropped. The base includes a raised base platform and the cover includes a depressed cover platform, which extends towards the base platform to create a space within which the book is securely held.
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This is a division, of application Ser. No. 973,683, filed Dec. 27, 1978, which is a continuation of application Ser. No. 497,738, filed Aug. 15, 1974, now abandoned.
BACKGROUND OF THE INVENTION
(1) Field Of The Invention
This invention is directed to condensation products and methods for the preparation of condensation products of phenol, urea, and formaldehyde which provide cellular plastic compositions useful as insulation material.
(2) Description Of The Prior Art
Heretofore, foamed materials derived from condensates of a phenol and formaldehyde have been prepared by mixing a liquid phenol-formaldehyde resin, a blowing agent, optionally a surfactant, and then a curing (i.e., hardening) agent, such as a strong acid, and applying heat to volatilise the blowing agent and harden the resin.
Such compositions and the methods of their preparation posed obvious disadvantages, particularly if large sections of rigid, foamed condensates were required. Big ovens or a large number of infra-red heaters were required to supply heat evenly over the whole surface. Since the foams possessed good heat-insulating properties, it was very difficult to supply heat to the interior of a large block of the foamed condensate. Irregular heating resulted in a non-uniform foam which was unsuitable for the purpose for which it was intended and which was structurally weak. Since external heaters or ovens are required to obtain a satisfactory rate of hardening, ("on-site") preparation of foams was difficult, or even impossible, and this was a further disadvantage of such compositions and methods.
In attempts to overcome these drawbacks, other substances have been included in the resin mixture which react exothermically with the curing agent and thus reduce or remove the need for applying heat to cure the resin. Solid substances which have been so used include phosphorus pentoxide, barium oxide, and calcium carbonate. However, such exothermically-reacting substances are sometimes unpleasant to handle on an industrial scale, the foams contain inert materials which add to the weight of the product, but serve no useful purpose, and since the unfoamed starting mixtures contain solids, it is difficult to obtain uniform suspensions, which will give uniform foams. This is especially true if a continuous method of foaming is employed. Alternatively, as shown by U.S. Pat. No. 3,692,706, liquids have been added which react exothermically to form a polymer under the influence of the curing agent. However, even the use of this expedient does not solve the major drawback of all these systems which is that they all require a chemical blowing agent. In other words, the phenol-formaldehyde resins cannot be foamed, placed, and set by simple mechanical agitation and pumping.
While insulation materials based on condensates of urea and formaldehyde have been foamed, placed and set by simple mechanical agitation and pumping, such materials have unsatisfactory to poor chemical and physical properties for many thermal and acoustical insulation uses for which such condensates are intended. For example, such condensates have poor compressive strength, tensile strength, shear strength, and their water solubility is too high for many insulation uses for which they are intended in the building industry. In addition, their flame spread characteristic is higher than desirable for many applications in the building industry where safety is an important feature.
Mixtures of phenol-formaldehyde and urea-formaldehyde condensates and certain urea-phenol-formaldehyde condensates are known in the art, see U.S. Pat. Nos. 3,077,458 and 3,549,473, but these materials have characteristics restricting their use to liquid films or binders.
SUMMARY OF THE INVENTION
It has now been found that an excellent thermal and acoustical insulation material having vastly superior tensile strength, shear strength, compressive strength, and water repellency, and much lower fuel contribution, and flame spread compared to prior art compositions can be obtained by preparing a phenol-urea-formaldehyde resin in which the phenol content of the resin varies from about 1 to about 20 percent by weight of the total resin content and which is maintained at a pH of about 6 to about 8 after the suitable degrees of reaction have been accomplished.
Thus, the present invention provides condensation products and methods for the preparation of condensation products of phenol-urea and formaldehyde which form foamed cellular compositions where, in the condensation product, the phenol is present in the amounts of from about 1 to about 20 percent by weight, the urea is present in the amount of from about 22 to about 43 percent by weight, and the formaldehyde is present in the am unt of from about 57 to 88 percent by weight, the ratio of formaldehyde to urea being in the range of from about 1.5 to about 4 parts formaldehyde to about 1 part urea, said condensation product having a viscosity at room temperature in the range of about 30 to 36 seconds on a No. 1 Zahn cup prior to the commencement of setting and a pH maintained in the range of from about 6 to about 8 prior to the commencement of setting.
DESCRIPTION OF THE INVENTION
The following indicates how typical compositions according to the invention may be produced.
Generally, an aqueous solution of uninhibited formaldehyde is first charged into a suitable vessel containing an agitator, a closed hot water system, and a cooling condenser. This is preheated to temperatures in the range of about 15° to 80° C. preferably about 30° C. and the pH is adjusted with a basic or caustic solution, such as sodium hydroxide, to about 7. Alternatively, the compositions of this invention may be produced by starting with an aqueous solution of urea-formaldehyde reaction products commercially available under the trade name "U.F. Concentrate-85". "U.F. Concentrate-85" is a clear, colorless, viscous liquid composed of formaldehyde, urea, and a small amount of water which is believed to be a mixture of methylolureas and formaldehyde. It contains about 15% water and approximately 85% solids, the latter combined in a formaldehyde to urea mol ratio of about 4.8 to 1. The "U.F. Concentrate-85" is charged into a suitable vessel containing an agitator, a closed hot water system, and a cooling condenser. This is diluted on an approximately 1:1 basis by weight with water and then preheated to temperatures in the range of about 15° to 80° C., preferably about 30° C., and the pH adjusted with a basic or castic solution to about 7.
Thereafter, the appropriate parts by weight of phenol are added in amounts necessary to achieve the desired weight percent of phenol in the end product and the pH is again adjusted with the base to maintain it at about 7. The urea or additional urea to be incorporated in the final product is added and the mixture is agitated to dissolve the urea, usually from about 10 minutes to about an hour, depending on the amount of urea added, at ambient temperature, i.e., about 30° C. Then the mixture is heated and reacted under constant agitation at reflux (98° C. to 100° C.) for approximately 15 minutes up to about an hour. At the end of this period and maintaining this temperature, an aqueous formic acid solution containing up to as much as about 20 percent formic acid (HCOOH) is added slowly over a period of time, usually 45 minutes, until the desired amount of formic acid is present in the reacting mixture, and until the reaction mixture is brought down to a pH of between 6 and 4.4, preferably about 5.5. While maintaining a temperature of approximately 100° C. and constant agitation, viscosities are taken at intervals of 5 minutes. When the viscosity reaches approximately 30 seconds on a No. 1 ahn cup, the reaction may be concluded as described hereinafter, depending on the product characteristics desired.
However, should a condensation product of higher viscosity be desired, the following simple test of water solubility is helpful as a preliminary quick indication of viscosity. A small quantity, such as ↓0.25 cc., is taken [by pipette] from the reaction mixture at intervals of 2 minutes and dropped into a beaker of distilled water at a temperature of 15° C. When droplets of the reaction mixture are observed to form a light white cloud, the viscosity should be about 31.5 to 32 seconds on the No. 1 Zahn cup. Should a still higher viscosity be desired, a 10 cc. sample of the reaction mixture can be taken at intervals of about 2 minutes. When mixing this sample with 40 cc. of distilled water at 15° C. yields a dense while cloud, the viscosity should be about 32.5 seconds. If the reaction is continued the condensate will become more viscous yielding even more opaque mixtures. More elaborate measurement techniques are also available, involving measurement of ohmic resistance/electrical conductivity or index of refraction.
The final viscosity of the condensate should be in the range of about 30 to about 36 seconds on a No. 1 Zahn cup. The viscosity can go up as high as 40 seconds, but the condensate should then be cut with water to bring the viscosity down to the desired range. For most end uses a viscosity of about 32.5 seconds is optimum.
When the desired final viscosity is reached, the mixture is cooled down rapidly and neutralized with a basic or caustic solution, such as sodium hydroxide, and removed from the reaction vessel. The final pH of the reaction product should be maintained at between 6 and 8, preferably at about 7.
The phenol-urea-formaldehyde resins of this invention, having viscosities and pH values in the ranges mentioned above, have long shelf lives of from over 2 to over 6 months and can be pumped mechanically through orifices as small as 1 mm, whereupon they set up extremely rapidly, in the order of about 5 to 150 seconds, depending on viscosity and age of condensate, to provide superior stable cellular thermal and acoustical non-combustible insulation particularly suited for cavities in building wall systems, masonry, foundations, slabs, and roofs.
Conventional foaming agents, hardening agents, etc., known in the phenol-formaldehyde and urea-formaldehyde art can be used in carrying out the invention. Optionally, conventional blowing agents known in the phenol-formaldehyde and urea-formaldehyde art may be used if desired but they are not necessary for utilization of the invention described herein.
The following specific examples illustrate the preparation of a phenol-urea-formaldehyde resin according to the present invention in which the weight percent of phenol in the final raw condensation product is approximately 2 percent in Example 1 and approximately 15 percent in Example 2.
EXAMPLE 1
8.4 parts by weight of 37 percent uninhibited HCHO (formaldehyde) is charged into a suitable vessel containing an agitator of low rpm, a closed hot water system and cooling condenser, and is preheated to 30° C. The pH is normally 4.6 to 5.0. This is adjusted by means of a 1 to 4 normal NaOH solution until a pH of 6.8 to 7.0 is obtained. 0.114 parts by weight of phenol of approximately 95% solution is added to the formaldehyde solution at 30° C. The pH is again checked and adjusted to 7.0. Immediately upon this neutralization, 3 parts by weight of dry urea (industrial grade) is added to the mixture now under constant agitation. This is agitated for a period of approximately 10 minutes to dissolve the urea. At this point the mixture is heated by means of a closed hot water system capable of producing temperatures up to 120° C. or by other means of producing this temperature, for example, an ethylene glycol bath. The mixture is then heated under constant agitation to reflux (98° to 100° C.) and reacted for a period of 15 minutes. At the end of this period and maintaining this temperature, a 10% solution of HCOOH (formic acid) is slowly added over a period of 30 to 45 minutes to bring the reaction mixture down to a pH of 5.5.
While maintaining 100° C. and constant agitation, viscosities are taken at intervals of 5 minutes. When viscosity reaches approximately 30 seconds on a No. 1 Zahn cup, a small quantity, such as 0.25 cc, is taken from the reaction mixture and dropped into a beaker of distilled water at a temperature of 15° C. and is observed. This test is for water solubility and when droplets of the reaction mixture start to form a slight white cloud, the viscosity should be about 31.5 to 32 seconds on a No. 1 Zahn cup. If the viscosity exceeds this, water is added slowly as not to stop reaction, and viscosity is brought to this point. The water solubility test is then taken at intervals of 2 minutes. When the resin forms a dense white cloud, the viscosity should be about 32.5 seconds, i.e., the desired viscosity. Here 10 cc of reaction mixture is taken and mixed with 30 cc distilled water at 15° C. This solution should form a smooth, white opaque cloud mixture. If not, the reaction is continued until opaque mixture is obtained. At this point the mixture is cooled down rapidly and neutralized to a pH of 7.0 with a solution of 2 normal NaOH and removed from the reaction kettle.
EXAMPLE 2
8.4 parts by weight of 37% uninhibited HCHO (formaldehyde) is charged into a suitable vessel containing an agitator of low rpm, a closed hot water system and cooling condenser, and is preheated to 30° C. The pH is normally 4.6 to 5.0. This is adjusted by means of a 1 to 4 normal NaOH solution until a pH of 6.8 to 7.2 is obtained. 1.311 parts by weight of phenol of approximately 95% solution is added to the formaldehyde solution at 30° C. The pH is again checked and adjusted to 7.0. Immediately upon this neutralization, 3 parts by weight of dry urea (industrial grade) is added to the mixture now under constant agitation. This is agitated for a period of approximately 10 minutes to dissolve the urea. At this point the mixture is heated by means of a closed hot water system capable of producing temperatures up to 120° C. or by other means of producing this temperature, for example, an ethylene glycol bath. The mixture is then heated under constant agitation to reflux (98° to 100° C.) and reacted for a period of 15 minutes. At the end of this period and maintaining this temperature, a 10% solution of HCOOH (formic acid) is slowly added over a period of 30 to 45 minutes to bring the reaction mixture down to a pH of 5.0. The reaction is continued at 100° C. and maintaining constant agitation until an opaque mixture is obtained with the water solubility tests described in Example 1. At this point the mixture is cooled down rapidly and neutralized to a pH of 7.0 with a solution of 2 normal NaOH and removed from the reaction kettle.
The chemical and physical properties of these resins are set forth below in tabular form and compared against a commercially available urea formaldehyde resin. In both resins the same type of foaming agent, i.e., an aqueous detergent mixture expanded by air was utilized.
______________________________________ Urea-For- Phenol-Urea-Formalde- maldehyde hyde Resin Resin Example 1 Example 2______________________________________Compressive Strength 4 9 17(lbs./in..sup.2)Tensile Strength 1 3.2 4.7(lbs./in..sup.2)Shear Strength 2 5.5 6.3(lbs./in..sup.2)Density 0.6 0.9 1.6(lbs./ft..sup.3)Toxicity Non-toxic Non-toxic Non-toxicWater Transmission (%) 3 1 <1Flame Spread 25 5 0-5Smoke Contribution 0 to 5 5 5 to 10Fuel Contribution 10 0 0Water Absorbancy/ 111/2 31/2 21/224. Hr. (by weight)Heat Disintegration 50 sec. 3 min. 29 sec. 4 min.(complete)3" × 3" × 2"at 3,600° F.______________________________________
The resins of this invention containing from about 1 percent to 2.0 percent phenol by weight give exceptionally excellent results for in-place foaming such as cavity fill for thermal and acoustical insulating foam. At these percentages of phenol, the products in a foam state have greatly reduced surface burning characteristics over the normal urea formaldehyde foams.
From about 2 percent to 5 percent phenol in the final raw condensation product provides finished foam products which have much greater compressive strengths for foam in-place cavities and also greatly reduces moisture transmission over conventional urea-formaldehyde products, in fact in many cases where the foam product is used, a vapor barrier may be omitted.
Foamed products upon curing containing from 5 to about 10 percent phenol achieve compressive strengths of approximately 10 to 15 lbs./in. 3 , thus finding utilization in the form of boards. Their shear strength is also greatly increased. The products are particularly highly resistent to flame spread. At these percentages the product also may be formed into pipe coverings which have excellent thermal insulation properties.
Foamed products containing from about 10 percent to about 20 percent phenol by weight are very heavy, normally having desities between 1.6 and 3.5 lbs./in. 3 . They may be used in place of styrene and urethane boards and are desirable because of their high resistance to flame. Such products are also much more water repellent than urea formaldehyde foams. At this range of phenol concentration, the use of additional foaming agent and increasing pressure allows one to foam the product without the need to add blowing agents.
Above these percentages of phenol, even with an increase in foaming agent and pressure, foaming by mechanical means is impossible or extremely difficult at ambient temperatures, which are the normal temperatures for application of these materials.
The resins of this invention are normally foamed at the site of use by using a portable applicator equipped with flexible hose for delivering expanded wet foam to areas to be insulated. Drying time depends on thickness, temperature, humidity, and the amount of ventilation. Under average summer conditions with normal attic ventilation, a 2" thick application will dry within 3 days. Winter temperatures do not affect the foaming process provided solution temperatures are kept above 50° F. during application.
Certain changes may be made in the compositions and processes herein described without departing from the scope and teachings and it is intended that all matter contained in the description is by way of illustration rather than limitation.
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This invention relates to cellular plastic compositions of condensation products of phenol-urea and formaldehyde useful for thermal and acoustical insulation and methods for their preparation in which the phenol is present in amounts of about 1 to about 20 percent by weight wherein the condensation product prior to foaming and setting as a rigid cellular plastic has a viscosity at room temperature of approximately 30 to 36 seconds, No. 1 Zahn cup, and a pH maintained in the range of about 6 to 8.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally concerns parking brakes, wheel locks, hill holders and like devices fitted to wheeled trolleys and conveyances, particularly to wheelchairs.
The invention particularly concerns a parking brake for a wheelchair.
2. Description of the Prior Art
2.1 General Background
Existing wheel chair wheel locks based on friction between a moveable portion of a brake, or lock, and the tire or wheel of the wheelchair suffer in effectiveness in that a limited area of contact between the brake and the wheel permit the wheel to slip and rotate under high lateral loads, such as during the egress of the wheelchair occupant from the wheelchair. It is desirable that wheelchair parking brake, or lock, should substantially preclude any further wheel rotation whatsoever, once engaged, nonetheless to being easy and reliable to engage and dis-engage.
2.2 Specific Background
U.S. Pat. No. 4,462,605 to Morgan, et. al. for a WHEELCHAIR HAVING ANTI-ROLLBACK MECHANISM shows propulsion wheels of a manually propelled wheelchair equipped with one-way engaging and one-way freewheeling clutch devices which cooperate with races fixed to the wheelchair frame, whereby unwanted backward movement of the wheelchair is prevented and forward movement at all times is enabled. An override mechanism including a spider attached to each hand propulsion ring disables the one-way engaging clutch devices when the wheelchair occupant intentionally moves the propulsion wheels in a backward mode. No controls separate from the manual propulsion wheels are present, assuring the chair occupant constant control of the chair through the hand propulsion rings at all times.
U.S. Pat. No. 4,538,825 to Delahoussaye, et. al., for a WHEELCHAIR ANTI-ROLLBACK MECHANISM shows the customary side hand propulsion ring adjacent to each main wheel of a manual wheelchair mounted through a lost motion connection between the propulsion ring and main wheel so that the propulsion ring can have limited rotational movement relative to the main wheel. A friction brake drum or partial drum fixed to the wheelchair frame inside of the main wheel is engaged by at least one of a plurality of circumferentially spaced over center friction locking devices pivotally held on the main wheel. Each over center friction locking device is moved by a release element to a non-locking position relative to the drum or partial drum in response to reverse movement of the propulsion ring by a chair occupant. Economy and ease of operation are provided for. The wheelchair occupant need not remove his or her hand from the propulsion ring when operating the anti-rollback mechanism.
U.S. Pat. No. 4,570,756 to Minnebraker, et. al., for a BRAKE DEVICE FOR WHEELCHAIRS shows a brake device for use with wheelchairs of the type having a main frame and a pair of spaced apart large diameter driving wheels, such as rear wheels. The brake device comprises a bracket or other mounting element for mounting to the wheelchair frame and a lever arm which is shiftable to a wheel locking position to move a brake tab into engagement with the rear wheel of a wheelchair to lock the wheel against further rotation. The lever arm is also capable of being shifted to a reverse or non-locking position so that it moves the tab out of engagement with the wheelchair driving wheel and to a position where it cannot be engaged with the driving wheel to permit free-wheeling movement thereof. The brake device is constructed so that the tab is moveable to a non-interfering position where it is generally parallel to the plane of rotation of the wheel and is not likely to be contacted by the hand of a user. In one embodiment, the tab is manually moveable to the non-interfering position. In another embodiment, the tab is automatically moved to the non-interfering position when the lever arm is shifted away from the locking position.
U.S. Pat. No. 4,691,933 to Strauss for a WHEELCHAIR PARKING BRAKE shows a wheel locking device for use on a wheelchair, including a locking bar connected to a shaft that is movably axially and rotationally within a fixed tube, by a single operating handle. As the operating handle is moved from a release position to a locking position, the shaft is first axially translated by means of a cam on the handle, and simultaneously rotated by means of a guide pin extending radially from the shaft and engaging a slot in the tube, to move the locking bar from a retracted position well clear of a wheel of the chair to an operative position located transversely with respect to the wheel circumference. Further movement of the operating handle translates the locking bar transversely into locking engagement with the wheel.
U.S. Pat. No. 4,749,064 to Jinno, et. al., for a BRAKE SYSTEM FOR A WHEELCHAIR shows a brake system for a wheelchair comprises a base plate fixed to a frame of the wheelchair and a swing lever pivotally mounted to the base plate and provided with a brake member engagable with a circumferential surface of a wheel of the wheelchair. A toggle joint mechanism composed of two pivotally interconnected links is pivotally mounted to the base plate and connected to the swing lever to move the swing lever between an extended braking position and a retracted inoperative position. An operating lever is pivotally mounted to the pivot which interconnects the two links of the toggle joint mechanism. The operating lever has cam surfaces engageable with the two links to depress the latter when the operating lever is moved in either of two directions by pushing it or pulling it. Such action drives the swing lever into braking engagement with the wheel. A biasing spring is provided to urge the links of the toggle mechanism towards retracted position.
U.S. Pat. No. 4,805,711 to Lautzenhiser for a MECHANICAL CONTROL MECHANISM FOR CONVEYANCE shows an electric wheelchair, or other conveyance, provided with a function control which includes a unitary control, and which is effective to control applying and releasing of power transmitted from an electric motor to a wheel, or to another type of propulsion element, and to control applying and releasing of a parking brake, in response to positioning of the unitary control.
U.S. Pat. No. 4,749,064 to Jinno, et. al., for a BRAKE SYSTEM FOR A WHEELCHAIR shows a brake system for a wheelchair comprises a base plate fixed to a frame of the wheelchair and a swing lever pivotally mounted to the base plate and provided with a brake member engagable with a circumferential surface of a wheel of the wheelchair. A toggle joint mechanism composed of two pivotally interconnected links is pivotally mounted to the base plate and connected to the swing lever to move the swing lever between an extended braking position and a retracted inoperative position. An operating lever is pivotally mounted to the pivot which interconnects the two links of the toggle joint mechanism. The operating lever has cam surfaces engageable with the two links to depress the latter when the operating lever is moved in either of two directions by pushing it or pulling it. Such action drives the swing lever into braking engagement with the wheel. A biasing spring is provided to urge the links of the toggle mechanism towards retracted position.
U.S. Pat. No. 5,174,418 for a WHEEL LOCK MECHANISM FOR A WHEELCHAIR shows a wheelchair wheel lock system is provided that can be adapted for either pull-to-lock or push-to-lock operation. The wheel lock system includes a function plate with first and second pivot holes. An operating lever is attached to the function plate, and rotation of the lever causes rotation of the function plate and thereby moves a contact arm into engagement with the wheel of the wheelchair to lock the wheel against movement. The operation of the wheel lock system is changed between push-to-lock and pull-to-lock by adapting the function plate to rotate about either the first pivot hole or the second pivot hole. The operating lever can be attached to the function plate in a variety of orientations, providing added flexibility in the operation of the wheel lock system.
U.S. Pat. No. 5,355,977 to Kuschall for a PARKING BRAKE FOR A WHEELCHAIR shows a parking brake fitted to the wheelchair frame largely regardless of the nominal position of the brake element, and conversely the position of the brake element can be exactly matched to the position of the rear wheel. A two-piece clamp connects a cylindrical bearer to a part of the wheelchair frame and allows the bearer's rotation and lengthwise displacement relative to the frame. One end of the bearer holds the pivoting brake element and locking lever. One arm of the locking lever acts together with the brake element and has two recesses. When the locking lever is moved to a released position, spring action forces the brake element to engage one of the recesses and to be located beside the rear wheel approximately perpendicular to the wheel's rotational axis. When the locking lever is moved to a braking position, the brake element engages the second recess and is located more or less parallel to the rotational axis of the rear wheel. This ensures that the brake element moves accurately to clearly defined end positions.
U.S. Pat. No. 5,472,066 to Schillo, et. al., for an ARRESTING BRAKE FOR A WHEELCHAIR relates to an arresting brake for a wheelchair, having a braking element which is articulated pivotally on a retaining element and, by pivoting a hand brake lever, can be pivoted into an arresting position in which the braking element bears, under pressure, on a wheelchair wheel or its tire. In order to provide a versatile arresting brake for wheelchairs, the invention proposes that the hand brake lever also be mounted on the retaining element, which is pivotally suspended on an adaptor which exhibits fastening device, for fixing it on the wheelchair frame, and a pivot pin which is located in the longitudinal direction of the wheelchair when the adaptor is mounted and about which the retaining element can be pivoted out of a positive locking catch position, which defines the braking function position, into a storage (rest) position located within the outer contour of the wheelchair.
Finally, as what may possibly be the closest prior art to the present invention of which the inventor is aware, U.S. Pat. No. 5,799,756 to Roberts, et. al., for SURELOCK WHEELCHAIR BRAKES concerns a brake system for a wheelchair having two assemblies, one for each of wheel. Each assembly comprises a mounting bracket adapted to be connected to a frame portion of a wheelchair, a handle pivotally attached at a pivot point to the mounting bracket, a cable having one end connected to the handle and another end connected to a pivot arm. The pivot arm is pivotally attached to one end of a cam rod. The rod is attached to another mounting bracket adapted to be connected to another frame portion of the wheelchair and has a latching mechanism connected to a portion of the rod and biased into engagement with a splined disc by a spring. The disc is adapted to be connected to a hub of the wheel chair. In use, when the occupant of the wheel chair pivots the handle past a certain rotary position with respect to the pivot point of the handle, either in a forward or rearward direction, the spring forces the latching mechanism into either a positive braking engagement with the disc, thereby locking the wheelchair against movement, or a released position in which the wheelchair is free to move. Different versions are available for wheelchairs having canted wheels.
The present invention will be seen to employ a disk affixed to a wheelchair wheel, but without the peripheral splines of the disk of Roberts, et al., which splines can detrimentally catch on clothing, wraps and the like worn or used by the occupant of the wheelchair. Additionally, the present invention will be seen to employ a plunging, as opposed to a pivoting, mechanism for locking the wheelchair wheel against movement relative to the wheelchair frame.
The present invention will further be seen to realize positive wheel locking by use of an different engagement mechanism that is differentiated from that of Roberts, et al., by being (i) smoother acting to engage and lock a wheel that is initially rolling, and (ii) self-aligning, meaning that the engaging parts will mesh together securely and well no matter what torsional forces on the wheelchair frame and wheels—as may be due to, for example, uneven terrain—may be present. Furthermore, with proper orientation of parts, no separate version of the wheelchair wheel lock of the present invention is necessary for wheelchairs having canted wheels: one version suits all applications.
SUMMARY OF THE INVENTION
The present invention contemplates a strongly-holding, zero-slip, feather-touch quick-action easy- and positive-actuating and releasing, lightweight, economical, universal, retrofittable parking brake and wheel lock for a wheelchair.
In accordance with the present invention an annular disk of a size and form that fits nearly all wheelchairs is mounted to the hub of the wheelchair's wheel at a position centered about the wheelchair's axle and between the wheelchair's wheel and the wheelchair's frame. The disk has and presents a circumferential array of holes, normally about 24 such in its circumferential peripheral, or exterior, region.
Meanwhile a sliding plunger controllably extends under spring force from a housing mounted to a wheelchair's frame. A distal end tip of the sliding plunger extends transversely into a juxtaposed complimentary hole of the annular disk, therein locking the disk against further rotation. Spring-loaded extension of the sliding plunger is prevented, loosing the wheelchair wheel for rotation, by pulling on a cable connecting between the proximal end of the sliding plunger and a lever selectively activated by an occupant of the wheelchair.
1. A Wheelchair Wheel Lock
Therefore, in one of its aspects the present invention is embodied in a wheelchair wheel lock. The wheel lock is employed on a wheelchair having a frame and an axle, the axle rotationally attaching wheels having wheel hubs.
The wheel lock includes an annular disk that attaches the hub of a wheelchair wheel at a position centered about the wheelchair axle between the wheelchair wheel and the wheelchair frame, thereby to rotate with the wheelchair wheel. The annular disk so attaches the hub by at least one attachment feature. The annular disk also has and presents, circumferentially arrayed in its annulus, a number of engagement features. These engagement features may suitably be mechanically engaged so as to prevent rotation of the disk, and of the wheelchair wheel to which the annular disk is affixed. In other words, they, and the annular disk, are sufficiently robust, and strong.
The wheel lock also includes a moveable member which is mounted to the frame of the wheelchair proximate the annular disk. The moveable member has a distal end of complimentary configuration to the engagement features of the disk. The moveable member is moveable under and by force controlled by an occupant of the wheelchair to extend at a first time into contact with at least one of the engagement features of the annular disk, therein to prevent rotation of the annular disk and of the wheelchair wheel. The moveable member is moveable under and by force oppositely applied so as to withdraw at a second time from any contact with the annular disk, therein to permit rotation of the annular disk and of the wheelchair wheel.
The annular disk is normally divided into interior and exterior, or peripheral, annular regions. The annular disk normally attaches the hub of the wheelchair wheel at an interior region of its annulus, while its circumferentially-arrayed annular features are located at the peripheral region of its annulus.
The annular disk's attachment feature(s) may vary. A number of bolts received into an equal number of bolt holes may be used. The bolts may attach the hub of the wheelchair wheel by bolting to bolt holes of complimentary size and position that are either pre-existing (for some brands of wheelchairs), or drilled and tapped (for other bands of wheelchairs) within the hubs of the wheelchair wheels. The bolts may be supplemented by washers, thereby to attach the hub of the wheelchair's wheel at by compression against the hub spokes. Finally, the central opening of the annular disk may be threaded, permitting it to fit to wheel chairs having threaded hubs.
The annular disk's circumferentially-arrayed peripheral-region engagement features are normally engaged along an axis transverse to a plane of the annular disk, and from a side of the disk opposite the wheel. This makes that the moveable member moves transversely to the plane of the annular disk so as to selectively engage, and disengage, the engagement features.
The engagement features are preferably holes, or apertures, and are more preferably racetrack-shaped apertures. The racetrack shape of the apertures accords some radial tolerance to fitting of the distal end of the moveable member within a juxtaposed aperture.
In greater detail, the moveable member preferably includes a mount, affixed to the frame of the wheelchair, that has a bore in which a sliding element may slide. A sliding element slides within the bore of this mount between (i) an extended position where a distal end of the sliding element contacts and engages the at least one of the multiplicity of engagement features, or apertures, of the annular disk, preventing the disk from rotating, and (ii) a retracted position where neither the annular disk nor any of the annular disk's multiplicity of engagement features, or apertures, are contacted.
The moveable member further includes a spring that positionally force biases the sliding element within the bore of the mount to its extended position. A cable pull, activated by the occupant of the wheelchair, serves to pull the sliding element within the bore of the mount and against the force biasing of the spring until the sliding element assumes its retracted position.
This cable pull preferably consists of a sheathed cable connected at one end to the sliding element; and at the other end to a lever actuator. The lever actuator is mounted to the frame of the wheelchair in a position convenient to the occupant of the wheelchair. The occupant may throw the lever to forcibly pull the cable within its sheath. Notably, sufficient frictional force is exerted in combination by the cable in its sheath, and by the lever actuator, so that once the lever actuator is set by the occupant of the wheelchair to a position moving the sliding element to its retracted position then each of the lever actuator, then the sheathed cable, and the sliding element, will thereafter hold their position then assumed. There is no necessity that the lever actuator should be held against the force of the spring by the occupant of the wheelchair.
2. A Wheelchair Parking Brake
Therefore, in its most preferred expression the present invention is preferably embodied in a parking brake, or wheel lock, for a wheelchair. As before the wheelchair has a frame having an axle rotationally attaching a wheel having a wheel hub.
The most preferred parking brake has an annular disk mounted to the hub of a wheelchair wheel, at a position centered about the wheelchair axle between the wheelchair wheel and the wheelchair frame, for rotation with the wheelchair wheel. This annular disk has and presents in its annular peripheral region a number of circumferentially arrayed holes.
A plunger housing is mounted to the frame of the wheelchair proximate the annular disk. A sliding plunger, having a distal end suitable to fit within a hole of the annular disk, slides under force (i) at least partially within the housing, and (ii) transversely to the plane of the annular disk so as to extend into and retract out of a hole;
A spring within the housing force biases the plunger to its extended position extending into a hole of the annular disk.
Meanwhile a lever operable by an occupant of the wheelchair connects to a cable extending between the lever and the sliding plunger. One position of the lever retracts and holds the sliding plunger against the force of the spring in position outside any hole of the annular disk. Another position of the lever permits the spring to force the sliding plunger to extend from the plunger housing and into a hole of the annular disk, therein to prevent rotation of the annular disk—which is connected to the wheel hub which is connected to the wheelchair wheel—relative to the plunger—which is at least partially within the plunger housing which is mounted to the wheelchair frame. Occupant-controlled extension of the sliding plunger by use of the lever thus serves to selectively lock, and unlock, rotation of the wheelchair's wheel.
The parking brakes, or wheel locks, are most commonly fitted to both wheels of the wheelchair, and can be independently or jointly controlled.
These and other aspects and attributes of the present invention will become increasingly clear upon reference to the following drawings and accompanying specification.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring particularly to the drawings for the purpose of illustration only and not to limit the scope of the invention in any way, these illustrations follow:
FIG. 1 shows a wheelchair parking brake in accordance with the present invention fitted to a wheel chair.
FIG. 2 shows an expanded and isolated view of the wheelchair parking brake in accordance with the present invention previously seen in FIG. 1 with its attachment to the frame of the wheel chair previously seen in FIG. 1 .
FIG. 3 is an exploded view showing the wheelchair parking brake in accordance with the present invention previously seen in FIGS. 1 and 2 in relationship to the frame of the wheel chair previously seen in FIGS. 1 and 2.
FIG. 4 is a detail plan view of a first embodiment of an apertured disk component of the wheelchair parking brake in accordance with the present invention previously seen in FIGS. 1-3.
FIG. 5 is a detail front plan view of mounting plate component of the wheelchair on which is mounted a parking brake in accordance with the present invention previously seen in FIGS. 1-3.
FIG. 6 is a detail side plan view of mounting plate component previously seen in FIG. 5 .
FIG. 7 is a cut-away view of the engagement of the plunger and disk components of the wheelchair parking brake in accordance with the present invention previously seen in FIGS. 1-3.
FIG. 8 is a detail perspective view of a second embodiment of an apertured disk component of the wheelchair parking brake in accordance with the present invention previously seen in FIGS. 1-3.
FIG. 9 is a detail perspective view of a second embodiment of an apertured disk component of the wheelchair parking brake in accordance with the present invention previously seen in FIGS. 1 - 3 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
Although specific embodiments of the invention will now be described with reference to the drawings, it should be understood that such embodiments are by way of example only and are merely illustrative of but a small number of the many possible specific embodiments to which the principles of the invention may be applied. Various changes and modifications obvious to one skilled in the art to which the invention pertains are deemed to be within the spirit, scope and contemplation of the invention as further defined in the appended claims.
A wheelchair parking brake 1 in accordance with the present invention is shown fitted at the hub 21 of a wheel 22 of a wheel chair 2 in FIG. 1 . An expanded and isolated view of (i) the same wheelchair parking brake 1 and (ii) its attachment to the frame 22 of the wheel chair 2 , both previously seen in FIG. 1, is shown in FIG. 2 .
In FIG. 2, an apertured disk 11 component of the wheelchair parking brake 1 is actually mounted to the wheel 22 , and is correspondingly shown in dashed line which more particularly deals with the components of the wheelchair parking brake 1 that are directly mounted to the frame 23 of the wheelchair 2 . A mounting plate 12 holds a plunger assembly 13 in position where a plunger 131 (further shown in FIG. 3) will extend and retract to enter and exit the apertures 111 of the apertured disk 11 . A sheathed cable 14 connects the plunger assembly 13 to the an actuating, lever, assembly 15 . A lever 151 (shown in FIG. 3) of the lever assembly 15 is positioned on the frame 23 of the wheelchair 2 where it may be conveniently accessed and activated by the hand of an occupant of the wheelchair both for applying and releasing the locking function of the wheelchair parking brake 1 . There is normally only one wheelchair parking brake 1 fitted to a wheel of the user's choice for the wheelchair 1 , although parking brakes can be affixed to both wheels. When the wheelchair parking brake 1 is retrofitted to an existing wheelchair then the same components, alternatively mounted, suffice to install the brake 1 on either wheel of the wheel chair 2 , with the plunger assembly 13 on either side of the wheel chair 2 .
An exploded view showing the wheelchair parking brake 1 in accordance with the present invention is shown in FIG. 3 . The view also shows portions of the frame 23 which are not, strictly speaking, part of the brake 1 . The apertured disk 11 is mounted to the wheel 22 (shown in FIG. 1) for rotation therewith, and is more particularly mounted to the wheel hub 221 that revolves about the wheel spindle 222 . The mounting illustrated is by action of (four) screws 112 , although other manners of mounting are possible. Various hardware permits that the apertured disk 11 stands off from the frame 23 of the wheelchair about the wheel hub 21 of the wheelchair (best observed in FIGS. 1 and 4) so that placement, or retrofitting, of this disk 11 in no way interferes with normal rotation of the wheel 22 of the wheelchair 2 (both shown in FIG. 1 ).
Meanwhile in FIG. 3, a plunger assembly 13 is mounted to the frame 23 by action of a mounting plate 12 , although other affixations including welding are possible. The plunger assembly is so mounted, and adjusted in position relative to mounting plate 12 and frame 23 as necessary, so that a distal end region of it's plunger 131 will pass through a hollow bore of associated nuts and fittings to selectively enter, or withdraw, from the apertures 111 of the disk 11 . The distal end of the plunger 131 is beveled to facilitate slippage over the apertured annular surface of a rapidly spinning disk 11 , and ultimate passage into an aperture of the apertured disk 11 when the disk 11 is either stopped, or sufficiently slowed in rotation.
Immediate locking of a turning disk 11 and wheel 22 can pitch the occupant of the wheelchair 2 from the wheelchair 2 , causing injury. Based on the force of spring 132 next explained, the wheelchair wheel lock of the present invention can be set to aggressively engage and lock even a rapidly rotating disk 11 and wheel 22 , but there are limits on the advisability of setting up the wheel lock to engage immediately under all speeds of wheel rotation. The plunger 131 is normally somewhat “soft” in its engagement, “lightly rattling” upon the surface of a spinning disk 11 , and finally engaging an aperture and nearly instantaneously stopping any residual rotation of the apertured disk 11 and the wheel 22 only when rotation has already greatly slowed, and has nearly stopped.
The movement of the plunger 131 is in response to (i) force of a spring 132 , which spring 132 tends to expel the plunger 131 from its bore and into contact with the disk 11 , and (ii) force of a proximal end region connection to an inner cable 141 of the sheathed cable 14 , which inner cable 141 pulls the plunger 131 against the force of the spring 132 , into the bore, and away from contact with the disk 11 . The inner cable 141 of the sheathed cable 14 connects at its end opposite to the plunger 131 and the plunger assembly 13 , to the lever 151 of the actuating assembly 15 .
This lever 151 as held by mount 152 to the frame 23 of the wheelchair 2 pivots about a pivot axis established by stud 154 so as to extend the inner cable 141 of the sheathed cable 14 to a greater or lessor extent. The stud 154 connects at a one, top, side to the mount 152 by washers, preferably of nylon, and the lock nut 153 . The pivoting connection of the lever 151 is more complex. The lower portion of the stud 154 slips a washer, typically made of metal, and passes thorough a one-way roller, or clutch, bearing 156 fitted within a pivot axis bore of the lever 151 . A washer and lock nut 155 permit tightening the lever 151 to the lower portion of the stud 1154 to a variable extent. The one-way roller, or clutch, bearing 156 is preferably part number RC-040708 available from Torrington, USA.
In operation, the one-way roller, or clutch, bearing 156 permits that the lever 151 will freely and easily pivot open, pulling the inner cable 141 of the sheathed cable 14 and withdrawing the plunger 131 (against the force of spring 132 ) from the apertured disk 11 . However, by action of this one-way roller, or clutch, bearing 156 , the lever 151 will hold position—permitting the wheel 22 to turn, and the wheelchair 2 to roll—without being held by the hand and fingers of the wheelchair occupant. When the lever is engaged by the occupant's fingers, and forcibly rotated so as to permit the plunger 131 to move under the further force of spring 132 to engage and to lock the apertured disk 11 , then this rotation cannot be realized by reverse rotation of the one-way roller, or clutch, bearing 156 , nor by slippage of the lever 15 about the lower portion of the stud 154 . Instead, the upper portion of the stud 154 slips and rotates in the region between the two washers, and in the bore of the mount 152 . The friction of this rotation can be adjusted by tightening or by loosening the lock nut 153 . Accordingly, rotation of the lever 151 is less difficult, and by action of the free rotation of a roller, or clutch, bearing in its permitted rotational direction, in the rotational direction whereby the wheel lock is released, and is more difficult, and by action of a shaft frictionally slipping within a bore and between nylon washers, in the rotational direction serving to set the wheel lock.
Alignments and tolerances of the sheathed cable 14 are established so that, quite naturally, a positioning of the lever 151 at one extreme of its arc of travel withdraws the plunger 131 securely away from the disk 11 whereas positioning of the lever 151 at the other extreme of its arc of travel permits the distal end of the plunger 131 to enter into the apertures 111 of the disk 11 under the force of spring 132 .
A detail plan view of a first embodiment of an apertured disk 11 component of the wheelchair parking brake 1 in accordance with the present invention is shown in FIG. 4 . The disk 11 is more properly in the shape of an annular ring, with a central opening sufficiently large so as to accommodate the hub 21 of the wheelchair 2 (shown in FIG. 1 ). The apertures 11 are preferably elliptical in shape to accommodate minor misalignment with the plunger 131 of the plunger assembly 13 . In accordance with the fact the preferred number of apertures is twenty-four (24), as illustrated, the angle D 1 is fifteen degrees (15°). The apertured disk 11 is typically 10 cm. outside diameter with a 3.5 cm. inside diameter to its center opening. A various number of threaded screw holes 113 , illustrated to be four in number, accommodate, in this embodiment, the screws 112 that affix the disk 11 to the hub 221 (shown in FIG. 3) of the wheelchair wheel 22 (shown in FIG. 1 ).
As shown in detail front plan view in FIG. 5, and detail side plan view in FIG. 6, the mounting plate 12 also preferably possesses an elliptical, or racetrack-shaped, central aperture 121 to accommodate necessary adjustments and alignments. This mounting plate is normally part of the wheelchair 2 , but can be supplied as part of the wheel brake 1 if required. The mounting plate 12 preferably also has and presents striations, normally placed by machining, to promote strong stable compressive mounting to the frame 23 (shown in FIG. 3) of the wheelchair 2 (shown in FIG. 1 ).
A cut-away view of the engagement of the plunger 131 into an aperture 111 of the disk 11 is shown in FIG. 7 . The action of the spring 132 to force the distal end of the plunger 131 into the aperture when distension of the inner cable 141 of the sheathed cable 14 so permits is illustrated.
A detail perspective view of a second embodiment of the apertured disk 11 a is shown in FIG. 8. A number of stand-offs topped with washers and screws permits the disk 11 a to be secured to the spokes of a spoked wheel chair wheel in position about the hub of the wheel. Similarly, a detail perspective view of a second embodiment of an apertured disk 11 b is shown in FIG. 9 . This embodiment of the disk 11 b is threaded at its central aperture to accommodate screwing onto the axle hubs of wheelchairs so having threaded axle hubs. The three embodiments in combination are estimated to fit to, and work with, over ninety percent of the wheelchairs in the U.S., and a large percentage worldwide.
In accordance with the preceding explanation, variations and adaptations of the wheelchair parking brake in accordance with the present invention will suggest themselves to a practitioner of the mechanical design arts.
In accordance with these and other possible variations and adaptations of the present invention, the scope of the invention should be determined in accordance with the following claims, only, and not solely in accordance with that embodiment within which the invention has been taught.
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A sliding plunger, normally about 1 cm. OD with a 0.5 cm tip distal end, controllably extends under spring force from a housing mounted to a wheelchair's frame transversely into a juxtaposed complimentary hole, preferably one of a circumferential array of approximately 24 such holes of racetrack shape, within an annular disk, typically 10 cm. OD with a 3.5 cm. ID center opening, that is mounted to the hub of the wheelchair's wheel at a position centered about the wheelchair's axle between the wheelchair's wheel and the wheelchair's frame. A cable extends from the sliding plunger's proximal end to a lever selectively activated by and occupant of the wheelchair to selectively permit that the sliding plunger should either (i) extend under spring force into a juxtaposed hole of the annular disk, locking the wheelchairs wheel against further rotation, or else (ii) withdraw easily from a hole, permitting wheel rotation.
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This application is a continuation of application Ser. No. 08/362,967 filed Dec. 23, 1994, abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method and a device for producing, automatically, metered amounts of coffee from instant coffee in powder form. The invention may also be applied to other drinks prepared from soluble powders exhibiting properties similar to those of instant coffee.
2. Description of the Prior Art
Various devices are known which make it possible to produce a metered amount of hot or cold coffee from powdered coffee which is mixed with water. In machines of this kind, for example in automatic drinks dispensers, a metered amount of drink in soluble powder form and a metered amount of hot or cold water are conveyed separately to a preparation chamber, for example a cup, and the mixture is produced either with the aid of a stirring member or simply by a movement imparted to the water.
However, such devices are limited to the delivery of drink in individual metered amounts of relatively small volume, this causing a considerable wait when a large number of metered amounts have to be prepared.
Of course, it is conceivable, if it is desired to prepare larger volumes containing a certain number of metered amounts, to increase the quantities of powder and of water but, unfortunately, the difficulty of achieving good dissolving rapidly increases with the volume of powder.
SUMMARY OF THE INVENTION
The present invention is proposed to overcome these drawbacks and to provide a method and a device for preparing metered amounts of coffee or other drinks from soluble powders, making it possible to very rapidly produce either a large number of individual metered amounts of drinks, or the volumes of drinks corresponding to a plurality of metered amounts, and this is achieved in a particularly simple manner and without using mechanical means liable to break down or to require careful maintenance.
The subject of the invention is a method of preparing metered amounts or pluralities of metered amounts of a drink such as, especially, coffee, from a soluble powder, wherein a concentrate of a drink such as coffee is produced by dissolving defined quantities of powder and of water, and then part or all of the concentrate is diluted in hot or cold water in order to produce a metered amount or a plurality of metered amounts of drinks.
Forming a large volume of liquid coffee concentrate in situ makes it possible to use, for the second step of the method according to the invention, means known already for preparing metered amounts of drinks from concentrates, for example in the field of fruit juices.
The automatic dissolving of large volumes of coffee in soluble powder form in relatively small volumes of liquid for the production of a concentrate is particularly difficult to achieve. As a consequence, according to one particularly preferred embodiment of the method according to the invention, concentrate is produced by dispersing water, in a gentle and homogeneous manner, over the entire upper surface of a volume, preferably spread out horizontally, of soluble powder. Under these conditions, it is found that the coffee powder is dissolved virtually completely without forming an appreciable insoluble residue. This dispersing of water, at the surface of the powder, may be carried out with the aid of spray nozzles judiciously distributed above the volume of powdered coffee, but it is preferred to achieve this by moderate sprinkling using water falling naturally from a plurality of holes in a wall located above the mass of powder, or preferably from a porous wall located above the mass of powder.
In another embodiment, in which the mass of powder has a large vertical height for a smaller surface area, it is possible to pour, directly but gently, water over the mass of coffee so as to form a liquid upper mass which progressively descends, dissolving the successive powder layers encountered as it passes, while the quantity of water is progressively topped up.
In the first embodiment of the invention, the coffee powder is preferably packaged in the form of horizontal trays.
In the second embodiment of the invention, the coffee can be packaged in relatively elongate bags.
It turns out that the coffee concentrate produced is not only easy to dissolve, in order to produce the drink, but is also preserved, without deterioration, for a period of several days, or indeed several tens of days.
In a particularly preferred embodiment of the invention, the desired quantity of drink concentrate is diluted in a hot or cold liquid, for example according to whether it is desired to prepare hot coffee or cold coffee, by suction using the Venturi effect, for example in accordance with European Patent EP-A-0,179,113.
It is thus possible to rapidly prepare a large number of individual metered amounts of coffee, or large volumes corresponding, for example, to a plurality of metered amounts, without using, at any stage in the method according to the invention, mechanical devices, so that any risk of breakdown is virtually eliminated and maintenance is reduced to its simplest expression.
The subject of the invention is also a device for the implementation of the method according to the invention, which device includes first means, using a defined large volume of soluble powder and a relatively small defined quantity of liquid such as water, for dissolving the powder in the liquid so as to produce a concentrate and second means for diluting part or all of the said concentrate in a liquid such as, for example, hot water in order to rapidly produce individual metered amounts or a plurality of metered amounts of drink.
In a first embodiment, said first means include an enclosure, preferably having a relatively large surface area, containing or receiving the powdered drink, and homogeneous spraying, sprinkling or wetting means supplying, in a homogeneous and gentle manner, liquid over the entire upper surface of the enclosure.
In a particularly preferred embodiment of the invention, this enclosure consists of a tray-shaped container in which the powdered coffee is preferably packaged, the device according to the invention having means for supplying water onto the surface of the coffee contained in the tray. Preferably, the tray is closed, at its upper face, by a double cover having a porous lower sheet and an impermeable, for example plastic or metal, upper sheet and the device includes means, such as a cannula for example, which are designed to penetrate into a space located between the two sheets of the double cover and to distribute the water in a homogenous manner in this space, the water subsequently flowing away uniformly downward through the porous sheet in order to progressively wet and dissolve the powdered coffee. Advantageously, preparation means are provided for producing one or more passages for the air to escape.
In a variant, the tray has a single, peelable or tearable, preserving cover and the device presents, permanently, a substantially horizontal porous sheet through which the water, supplied in suitable quantity, is uniformly distributed over the surface of the tray.
In another variant, this sheet is replaced by other water distribution means, for example a plurality of homogeneous perforations extending over the entire surface area above the tray or else by means for gently spraying the surface.
In another, less preferred variant, the coffee may not be contained in a tray but is poured into an enclosure, for example a tray-shaped container presented by the device, with, however, the drawback of requiring this enclosure to be cleaned from time to time.
The drink concentrate in the tray is preferably taken off via the lower part of the tray, for example by penetration of an evacuating needle, for example into a collecting well located at the lower part of the tray.
In another embodiment of the invention, for example in the case of powdered coffee contained in a sealed bag more tall than wide, it-is possible either to supply the water in accordance with the embodiments which have just been described or to pour water directly over the surface of the mass of powdered coffee, for example right inside the suitably opened bag, for example with the aid of a water supply pipe. Preferably, the water is supplied, for example by spraying, at the top of the bag with a flow rate such that a liquid upper mass is formed which descends progressively, dissolving the successive coffee powder layers encountered, while the quantity of water is progressively topped up.
The coffee bag may advantageously, in this case, include, toward its upper part, a plastic cap or similar piece which can be easily pierced for the passage of a water distribution member at the upper part of the bag, such as, for example, a spray nozzle.
This cap may advantageously include a generally cylindrical part of small height, a base connected peripherally to one of the bases of the cylindrical part in order to form a fixing zone, for example by adhesive bonding, to the coffee bag at its upper part, and a sealing cover which can be easily opened, when the bag is put into the machine for producing the coffee concentrate, for the passage of the spray head. Furthermore, this cap may advantageously include tearing means such as, for example, one or more sharp points extending beyond said base in order to partially perforate and tear the coffee bag when the cap is applied against the wall of the coffee bag and when the cap is fixed against this wall, for example by adhesive bonding.
Said second means of diluting the coffee concentrate may be any means such as those used in machines for dispensing drinks based on concentrate, for example fruit juice concentrate.
However, it is particularly preferable that said second means include a suction chamber, using the Venturi effect, connected to the liquid source, for example to a water tank equipped with means for heating the water, a suction line connecting the coffee concentrate, in its tray for example, to said suction chamber, which comes out into a dispensing line. Preferably, a nonreturn valve is located in the suction line.
In an advantageous embodiment, the device may thus include a water source, for example a hot water source, a line for taking off hot water ending in said suction chamber or nozzle, possibly a branch line for directly dispensing hot water intended for other applications, said suction line coming out into the enclosure containing the liquid concentrate, a source of liquid intended to be supplied to said enclosure for dissolving the powder and a line between said source and said enclosure. Preferably, there is only one liquid source and, in this case, a line for dissolving leaves the source and is directed toward the upper part of the enclosure.
The device according to the invention can be designed in a particularly compact manner, the enclosure containing the concentrate, for example the tray, being preferably located at the upper part of the device so that the suction line is substantially vertical.
In the case in which the concentrate is produced right inside a coffee bag whose height is large compared to its area and in which the abovementioned cap has been intended to be placed at the upper part of the bag, this bag may advantageously be used not only for the passage of a water supply means in order to produce the coffee concentrate, but also for the passage of a dip tube whose lower end is directed toward, and stops at a certain distance from the bottom of the bag and whose upper part is connected or is connectable to the suction means such as, for example, a mixing device of the Venturi type.
For this purpose, the device diluting the concentrate, for the preparation of the metered amounts, may include such a dip tube, which is preferably removable, that is inserted into the coffee packet, before or after forming the concentrate, for example through the passage provided in the cap, or a second passage provided in the cap and separated from a first passage through which the spray nozzle may pass, dissolving the coffee powder. However, in another embodiment, the dip tube, in this case preferably made of an inexpensive and disposable material, such as foodgrade plastic, may form an integral part of the cap which includes, in this case, on the one hand, the passage permitting insertion of the water spray nozzle and, on the other hand, on the internal side of the bag, the dip tube which extends down into the coffee powder to close to the bottom, and, on the external side, a connector permitting easy connection to a nozzle on the coffee machine leading toward the Venturi or vacuum-creating member, mixing the concentrate with water in order to form the metered amounts.
Adjustment of the coffee metering may advantageously be carried out by calibrating the diameter of a suction hole for the concentrated coffee. This diameter may be determined by a pierced disc located at any point between the point at which the concentrated coffee is sucked out and the chamber of the Venturi.
By way of example, the- invention enables 2.2 liters of concentrate to be produced in 30 seconds after which it is possible to produce, with the aid of a three-kW electrical heating element, one liter of coffee per minute at a temperature of 68° to 73° C., and this is achieved without using any driving element other than simple solenoid valves.
Other advantages and characteristics of the invention will appear on reading the following description, given by way of nonlimiting example and with reference to the appended drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents a general diagrammatic view of a device according to the invention;
FIG. 2 represents a sectional view of a tray of instant coffee powder according to the invention;
FIG. 2a represents a sectional view of a part of a tray similar to the tray of FIG. 2, with a venting passage;
FIG. 3 represents a view similar to FIG. 2 for a variant of the invention;
FIG. 4 represents a diagrammatic view of the enclosure for another embodiment of the invention;
FIGS. 5 and 6 represent a view from below and a side view of a cap of a coffee bag;
FIGS. 7 to 9 represent views of this cap in the operating position on a head of the device for producing metered amounts of coffee.
FIG. 10 represents a diagrammatic view of the coffee bag in such a machine.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The coffee machine according to the invention is fed via the portable water main 1. This machine includes, beyond a valve 2, a device 3 for filtering and purifying the water, based on active charcoal.
On leaving this filtration device 3, the water feed pipe includes a relief valve 4 which makes it possible to set and adjust the use pressure inside the machine, for example around 1.4 bar. A nonreturn valve 5 enables the relief valve and the purification apparatus to be isolated from the rest of the machine.
Downstream of this valve 5, the water feed line is divided into two branches 6 and 7. The branch 6 forms a first pipe which connects the water feed to an enclosure 8 which contains the instant coffee powder. A solenoid valve 9, normally closed, is placed in this first pipe 6 and can be opened by manually actuating a push button 10.
The second branch 7 of the line forms a second pipe which, in the example represented, passes through a boiler 11 and ends at a member 12 for drawing off the drink, this member 12 being constituted by a solenoid valve which is normally closed and manually actuated to open by a push button 13.
This second pipe 7, between the boiler 11 and the solenoid valve 12, and in the proximity of this solenoid valve 12, includes a suction device 14, for example a Venturi nozzle, enabling a partial vacuum to be generated in a third pipe 15. This third pipe 15 comes from the enclosure 8. The pipe 15 possesses a nonreturn valve 16 preventing water from the pipe 7 to flow toward the pipe 15.
Upstream of the Venturi 14, the pipe 7 possesses a branch line 17 which is also equipped with a drawing-off member 18 namely a solenoid valve which is normally closed and actuated to open by a push button 19, enabling only hot water to be drawn off.
On the second pipe 7 is represented an expansion vessel 7awhich, on heating the water in the boiler 11, enables the pressure prevailing in this pipe to be limited to approximately 3 bar. The unidirectional valve 5 protects the relief valve 4 from this overpressure.
The enclosure 8 for preparing the coffee concentrate has a parallelepipedal shape whose largest base is horizontal. The enclosure 8 is divided into two parts or volumes by a horizontal sheet 20 whose function will be explained below. The first volume 21, located above the sheet 20, receives, in its upper part, the outlet of the water supply line 6. The lower volume 22, forming the second part of the enclosure, is filled, over the greater part of its height, with a layer of instant coffee in powder form. A small collecting well 23 permits the outlet, into the enclosure, of the pipe 15.
The horizontal sheet or wall 20 is made of a porous or perforated permeable material the function of which is to let through, uniformly and in a homogeneous manner, the water coming from the line 6 into the volume 21 in order for this water to be poured downward, gently and in a homogeneous manner, over the layer of powdered coffee in the volume 22 in order to provide homogeneous wetting of the layer via the top.
This sheet may be made of any material permitting uniform and homogeneous pouring of the water. It may, for example, be made from fibrous layers, for example inorganic or organic fibers. It may also consist of a permeable or porous textile sheet made of a woven or nonwoven fabric, or else made of a metallic material, for example metal fibers or a metal fabric, or else the sheet may consist of a porous membrane of the usual type or made of a porous layer of a sintered material. The sheet 20 may also consist of a metal sheet or a metal or nonmetal wall provided with a plurality of fine perforations enabling the water to fall as drops onto the upper layer of instant coffee.
The operation is as follows:
By actuating the manual control button 10, the solenoid valve 9 is opened so that a defined quantity of water coming from the filter 3 is supplied via the pipe 6 to the enclosure 8. The quantity of water is adjusted, for example by means of a delay counter of the solenoid valve 9. The water which is inlet into the enclosure 8. spreads out in the upper volume 21 above the porous sheet 20 and starts to spread uniformly downward through the sheet in order to impregnate the layer of coffee powder which is progressively dissolved, and when the predetermined quantity of water has been supplied into the enclosure and has passed through the sheet 2, it is found that all the coffee powder in the volume 22 has been dissolved and the volume 22 is filled with a coffee concentrate. The proportions of coffee and water are preferably 11/2 in volume.
One or more air vents (not shown) are provided at the upper part of the enclosure 8 so as to allow air to escape progressively as water arrives and dissolves the powdered coffee.
Once the powdered coffee has been dissolved and forms the concentrate, it is possible to draw off the desired quantities of coffee. In order to do this, the push button 13 is pressed, thereby supplying a flow of hot water coming from the boiler 11 through the Venturi 14 and causes a partial vacuum in the vertical line 15. This partial vacuum sucks out the concentrate in the enclosure 8, which concentrate is mixed, inside the Venturi, with water coming from the boiler in a proportion of 1/10 in order to form the coffee, ready to be consumed, which will be poured into a cup.
By suitably delaying the solenoid valve 12, it is possible to obtain, according to choice, cups of coffee or large quantities of coffee in coffee pots.
The machine according to the invention may be designed in a compact manner, by being placed, for example, inside a cowl and providing the enclosure 8 in the upper part of it, the other elements being arranged in a compact manner at a lower level.
Reference is now made to FIG. 2.
In a particularly advantageous embodiment of the invention, the enclosure 8 is produced by a tray 24, for example made of thermoformed plastic. This parallelepipedal tray has a peripheral upper rim 25a over which is stretched and to which is adhesively bonded the porous sheet 20. Placed above the porous sheet 20 is an impermeable semirigid wall 25, for example made of plastic or a metal foil or a composite material, as used for forming food covers. This wall 25 has the shape of a shallow inverted tray so as to determine, between it and the sheet 20, the upper volume 21.
The powdered coffee is thus packaged by the manufacturer who delivers the trays filled with powder to the operators of the machines according to the invention.
The line 6 is continued by a bevelled perforating cannula 26 which is made to penetrate through the upper wall 25 so as to supply water from- the line 6 into the volume 21. Likewise, the well 23 at the lower part of the tray may be perforated by a bevelled cannula 27 penetrating into the well 23 in order to establish communication between the inside of the tray and the line 15. Furthermore, this line destroys the tray, which may no longer be reused. Venting of the air may be carried out via one or more vertical cannulas 28 which penetrate slightly into the chamber 21 through the upper wall 25.
If it is estimated that the air is not evacuated sufficiently well through the porous sheet 20, it is possible to vent the air from the lower volume 22 via a vent ending in the volume. This may be achieved, for example, by locally interrupting the sheet 20 in order to form a passage ending in the open air, the impermeable wall 25 extending hermetically around this passage. Such a construction has been represented in the diagram 2a.
For the passage of the cannula 26, it is possible to provide reliefs or depressions in the wall 25 so as to facilitate the water supply.
The wall 25, instead of being semirigid, may also consist of a permeable membrane 1, of the food-cover kind, through which the cannula may pass.
Referring to FIG. 3, an embodiment example may be seen in which a tray is still used but this forms only part of the enclosure. For this purpose, the apparatus comprises a lower support 29 in which a tray 30 filled with powdered coffee may be housed after the upper cover (not represented), closing the upper part of the tray, has been deposited beforehand. A second element 31 has a chamber 32 acting as the volume 21 and closed off at its lower part by the porous sheet 20. Having laid the tray in the support 29, this causing perforation of its well 23 by the cannula 27, a peripheral seal 33 provides sealing when the element 31 is applied to the support 29. Water is supplied via a passage 34 connected to the pipe 6, the air being vented via vents 35.
Finally, in another embodiment, the machine provides a vertical cylindrical container 36 in which a cylindrical coffee bag 37 may be placed after having largely opened it beforehand. A device 38, located at the upper part of the container, has a porous sheet 39 which can also be replaced by a perforated sheet and is fed with water via the pipe 6. The water is supplied into the internal volume of the device 38, then spreads out into droplets and falls onto the underlying coffee contained in the bag 37 whose bottom has been perforated by a cannula 27 connected to the line 15. In this case, a wide passage 40 is provided in the upper part for easy venting of the air.
In order for the water to descend homogeneously, over the entire surface, for example through a porous sheet such as 20, or a perforated membrane, provision may be made to establish a pressure in the volume above the sheet in order to force the water through the sheet in a homogeneous manner. Conversely, a partial vacuum may be established in the volume containing the coffee powder, for example in the volume 22 of the tray, for example through the venting passage (FIG. 2a). In these embodiments, the sheet 20 is preferably rigid or rigidified.
Referring to FIG. 10, an elongate vertical bag of instant coffee 41, of a commercially common type, may be seen. A cap 42 has been fixed to its upper part. The bag is inserted into a vessel 43 of a machine for preparing metered amounts of coffee ready for consumption and a dip tube has been represented, at 44, which penetrates into the bag through an opening in the cap 42 in order to suck out the coffee concentrate.
Referring to FIGS. 5 and 6, it may be seen that this cap 42 advantageously has a cylindrical body 45 of substantially semicircular cross section, one of the bases of which connects with a shoulder or seat 46 of which that face opposite the one seen in FIG. 5 permits adhesive bonding to the wall of the bag 41. The seat 46 has a central passage 47. This passage has substantially a semicircular cross section. The cylinder 45 is solid, but has a blind hole 48 open on the side where the seat 46 is and closed on the other side of the cylinder. A second, transverse, hole 49 connects the blind hole 48 to the sidewall of the cylinder.
Part of the periphery of the seat 46 has a peripheral groove 53 which will serve for positioning on and fixing to the coffee machine. Finally, a removable cover, not represented, is fixed to that face of the seat visible in FIG. 5 in order to mask, in a sealed manner, the holes 47 and 48.
Before putting the cap on the coffee bag and fixing it thereto, for example by adhesive bonding, a hole has been made beforehand in the bag, this hole providing communication from the inside of the bag with the two passages 47 and 49.
Once the bag 41 has been placed in the container 43 of the machine, the cap 42 of the bag, the cover of which has been removed, is applied against a head 50 which has retention means, not represented, enabling the cap 42 to be immobilized in the vertical position represented, by interacting with the groove 53. In this position, a water spray nozzle 51 mounted so as to be fixed in the head 50, and making an angle of 45° with the vertical, penetrates into the passage 47. This nozzle 51 is connected via a pipe, not otherwise described, to a water feed source.
Before adhesively bonding the cap to the coffee bag, an elongate flexible dip tube 44, the lower opening of which is located toward the bottom of the bag, is forcibly inserted into the hole 49. When the cap has been placed in its position on the machine, a tubular connection piece 52 is made to penetrate, in a sealed manner, into the passage 48, this connection piece 52 being connected, via a suitable line, to a known device for mixing using suction by virtue of a vacuum-creating member such as a Venturi.
The operation is as follows. The bag having thus been placed with the cap against the head 50, water is introduced by spraying or by another form of injection via the nozzle 51 with a flow rate sufficient for a volume of water to accumulate at the surface of the coffee powder. This volume of water will subsequently descend, progressively dissolving the underlying layers of coffee which it encounters and, during this period, water continues to be fed until the entire volume of water necessary for the concentrate has been sprayed. The descent of the volume of water, in which volume the coffee is concentrated, progressively, dissolves the powder completely. Once the powder has dissolved, the coffee concentrate is sucked out via the tube 44, the passage in the cap, the connection piece 52 and the suction and mixing device, and it is thus possible to dispense the metered amounts of coffee.
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In the method for preparing metered amounts of a drink in situ such as coffee, from soluble powder, a concentrate of a drink is produced by dissolving determined quantities of soluble powder with water. Then part or all of the concentrate is diluted in hot or cold water in order to produce a metered amount of a drink. The device for the implementation of the method includes an enclosure using a defined large volume of soluble powder and a relatively small defined quantity of liquid such as water, for dissolving the powder in the liquid so as to produce a concentrate in situ, and device for diluting part or all of the concentrate in a liquid in order to rapidly produce individual metered amounts of a drink.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119 to German patent application DE 20 2014 101 047.5, filed Mar. 10, 2014, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to collapsible containers. More particularly, open-top, shape-retaining collapsible containers or vessels for kitchen and home use are provided, including laundry baskets, buckets, and colanders, with improved structural strength in a collapsible region compared to existing collapsible containers.
BACKGROUND OF THE INVENTION
[0003] It is desirable for a household container to be able to collapse to relatively compact dimensions for storage or transport when the container is either not in use or being used to hold less than its maximum volume capacity of contents. Collapsible kitchenware and houseware containers of various types exist to accommodate these general needs. For example, one type of existing collapsible colander includes a stiff or rigid top section connected to a stiff or rigid bottom section by a foldable wall section that snap-folds between or among two or more positions, including at least a fully expanded position and a fully collapsed position, and in some instances, one or more intermediate, partially collapsed positions. However, because the material used to make the foldable wall section must be flexible enough to fold, it typically offers little or no resistance to deformation caused by lateral forces, such as an object bumping into or pressing against the side of the container, or a user attempting to grasp or lift the container by the flexible wall section, which could result in the contents being damaged, undesirably shifted, or spilled.
[0004] A need therefore exists for kitchenware and houseware containers that are collapsible and expandable; self-supporting in at least a fully collapsed and a fully expanded state, if not in one or more intermediate, partially expanded states; and resistant to structural deformation over at least a portion of a collapsible wall region.
BRIEF SUMMARY OF THE INVENTION
[0005] The present invention provides improved collapsible household containers and methods of making them. According to one aspect of the invention, a collapsible container is provided, comprising a generally annular top tier; a bottom tier including a generally horizontal support surface; and a collapsible wall section connecting the top tier to the bottom tier, the collapsible wall section including at least three stacked, generally annular tiers, at least a middle one of which is rigid, being formed of a different material than adjacent flexible tiers disposed above and below the middle tier. The top and bottom tiers of the container may also be rigid and formed of a different material than the flexible tiers of the collapsible wall section. The collapsible wall section, top tier, and bottom tier collectively define a container body having a top opening, a generally closed bottom comprising the generally horizontal support surface of the bottom tier, and a generally closed periphery comprising at least a part of the top tier and at least a part of the collapsible wall section. The flexible tiers are configured to fold between relatively expanded and relatively collapsed positions. The size of the container volume can be increased by folding at least one of the flexible tiers from a relatively collapsed to a relatively expanded position and can be decreased by folding at least one of the flexible tiers from a relatively expanded to a relatively collapsed position. Preferably, the flexible tiers are stable in relatively expanded positions and relatively collapsed positions, so that the container is self-supporting in each of its relatively expanded and relatively collapsed states.
[0006] Preferably, to facilitate snap-through movement between the folded and unfolded states, each flexible tier is provided with two living hinges comprising very narrow annular bands of flexible material, at which the material suddenly tapers down to a sharply reduced thickness, at the top and bottom ends of the flexible tier. Beyond the ends of the flexible tier, the material suddenly tapers back out to an increased thickness, and a wider (i.e., taller) band of the flexible material of increased thickness is disposed between each living hinge and the adjacent rigid tier of a different material, where applicable. In addition to facilitating snap-through movement between states, the thinned regions also permit each flexible tier to fold more compactly against adjacent tiers, promote stability in the folded state by minimizing forces tending to straighten the material at the bent region, and promote the formation of a folded crease at a precise, consistent location each time the tier is folded.
[0007] In certain embodiments, which correspond to methods of making containers according to another aspect of the invention, the middle tier is composed of a polypropylene, metal, or nylon material, and the flexible tiers are composed of a silicone material or a thermoplastic elastomer. For example, flexible thermoplastic elastomer tiers may be connected to the rigid middle tier by overmolding. Optionally, and particularly in the case of a metal or nylon rigid tier, the connection between the rigid tier and an adjacent flexible tier (for example made of silicone) may be strengthened by adhesive material disposed in adhesive contact with a surface of the middle tier and an adjacent surface of the flexible tier. Alternatively, other suitable means such as mechanical fasteners may be employed to connect a rigid tier to an adjacent flexible tier.
[0008] In some embodiments, each tier of the container is at least substantially imperforate, so that the container can serve to hold liquid. In other embodiments, the container has perforations serving to drain liquid and/or facilitate aeration, as in colanders, dish drainers, buckets adapted as sand sifters, and certain embodiments of laundry baskets.
[0009] In still other embodiments, at least a portion of at least one of the tiers is air permeable to permit some airflow into and out of the container without passing through the top opening.
[0010] In yet other embodiments, the top tier comprises at least one attached handle.
[0011] According to another aspect of the invention, a collapsible dish drainer is provided having a collapsible wall structure generally as described above. The bottom tier of the drainer includes a generally horizontal support surface with a drain and a plurality of parallel, upstanding partitions arranged to support dishware standing on edge between adjacent partitions. Advantageously, said drain is configured to be plugged by an insertable drain plug to render the body of the drainer at least substantially watertight. Together with the drainer, a separate, collapsible domed lid may be provided. The domed lid may have a substantially similar structure to that of the drainer itself, but slightly smaller and imperforate, while also including a handle set into a generally horizontal panel of its top tier. The lid is configured to be supported on said top drainer tier in a mating configuration with the top tier of the drainer, whether the collapsible lid is oriented right-side-up (i.e., with its opening facing down) or upside-down. When upside-down, the collapsible lid is configured to nest inside the drainer body, at or below the highest portion of the top drainer tier and at least substantially within the interior volume below the drainer top opening, when the drainer and the lid are both in fully expanded states. Then, the lid is configured to collapse together with the drainer, remaining at or below the highest portion of the drainer top tier and at least substantially within the drainer volume when the drainer and the lid are both in fully collapsed states.
[0012] According to yet another aspect of the invention, a collapsible cup is provided. The collapsible cup may advantageously be used as a drinking cup or a measuring cup, for example. The collapsible cup includes a collapsible wall structure, substantially as described above, and a handle pivotally connected to its top tier. When the cup is fully collapsed, the handle is configured to pivot into a position in which a portion of the handle extends beneath and generally parallel to the bottom tier of the cup.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a perspective view of a collapsible laundry basket according to one aspect of the invention, in a fully expanded state.
[0014] FIG. 2 is a perspective view of the laundry basket shown in FIG. 1 , in a fully collapsed state.
[0015] FIG. 3 is a side elevation view of the laundry basket shown in FIG. 1 , in a fully collapsed state.
[0016] FIG. 4 is a fragmentary cross-sectional view of a wall structure of the laundry basket shown in FIG. 1 , in a partially collapsed state.
[0017] FIG. 5 is a fragmentary cross-sectional view of a wall structure of the laundry basket shown in FIG. 1 , in another partially collapsed state.
[0018] FIG. 6 is a perspective view of a collapsible bucket according to another aspect of the invention, in a fully expanded state.
[0019] FIG. 7 is a perspective view of the bucket shown in FIG. 1 , in a fully collapsed state.
[0020] FIG. 8 is a side elevation view of the bucket shown in FIG. 1 , in a fully collapsed state.
[0021] FIG. 9 is a perspective view of a collapsible colander according to another aspect of the invention, in a fully expanded state.
[0022] FIG. 10 is a perspective view of the collapsible colander shown in FIG. 9 , in a fully collapsed state.
[0023] FIG. 11 is a side elevation view of the collapsible colander shown in FIG. 9 , in a fully collapsed state.
[0024] FIG. 12 is a perspective view of a collapsible cup according to still another aspect of the invention, in a fully expanded state.
[0025] FIG. 13 is a perspective view of the cup shown in FIG. 12 , in a fully collapsed state.
[0026] FIG. 14 is a side elevation view of the cup shown in FIG. 12 , in a fully collapsed state.
[0027] FIG. 15 is a bottom perspective view of the cup shown in FIG. 12 , in a fully collapsed state.
[0028] FIG. 16 is a top perspective view of a collapsible dish drainer according to yet another aspect of the invention, in a fully expanded state.
[0029] FIG. 17 is a top perspective view of the dish drainer shown in FIG. 16 , in a fully collapsed state.
[0030] FIG. 18 is a side elevation view of the dish drainer shown in FIG. 16 , in a fully expanded state.
[0031] FIG. 19 is a side elevation view of the dish drainer shown in FIG. 16 , in a fully collapsed state.
[0032] FIG. 20 is a bottom perspective view of the dish drainer shown in FIG. 16 , in a fully collapsed state.
[0033] FIG. 21 is a top perspective view of the dish drainer shown in FIG. 16 , having a collapsible lid placed thereon, the lid in a fully expanded state.
[0034] FIG. 22 is a top perspective view of the dish drainer shown in FIG. 16 , having a collapsible lid placed thereon, the lid in a fully collapsed state.
[0035] FIG. 23 is a side elevation view of the dish drainer shown in FIG. 16 , having a collapsible lid placed thereon, the lid in a fully expanded state.
[0036] FIG. 24 is a top perspective view of the dish drainer shown in FIG. 16 , having an upside-down collapsible lid nested therein, both drainer and lid in fully expanded states.
[0037] FIG. 25 is a top perspective view of the dish drainer shown in FIG. 16 , having an upside-down collapsible lid nested therein, drainer and lid in fully collapsed states.
[0038] FIG. 26 is a side elevation view of the dish drainer shown in FIG. 16 , having an upside upside-down collapsible lid nested therein, drainer and lid in fully collapsed states.
[0039] FIG. 27 is a side elevation view of the dish drainer shown in FIG. 16 , having an upside-down collapsible lid nested therein, both drainer and lid in fully expanded states.
DETAILED DESCRIPTION OF THE INVENTION
[0040] Collapsible kitchenware and houseware containers with improved shape retention and structural integrity in accordance with the present invention are described in this section, with reference to a collapsible laundry basket 10 depicted in FIGS. 1-5 , a collapsible bucket 26 depicted in FIGS. 6-8 , a collapsible colander 42 depicted in FIGS. 9-11 , a collapsible cup 58 depicted in FIGS. 12-15 , and a collapsible drainer 78 depicted in FIGS. 16-27 .
[0041] Turning to FIGS. 1-5 , a laundry basket 10 according to one embodiment of the invention are described and illustrated. Laundry basket 10 includes a rigid top tier 12 , a rigid bottom tier 14 , and a collapsible wall section 16 that may be collapsed and expanded to vary the overall height dimension of laundry basket 10 and thus the available volume for laundry. Wall section 16 , in turn, includes a rigid middle tier 18 between two flexible tiers 20 and 22 . Additional tiers may be included in the collapsible wall section, preferably adhering to the alternating arrangement in which a flexible tier is connected above and below each rigid tier.
[0042] Optionally but preferably, laundry basket 10 includes integrally formed or otherwise connected or attached handles, such as handles 24 shown as being integral to top tier 12 . Additional lower handles may be formed as slot openings in middle tier 18 . Also, the body of laundry basket 10 may include lateral openings (not shown) to allow its contents to air out, as is particularly beneficial when laundry basket 10 is used as a hamper for dirty laundry. The lateral openings may be formed in rigid middle tier 18 and/or in any flexible tier.
[0043] Flexible tiers 20 and 22 are illustrated as having two stable positions, one unfolded and one folded, respectively corresponding to relatively expanded and collapsed states of laundry basket 10 . A fully expanded state of laundry basket 10 is illustrated in FIG. 1 , showing both flexible tiers 20 and 22 in their unfolded positions, while a fully collapsed state of laundry basket 10 is illustrated in FIGS. 2 and 3 , showing both flexible tiers 20 and 22 in folded positions. In its fully expanded state, laundry basket 10 provides its maximum laundry volume capacity, while in its fully collapsed state, laundry basket 10 is at its most compact, which is particularly beneficial for storage.
[0044] Two partially collapsed states of laundry basket 10 are illustrated by the fragmentary side sectional views shown in FIGS. 4 and 5 , in which only flexible tier 20 or only flexible tier 22 is folded, respectively. Thus, it is illustrated that each of flexible tiers 20 and 22 may be folded and unfolded separately and independently to transform the shape of laundry basket 10 to its fully expanded, fully collapsed, and two partially expanded states illustrated in the Figures. Multiple advantages are provided by the partially collapsed states of laundry basket 10 . For instance, when filling a laundry basket with clean laundry, it is often convenient to place the basket on a high surface near a dryer containing a load of clean laundry. The partially collapsed position of laundry basket 10 facilitates this process by making it easier to reach clean clothes over the top of laundry basket 10 . In addition, when carrying a volume of laundry smaller than the maximum capacity of laundry basket 10 , partially collapsing laundry basket 10 may make it more comfortable to carry. For example, when holding laundry basket 10 from underneath by bottom tier 14 , laundry basket 10 will be easier to see over or around if in its collapsed state. On the other hand, when walking while holding laundry basket 10 by handles 24 , partially collapsing laundry basket 10 may help to prevent one's knees from bumping into laundry basket 10 , without having to hold the handles of laundry basket 10 as high as would be necessary if it were fully expanded. Lower handles formed in middle tier 18 (not shown), for example in the form of elongate slots with rounded ends, may also assist in this regard, whether or not laundry basket 10 is fully expanded.
[0045] With reference to FIGS. 6-8 , a collapsible bucket 26 according to the invention is illustrated. Bucket 26 includes a rigid top tier 28 , a rigid bottom tier 30 , and a collapsible wall section 32 including a rigid tier 34 disposed between flexible tiers 36 and 38 . The fully expanded, fully collapsed, and partially collapsed states of bucket 26 , illustrated in the drawings, are substantially analogous to those of laundry basket 10 . Optionally, but preferably, bucket 26 includes a handle 40 connected to its top tier. Unlike laundry basket 10 , which may advantageously include perforations to facilitate aeration, the body of bucket 26 is preferably imperforate so as to retain water or other liquid, although in certain embodiments not shown, bucket 26 may include a perforated bottom, for example, to serve as a sand-sifter for beach or sandbox amusement. Advantageously, when bucket 26 is filled with liquid, the collapsing action of wall section 32 provides a way of emptying at least some of the liquid contents, by simply pressing down on top tier 28 to cause wall section 32 to collapse, allowing the liquid to overflow. This avoids the need for lifting and/or inverting bucket 26 , at least until the liquid level is lower, making those steps less strenuous.
[0046] Turning to FIGS. 9-11 , a collapsible colander 42 embodying another aspect of the invention is illustrated. Colander 42 includes a rigid top tier 44 , a rigid bottom tier 46 , and a foldable wall section 48 comprising at least one rigid middle tier 50 and at least two flexible tiers 52 and 54 above and below middle tier 50 . Bottom tier 46 includes perforations 56 typically to facilitate draining water from rinsed salad greens, boiled pasta noodles, or other damp foods, as well as cooperating with tiers 54 , 50 , 52 , and/or 44 to form a concave, curved surface to facilitate overturning contents. As in the other collapsible containers according to the invention, fully expanding collapsible colander 42 provides its maximum volume capacity, while fully collapsing it provides for most compact storage. In the case of collapsible colander 42 one benefit of a partially collapsed state may be to minimize the refrigerator space occupied by a leftover salad or other dish prepared, and conveniently put away, in colander 42 .
[0047] With reference to FIGS. 12-15 , collapsible cup 58 embodying another aspect of the invention is illustrated. Cup 58 includes a body portion 60 comprising rigid top tier 62 , a rigid bottom tier 64 , and a foldable wall section 66 comprising at least one rigid middle tier 68 and at least two flexible tiers 70 and 72 above and below middle tier 68 . As in the other collapsible containers according to the invention, fully expanding collapsible cup 58 provides its maximum volume capacity, while fully collapsing it provides for most compact storage. Cup 58 also includes a handle 74 pivotally connected to top tier 62 for movement between a use position shown in FIG. 12 and a compact or stowed position shown in FIGS. 13-15 . It will be understood from FIGS. 12-15 that cup 58 must be collapsed before folding handle 74 to the stowed position, and conversely, handle 74 must be moved to the use position before expanding cup 58 . Preferably, a suitable mechanism is provided for resisting movement of handle 74 away from the use position, so that the weight of liquid contained in cup 58 does not cause body portion 60 of cup 58 to pivot towards handle 74 when cup 58 is held by the handle, resulting in user annoyance and/or possible spillage. Examples of suitable mechanisms may include a detent for “snapping” handle 74 into and out of the use position and/or a tight-fitting pivot joint 76 providing frictional resistance over its full range of motion or only a partial range of motion near the use position. A similar retention mechanism may also be provided for keeping handle 74 in the stowed position. As an ancillary benefit, should flexible tiers 70 and 72 of foldable wall section 66 exhibit some degree of hysteresis, for example tending to spontaneously unfold when cup 58 is collapsed after being kept continuously in its fully expanded state for a long period of time, a retention mechanism for holding handle 74 in its stowed position may also help to retain body portion 60 of cup 58 in its fully collapsed state until the material of flexible tiers 70 and 72 returns to its normal behavior.
[0048] Turning to FIGS. 16-27 a collapsible dish drainer 78 embodying another aspect of the invention is illustrated. Dish drainer 78 includes a drainer body 80 comprising rigid top tier 82 , preferably including a rim with a downturned portion defining a peripheral channel 83 for ease of lifting, as shown in FIG. 20 ; a rigid bottom tier 84 , and a foldable wall section 86 comprising at least one rigid middle tier 88 and at least two flexible tiers 90 and 92 above and below middle tier 88 . As in the other collapsible containers according to the invention, fully expanding collapsible dish drainer 78 provides its maximum volume capacity, while fully collapsing it provides for most compact storage. Dish drainer 78 includes an array of upstanding slender partitions 94 whose gap spacing, individual length, individual height, and other relevant dimensions are suited for retaining typically sized plates, bowls, and other dishes on edge between pairs of adjacent partitions 94 Additionally, although the spacing between partitions 94 in the illustrated embodiment of drainer 78 is generally uniform, multiple arrays of partitions having distinct spacing and/or individual dimensions may instead be provided as appropriate to accommodate differently shaped individual dishes or sets of dishes.
[0049] Dish drainer 78 also includes a perforated drain 96 to permit water drained from dishes in drainer 78 to drain out, for example into a sink or wash basin. Perforations 98 of drain 96 are set at the bottom surface of a depression having an imperforate wall section 100 . As best seen in the side elevation views of drainer 78 (such as FIG. 18 ), the shape of bottom tier 84 is such that when its lowest portion rests on a horizontal surface to support drainer 78 , the bottom of drain 96 is raised above the horizontal surface to permit free draining flow through perforations 98 and to inhibit soiling of drain 96 , either by contact of drain 96 with the horizontal surface itself, or by backflow of accumulated liquid on the horizontal surface (such as the bottom of a sink basin) through perforations 98 . Drain wall section 100 has a slight inward taper toward the bottom surface of the depression to facilitate covering and sealing drain 96 with a resilient drain plug 102 . Advantageously, this permits drainer 78 to perform the additional function of a dish pan for soaking and/or hand washing dishes, while in its expanded state and having drain plug 102 inserted, as in the configuration illustrated in FIG. 16 . However, as an alternative to the illustrated drainer 78 having a localized drain 96 , it will be understood that a dish drainer having perforations extending across its entire bottom surface (not shown in the Figures) may have its own advantages, such as more rapid and/or complete draining of water from the interior surfaces of the drainer body, and/or better aeration to facilitate faster evaporation of water from the dishes and drainer.
[0050] Optionally but advantageously, drainer 78 may be provided together with a complementary lid. In particular, a lid 104 may be provided which is also collapsible, including a stiff or rigid panel 106 , a foldable wall section 108 , and a stiff or rigid rim 110 . Foldable wall section 108 of lid 104 is illustrated in the Figures as being entirely composed of a resilient, flexible material, including flexible tiers 112 , 114 and a middle, stiff tier 116 that is made thicker and/or less tapered than flexible tiers 112 , 114 , so as to retain its orientation when flexible tiers 112 , 114 fold relative to it. Rim 110 of lid 104 is sized to nest in a stepped portion 118 of drainer top tier 82 shown in FIGS. 16 and 17 , in both a right-side-up orientation as shown in FIGS. 21-23 and an upside-down orientation as shown in FIGS. 24-27 . Likewise, when collapsible lid 104 is first nested upside down in collapsible drainer 78 , both lid 104 and drainer 78 being initially fully expanded (see FIG. 24 , and the side elevation view of FIG. 27 , which also illustrates that lid 104 fits entirely below the highest portions of drainer top tier 82 ), foldable lid wall section 108 is configured to collapse together with foldable drainer wall section 86 in a nested configuration illustrated in FIGS. 25 and 26 , achieving the same contraction of the height dimension of drainer 78 as when drainer 78 is collapsed by itself.
[0051] Drainer 78 has several different use configurations, making it adaptable to different circumstances and user preferences, as well as different uses. For example, it has already been noted that drainer 78 may also serve as a dish pan for soaking and hand washing, when in an expanded state and having drain plug 102 inserted. When drainer 78 is employed in this way (or in any other configuration without lid 104 placed thereon), lid 104 in its upside-down, expanded configuration may simultaneously be used as another slightly smaller dish pan independent of drainer 78 , for example to provide more volume for simultaneous soaking of more dishes. Alternatively, lid 104 may be placed over drainer 78 in its right-side-up orientation, either expanded (to provide more height clearance for tall dishes) or collapsed (for a more compact vertical profile), for example as desired for the purpose of protecting dishes in drainer 78 from inadvertent soiling or contamination while they are being soaked, as shown in FIGS. 21-23 . To facilitate easy removal of lid 104 , an inset handle 120 may be provided on the top side of lid panel 106 .
[0052] When used for draining water from damp, clean dishes, on the other hand, drainer 78 may either be in a collapsed or an expanded state. The collapsed state provides the most unobstructed access to the bottom tier 84 of drainer 78 , which may be particularly desirable for repetitive loading of dishes thereon from a lateral location, such as from a kitchen sink next to a counter (not shown) on which drainer 78 is placed, after washing each dish in the sink. (In such a situation, although not illustrated in the Figures, a conventional dish drainer tray, having three raised sides and one draining side placed over an edge of the sink, may beneficially be placed on the counter underneath drainer 78 to direct water drained from drainer 78 into the sink.) On the other hand, the expanded state of drainer 78 makes use of foldable wall section 86 and top tier 82 as partial splash guards to protect dishes from being soiled by splashing from lateral directions, which may likewise be desirable in the aforementioned situation of washing dishes in an adjacent sink while clean dishes are held in drainer 78 . Alternatively, omnidirectional splash protection for dishes in drainer 78 may be provided by placing lid 104 over drainer 78 , either in its expanded position shown in FIGS. 21 and 23 (again, to accommodate tall dishes or utensils, for instance), or its collapsed position shown in FIG. 22 .
[0053] Still another function of drainer 78 with lid 104 placed on it may be to protect dishes placed in drainer 78 for transportation and/or storage. In this context, lid 78 may both help to keep airborne particles from entering drainer 78 and settling on dishes stored therein, but also may permit boxes, containers, or other items to be conveniently stacked on top of drainer 78 without resting directly on the dishes.
[0054] Of course, in the context of containers according to the present invention, as in common parlance, it will be understood that “stiff,” “rigid,” and “flexible” are relative terms. Thus unless further specified, referring to a tier of a wall structure as “stiff” herein simply means, at a minimum, that the tier is stiff enough to impart a force to its neighboring flexible tier or tiers sufficient to fold the flexible tier or tiers between relatively folded and unfolded stable positions (optionally causing the flexible tiers to “snap” between positions), without itself folding (i.e., without inverting its vertical orientation, with respect to the top and bottom of the container). On the other hand, a tier that is considered “rigid” for purposes of the invention typically will not even appreciably yield or deform, let alone fold, in the direction of the force imparted to fold the flexible tiers, in response to either that force or other typical loads associated with normal use of the container. Still further, a rigid tier preferably will not appreciably deform in any direction during normal use of the container. A “rigid” tier that exhibits the latter characteristic of not appreciably deforming in any direction is typically formed of a different material than the flexible tiers, rather than the same material in a different size or geometric configuration.
[0055] Although each flexible tier of the various household containers described herein is illustrated as having only two stable positions, it is also within the scope of the invention to provide one or more flexible tiers having a plurality of stable partially expanded positions, for example by providing one or more flexible tiers having a stepped profile comprising a series of accordion-like pleats of flexible material, the pleats comprising peripheral bands of material oriented in alternating directions and connected to adjacent bands by living hinges, so that each pleat can be independently folded and unfolded (not shown), being stable in either state. Also, a wall structure of a container according to the invention need not have the exact shapes of the containers shown in the Figures, but may have any suitable shape, such as round, oval, rectangular with rounded corners, or other shape as desired. For example, successive accordion pleats may be stable in relatively “bent” orientations, in which part of the circumferential length of a pleat is folded and the remainder of the length is unfolded.
[0056] Household containers according to the invention may be constructed of any suitable materials that impart relative stiffness or rigidity to the top tier, middle tier, and bottom tier; and relative flexibility to the flexible tiers, while permitting the tiers to be durably attached to their neighboring tiers. For example, the top tier, bottom tier, and/or middle tier may be composed of polypropylene, the flexible tiers being a thermoplastic elastomer overmolded onto the polypropylene. Alternatively, the top tier, bottom tier, and/or middle tier may be composed of metal or nylon, the flexible tiers being a silicone material overmolded onto the metal or nylon with adhesive glue between the two materials to strengthen their connection.
[0057] With the exception of lid 104 of collapsible dish drainer 78 (which may itself serve as a collapsible container independently of drainer 78 ), the middle tiers of the foldable wall sections of the various illustrated containers according to the present invention are shown and described above as being of a rigid material that is different from the flexible material of the adjoining flexible tiers. However, the structural strength and shape retention provided by a rigid middle tier of a different material is only one of many advantages provided by household containers of the present invention, and where desired, components that are merely “stiff,” and optionally made of the same material as the flexible tiers, but formed with shapes and/or dimensions that promote stiffness, may be substituted in the place of “rigid” components of containers of the invention, while still retaining other advantages over existing containers.
[0058] While the invention has been described with respect to certain embodiments, as will be appreciated by those skilled in the art, it is to be understood that the invention is capable of numerous changes, modifications and rearrangements, and such changes, modifications and rearrangements are intended to be covered by the following claims.
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Collapsible household containers having a foldable wall section with shape-retaining characteristics are disclosed. In particular, collapsible laundry baskets, buckets, colanders, dish drainers, and cups are provided. The folding region may include foldable tiers of a flexible material, each tier having at least one stable, relatively expanded position and at least one stable, relatively collapsed position; and an intervening, non-folding tier composed of a different, relatively rigid material.
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FIELD OF THE INVENTION
The invention relates to a running board for a motor vehicle, a motor vehicle including a running board, and a method for installing a running board to a motor vehicle.
BACKGROUND OF THE INVENTION
Many types of vehicles, including sports utility vehicles, pick up trucks, and vans, are raised off the ground farther than normal passenger automobiles. The increased height of the floor of the passenger cab from the ground makes it difficult to enter and exit these vehicles. In addition, if the vehicles are driven over rough terrain, their lower body panels and door panels are susceptible to being scratched, dented, or otherwise damaged by rocks or other ground debris. Accordingly, running boards provide a stepping surface to assist the driver and passengers in entering and exiting these vehicles. In addition, the running boards protect the body of the vehicles from being damaged from below.
Running boards commonly include a least two different materials that are attached together, namely, a first material for the body of the running board and a second material for the stepping surface of the running board. There exist numerous references describing various running board designs. For example, see U.S. Pat. No. 6,173,979 to Bernard; U.S. Pat. No. 5,713,589 to Delgado et al.; U.S. Pat. No. 1,861,430 to Bronson; 300,536 to Holloway et al.; U.S. Pat. No. 4,935,638 to Straka; U.S. Pat. No. 2,122,240 to Smith; and U.S. Pat. No. 2,021,522 to Schacht.
SUMMARY OF THE INVENTION
A running board is provided according to the invention. The running board includes a deck, a mat, and a step cover. The deck includes a step portion and a support structure for supporting the step portion. The mat provides a stepping surface and is positioned on the step portion of the deck with a portion thereof sandwiched between the deck and the step cover. The step cover is attached to the deck to aid in securing the mat in position.
A motor vehicle is provided according to the invention. The motor vehicle includes a running board positioned along the side of the vehicle behind the front wheels of the outer doors. The motor vehicle can include a pair of opposed running boards, one provided beneath the driver's side door and one provided beneath the passenger's side door. Each running board can include a deck, a step cover, and a mat, wherein a portion of the mat is sandwiched between the deck and the step cover.
A method for installing a running board is provided according to the invention. The method includes the steps of attaching a mat to a running board by placing a step cover over a portion of the mat and affixing the step cover to the running board, and attaching the running board to the vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a running board according to the principles of the present invention attached to a motor vehicle.
FIG. 2 is a perspective view of the running board of FIG. 1 , partially exploded.
FIG. 3 is side elevation view of the mat of FIG. 1 .
FIG. 4 is a bottom perspective view of the running board of FIG. 1 showing the brackets attached to the running board with parts removed for clarity.
FIG. 5 is a perspective view of an alternative embodiment of the mat of FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 , a running board according to the invention is shown at reference numeral 10 . The running board 10 is shown attached to a motor vehicle 12 . The running board 10 is provided beneath the vehicle doors 14 so that it functions as a step for someone entering or exiting the vehicle 12 . The running board 10 can be provided on any type of motor vehicle where a step is desired to assist entering or exiting the vehicle 12 . Some of the various types of vehicles 12 that can be provided with running boards include pickup trucks, sports utility vehicles, vans, hauling trucks, and many others. The running board 10 according to the invention can be provided beneath a single door or it can be provided so that it extends from the front doors to the rear doors of a motor vehicle 12 .
Referring to FIG. 2 , a running board 10 according to the invention is shown. The running board 10 includes a deck 100 having a top side 102 , a bottom side 104 , a front side 107 , a back side 109 , a first end 106 , a second end 108 , a first step portion 103 , and a second step portion 105 .
As shown, the deck 100 can include a flat surface portion on the top portion 102 of the deck 100 . As shown, the bottom portion 104 and the top portion 102 connect at the front surface 107 , but do not connect at the back side 109 . The first end 106 and the second end 108 of the deck 100 are not “finished off” or enclosed. In other words, the deck 100 terminates in ends 106 , 108 that have exposed cross-sectional profiles. The deck 100 further includes two step portions 103 and 105 . The step portions, also referred to as step members or step zones, 103 , 105 are located below the doors 14 of the vehicle 12 and are sized to support the weight of a person to aid the entry and exit of the person from the vehicle 12 . The deck 100 can be fabricated from aluminum; however, it should be appreciated that the deck 100 could be fabricated from steel, plastic, or any number of other materials or combinations thereof. It should further be appreciated that the deck 100 need not include the above-described structure so long as it is configured to support a person's foot while the person enters and exits a vehicle.
In particular, it should also be appreciated that in alternative embodiments the top surface 102 of the deck 100 need not be flat. For example, the top portion 102 could be rounded or have any other surface profile. In addition, the top portion 102 and the bottom portion 104 could be continuous, as they would be in a square or cylindrical tube shaped deck. In addition, the ends 106 , 108 rather than left open, could be finished off. Also, the deck 100 could include more or less step portions 103 , 105 depending on, for example, the number of doors 14 on one side of the motor vehicle 12 . Moreover, it should be appreciated that the surface of the deck 100 can be painted, coated, or otherwise finished as desired.
Still referring to FIG. 2 , mats 40 , 50 and step covers 20 , 30 are shown relative to the deck 100 . The first mat 20 is positioned over the first step portion 103 and the second mat 50 is positioned over the second step portion 105 . The first step cover 20 is position over a portion of the first mat 40 and attached to the deck 100 . Similarly, the second step cover 30 is position over a portion of the second mat 50 and attached to the deck 100 . As shown, the first step cover 20 encloses, or finishes off, the first end 106 of the deck 100 and the second step cover 30 encloses, or finishes off, the second end 108 of the deck 100 .
Still referring to FIG. 2 , the step covers 20 and 30 are shown. The step cover 30 is not referenced separately in detail since it is a mirror reflection of step cover 20 . Step cover 20 can include a top surface 21 , a bottom surface 23 , a first end 24 , and a second end 22 . The top surface 21 can include a plurality of elongated cutouts 26 separated by extensions 27 that are arranged perpendicular to the longitudinal axis of the step cover 20 . In the embodiment shown, the step cover 20 includes thirteen cutouts 26 . It should be appreciated that the step cover 20 could include any number of cutouts 26 each being any shape or size and arranged on step cover 20 in a variety of different patterns. The step cover 20 can be attached to the deck 100 by a number of fasteners 115 . The fasteners 115 are shown as mechanical devices; however, it should be appreciated that they could also be chemical adhesives or any other materials that would be suitable for attaching the cover 20 to the deck 100 .
As shown, the first end 24 of the step cover 20 wraps toward the inner edge 29 of the step cover 20 such that it encloses or finishes off the end 106 of the deck 100 . Once the step cover 20 is installed, it hides the first end 106 of the deck 100 from view. The second end 22 extends past the portion in which cutouts 26 are formed to form a flange 25 that is orientated in a plane parallel to the plane defined by the portion of the step cover 20 that includes cutouts 26 . The flange 25 at the second end 22 can abut, or rest on, the top surface 102 of the deck 100 . It should be appreciated that in some embodiments the first end portion 24 can be open and therefore not enclose the first end 106 of the deck 100 . In addition, in some embodiments the second end 22 of the step cover 20 can be coplanar with the portion of the step cover 20 that includes cutouts 26 rather than coplanar with the surface 102 of the deck 100 .
Still referring to FIG. 2 , the step cover 20 includes a front edge portion 28 that is constructed to extend over the front side 107 of the deck 100 . When installed, the front edge portion 28 of the step cover 20 hides a portion of the step portion 103 of the deck 100 from view. However, it should be appreciated that in some embodiments, the step cover 20 does not include an edge portion 28 and the edge of the deck 100 in the step portion 103 is exposed even after the step cover 20 is installed. In addition, it should be appreciated that the surfaces of the step cover 20 can be painted, coated, or otherwise finished as desired. In the embodiment shown, the edge portion 28 is fastened to the deck by fasteners 115 . The cover 20 is fastened to the deck at a location in which there is no matt 40 , 50 below. This feature of the cover 20 makes it possible to fix the mat 40 to be fixed to the deck 100 without beaching the integrity of the mat 40 . In other words, attaching the mat 40 to the deck 100 does not necessarily require screwing or bolting thought the mat 40 . However, it should also be appreciated that the cover 20 alternatively could nonetheless be fastened to the deck 100 through the mats 40 and 50 .
In the embodiment shown, the cover 20 is constructed of a plastic material. However, it should be understood that the materials used to construct the cover 20 can vary. For example, in some embodiments, the same material used to construct the deck 100 can be used to construct the cover to provide a more uniform appearance.
Referring to FIGS. 2-3 , a mat 40 is shown. The mat 40 is identical to the mat 50 , therefore only the mat 40 is described in detail below. The mat 40 includes a first end 47 , a second end 46 , a front edge 48 , a back edge 49 , and a top major surface 43 having raised portions 42 positioned thereon. The mat 40 is sized to fit on the deck 100 of the running board 10 under the step cover 20 . The raised portions 42 of the mat 40 are shaped to extend through and interlock with the step cover 20 such that once the step cover 20 is attached to the deck 100 , the mat 40 is also secured to the deck 100 . In particular, the thirteen raised portions 42 are elongated in shape and are arranged perpendicular to the longitudinal axis of the mat 40 . In the embodiment shown in FIGS. 2 and 3 the mat 40 has a flat bottom surface.
In some embodiments the mats 40 is constructed of plastic or rubber material (natural or synthetic). In the particular embodiments shown in the Figures, the mat 40 is constructed from a urethane material having similar properties to the material used to construct the sole so athletic shoes. Soft resilient material that otherwise may not be strong enough to be used to construct a mat for attachment to conventional running board can be used to construct the mat 40 since, in some embodiments, the cover 20 at least partially protects and secures the mat 40 in place. However, it should be appreciated that the mat 40 can be constructed of many different types materials including non-resilient materials.
It should also be appreciated that the raised portions 42 of the mat 40 need not, as described above, interlock with the step cover 20 such that the step cover 20 once attached secures the mat 40 in position on the deck 100 . The mat 40 can be independently secured to the deck 100 via mechanical fasteners, adhesives, tapes, and other means. In fact, in some embodiments the mat 40 need not include any raised portions 42 . Alternatively, in some embodiments the cover portion 20 , once attached to the deck 100 , compresses or sandwiches portions of the mat 40 and thereby aids in securing the mat 40 in position on the deck 100 .
Now referring to FIG. 4 , the running board 10 includes a bracket assembly 130 . The bracket assembly 130 includes a plurality of brackets 110 each having a first end 116 and a second end 118 . Both ends 116 , 118 include holes, or slots, for receiving fasteners 114 . The first ends 116 are attached to the deck 100 and the second ends 118 are attached to the vehicle 12 . The brackets 110 can be constructed to attach to the rocker panel and/or frame of the vehicle 12 . Since the rocker panel and frame structure vary according to make and model, the exact geometry of the brackets 110 vary accordingly. It should be appreciated that the brackets 110 can be constructed of steel or any other suitable material.
Still referring to FIG. 4 , the fasteners 114 are received in channels 117 and 119 that run along the underside of the deck 100 . The channels 117 and 119 of the deck 100 enable the deck 100 to be attached to brackets 110 located at a number of different locations along the deck 100 . The channels 117 and 119 of the deck 100 can run along the entire length of the deck 100 or only exist in regions of the deck 100 that are most likely to be attached to the brackets 110 .
Referring to FIG. 4 , bracket covers 121 are shown attached between the deck 100 and the brackets 110 such that they hide the brackets 110 from clear view once the running board 10 is attached to the vehicle 12 . Each bracket cover 121 includes a first end 124 adapted to cover the first end 116 of the bracket 130 and a second end 122 adapted to cover the second end 118 of the bracket 130 . In the embodiment shown, four brackets 110 attach the running board 10 to the vehicle 12 . It should be appreciated that there are many alternative ways to connect the deck 100 to the vehicle 12 . For example, the deck 100 could include arms that are integral with the deck 100 that extend outwardly and upwardly to attach to the vehicle 12 .
An alternative embodiment of the mat 40 is shown in FIG. 5 . The mat 40 ′ shown includes a cross-sectional profile that is shaped to match the cross-sectional profile of the deck 100 to provide a snug fit between the mat 40 ′ and the deck 100 . In particular, the mat 40 ′ includes a front edge 48 ,′ a rear edge 49 ,′ a first end 47 ,′ a second end 46 ,′ and a top major surface 43 ′ having raised portions 42 ′ thereon. The front edge 48 ′ and the rear edge 49 ′ extend away from the top major surface 43 ′ in a downward direction tracking a portion of the curved surface of the deck 100 .
The above specification, examples, and data provide a complete description of the installation and composition of the invention. Since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended.
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A running board is provided by the invention. The running board includes a deck, a stepping surface material, and a step cover. The stepping surface material includes raised portions that prevent foot slippage. The cover portion partially overlaps the stepping material to secure it in a place on the deck. A motor vehicle with a running board and methods for installing the running board are also provided.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit under 35 U.S.C. §119(e) of pending U.S. provisional patent application Serial No. 60/291,327, filed May 17, 2001, and priority under 35 U.S.C. §119(a)-(d) of French patent application No. FR-01.04328, filed Mar. 30, 2001.
TECHNICAL FIELD
The present invention relates to a fluid dispenser assembly comprising a fluid dispenser defining a substantially flat body provided with a dispensing orifice and with a removable closure member that masks the dispensing orifice prior to use. The dispenser assembly further comprises packaging encasing the dispenser while leaving the removable closure member accessible so that it can be removed from the body, thereby unmasking the dispensing orifice. Such dispenser assemblies can be used in the fields of perfumes, of cosmetics, or indeed of pharmaceuticals.
BACKGROUND OF THE INVENTION
Document FR 2 791 645 describes a fluid dispenser having a substantially flat body and a removable closure member which masks the dispensing orifice defined by the body. That fluid dispenser does not have any packaging encasing the body of the dispenser.
Document FR 2 784 361 describes a dispenser assembly comprising a fluid dispenser having a body and a removable closure member, and packaging encasing the body while leaving the removable closure member accessible so that it can be removed or folded back on the body. However, the dispenser assembly in that document is of significant thickness which prevents it from being included in a magazine by way of an advertising sample. In contrast, the dispenser described in FR-2 791 645, whose body is made up of two plane sheets that are bonded together over their peripheries so as to define a fluid reservoir between them, can be used for such a purpose. Prior to being used, the reservoir, which contains only a tiny quantity of substance, is constrained to remain at its minimum volume, and air is prevented from entering the reservoir by the presence of the removable closure member. Thus, the body of the dispenser is of small thickness, i.e. it is no thicker than 2 mm. It can therefore be included between the pages of a magazine.
Unfortunately, it is not easy to take hold of the dispenser in Document FR-2 791 645 because none of its faces are plane. In order to dispose such a dispenser in a magazine, machines are used that are equipped with suction-pad systems which take hold of the dispensers and remove them from a bin in which they are stacked vertically. It is essential for the dispenser to have at least one substantially plane face so that it can be taken hold of by the suction-pad system. In addition, it is necessary for the dispenser to be of standard dimensions and of simple geometrical shape, e.g. square or rectangular. That makes it easier to put it in place in the bin and to unload it from the bin by means of the suction-pad system.
BRIEF SUMMARY OF THE INVENTION
An object of the present invention is to remedy the above-mentioned drawbacks of the prior art by defining a dispenser assembly that has at least one substantially plane zone enabling it to be taken hold of by means of a suction-pad system. Another object of the invention is to provide a dispenser assembly in which the packaged dispenser has a shape that is independent of the shape of the packaging. Thus, the packaged dispenser can have a shape that is very pleasing in appearance, e.g. comparable to a stylized bottle, while the packaging as a whole has a simple geometric shape so that it is suitable for being easily manipulated, stored, or issued.
To achieve these objects, the invention makes provision for the packaging to comprise a casing portion containing the body of the dispenser, and a substantially plane portion connected to the casing portion by zones of least resistance, so that the casing portion can be separated from the plane portion by breaking the zones of least resistance. The casing portion is the portion that packages the body of the dispenser, and it can have a shape of very elaborate design, while outside of the plane portion connected to the casing portion can have a simple geometrical shape, e.g. square or rectangular.
Advantageously, the plane portion surrounds the casing portion at least in part. The casing portion may also lie entirely within the plane portion, so that the casing portion occupies a central portion of the packaging and the plane portion occupies a peripheral portion surrounding the casing portion. It is also possible for the casing portion to constitute a portion of an edge of the packaging.
According to a characteristic of the invention, the packaging is provided with a first cutout in which the removable closure member is received, said first cutout being situated between the casing portion and the plane portion. Thus, after removing the casing portion, the removable closure member is completely unobstructed so that it can be easily torn off or folded back so as to unmask the dispensing orifice.
According to another characteristic, the packaging is provided with an empty second cutout at which it is possible to take hold of the casing portion so as to detach it from the plane portion, said second cutout being situated between the casing portion and the plane portion. This empty second cutout is particularly useful when the casing portion lies entirely within the plane portion: it is then possible to take hold of the casing portion by inserting a finger through the empty cutout to take hold of the casing portion at a place on its periphery.
In another advantageous embodiment of the invention, the packaging comprises a backing first sheet and a cover second sheet, the casing portion and the plane portion being formed by the backing sheet and the cover sheet connected together.
Advantageously, the sheets in the casing portion are connected together over the periphery of the casing portion, except at the removable closure member, the body of the dispenser being fixed between the two sheets. In addition, the sheets in the plane portion are connected together over the periphery of the plane portion. Preferably, the backing sheet and the cover sheet form a single piece that is folded in half along one side. The packaging can thus be made of a single sheet of paper, of card, of plastic, of metal, or of a composite of these materials, which sheet is firstly cut out and then folded in half and fixed together, e.g. by adhesive or heat-sealing. Prior to that, the dispenser is naturally disposed between the two sheets, and preferably fixed, e.g. by adhesive, to the backing sheet where it defines the casing portion, before the two packaging sheets are finally sealed. In the casing portion, the two sheets are not touching outside their peripheries, since they receive the fluid dispenser between them. However, the backing sheet and the cover sheet may be touching in the plane portion, so as to define a substantially plane surface zone suitable for being taken hold of by the suction-cup system.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is described more fully below with reference to the accompanying drawings which show an embodiment of the invention by way of non-limiting example.
In the: figures:
FIG. 1 is a perspective view of a dispenser assembly of the invention with its packaging open so as to leave the fluid dispenser visible;
FIG. 2 is a plan view of the fluid dispenser used in the dispenser assembly of FIG. 1;
FIG. 3 is a perspective view on a smaller scale of the dispenser assembly of FIG. 1 in the finished state; and
FIG. 4 is a diagrammatic perspective view of the casing portion with its dispenser and the removable closure member removed.
DETAILED DESCRIPTION
The fluid dispenser assembly of the invention comprises a fluid dispenser 1 and packaging 2 in which the dispenser 1 is received.
The dispenser 1 may be of the type described in Application FR 2 791 645 which is incorporated herein by way of reference. The dispenser 1 includes a body 10 that is substantially flat and that is made up of one or two flexible sheets bonded together over their peripheries. The two sheets of the body 10 thus together define an internal volume which serves as a fluid reservoir. Advantageously, the body is also provided with a support and dispensing part which defines a dispensing orifice and which communicates with the reservoir. In a practical embodiment, the support and dispensing part may be constituted by a piece of plastic fixed between the two sheets, e.g. by heat-sealing. This support and dispensing part may also serve to support a piece of porous material capable of becoming soaked with fluid. The piece of porous material extends inside the reservoir and it communicates directly with the outlet orifice. In addition, the reservoir may contain a spring element such as a resilient blade against which it is possible to press through the sheets. As a result, one of the sheets constitutes an actuating wall 11 or both of the sheets constitute actuating walls, against which the user presses to expel the fluid from the reservoir through the piece of porous material and through the dispensing orifice. In addition to the body 10 , the dispenser 1 further includes a removable closure member 15 which masks the dispensing orifice 12 prior to use. The removable closure member 15 may be made integrally with the support and dispensing part, or else it may be made integrally with the sheets of the body 10 . Before the removable closure member 15 is removed, the reservoir 10 is constrained to remain at its minimum volume, so that it contains almost nothing but the fluid. As soon as the removable closure member is removed, air can penetrate into the reservoir through the dispensing orifice 12 so that the spring member that is situated inside the reservoir can relax towards its rest position, thereby increasing the volume of the reservoir. By pressing on the actuating wall(s) 11 , the fluid is dispensed in two-phase manner via the dispensing orifice 12 .
A dispenser identical to the dispenser in Document FR 2 791 645 is used in the dispenser assembly of the invention, and it is shown diagrammatically in FIGS. 1 and 2. Naturally, it is possible to use other types of fluid dispenser in which the fluid is dispensed by pushing in an actuating wall. The only requirement is that the body of the dispenser must be relatively flat. In this example, the body 10 of the dispenser 1 is no thicker than in the range 2 mm to 3 mm. Naturally, the dispenser 1 is put in place in the packaging 2 with the removable closure member 15 connected to the body, so that the body 10 of the dispenser is still substantially flat and thin.
The packaging 2 is made up of two sheets of paper, of card, of plastic, of metal, or of a composite thereof. For example, it is possible to use a composite film of paper and of plastic. The two sheets referenced 21 and 25 may be exactly identical. They may also be connected together along a line 215 which serves as a hinge line and which subsequently defines an external side of the packaging. Thus, the two sheets may be made up of the same sheet folded in half along the line 215 . Naturally, it is also possible for the packaging 2 to be made up of two totally separate sheets 21 and 25 .
Each sheet 21 and 25 is precut symmetrically about the line 215 so that the precuts are superposed on one other once the sheet 25 is folded over on the sheet 21 . More particularly, the precuts essentially define two types of portion, namely a respective casing portion 23 or 27 of each of the sheets 21 and 25 , and a respective peripheral portion 22 or 26 of each of the sheets 21 and 25 . Once folded in half as shown in FIG. 3, the casing sheet portions 23 and 27 define a casing portion 3 and the peripheral sheet portions 22 and 26 define the peripheral portion 4 . The precuts on the sheets 21 and 25 may be constituted by slots 224 and 268 interrupted by bridges of material 223 , 267 . Once folded in half, the slots and the bridges of material are mutually superposed so as to form the slots 44 and the bridges of material 43 as shown in FIG. 3 . Thus, the casing portion 3 is connected to the peripheral portion 4 by the bridges of material 43 , and it is separated therefrom by the slots 44 .
Each of the sheets 21 and 25 is also provided with respective empty cutouts 211 & 212 or 251 & 252 . The empty cutouts 211 and 251 form the cutout 35 and the cutouts 212 and 252 form the cutout 34 , once the two sheets are folded over on each other as shown in FIG. 3 . The empty cutout 35 serves to receive the removable closure member 15 of the dispenser 1 , while the cutout 34 remains empty and serves as a handle recess for facilitating taking hold of the casing portion 3 for the purpose of separating it from the peripheral portion 4 along the slots 44 by breaking the bridges of material 43 .
The sheets 21 and 25 may be exactly symmetrical, but one of the sheets (sheet 21 in this example) may serve as a backing sheet for the fluid dispenser 1 , as can be seen in FIG. 1 . In other words, the dispenser 1 may be disposed on and advantageously fixed to the backing sheet 21 at its casing portion 23 . It is possible to stick one of the sheets of the body 10 to the casing sheet portion 23 by means of a suitable adhesive. The dispenser 1 is positioned on the sheet portion 23 so that its removable closure member 15 is received in the cutout 211 which, together with the symmetrical cutout 251 , forms the cutout 35 in the FIG. 3 . Thus, the dispensing orifice 12 is accurately disposed on the periphery of the cutout 35 . The periphery 230 of the casing sheet portion 23 may advantageously be coated with a suitable adhesive that extends around the dispenser 1 , as shown in FIG. 1 . Once the cover sheet 25 has been folded over onto the backing sheet 21 , the casing sheet portion 27 sticks to the casing sheet portion 23 at their corresponding peripheries. Thus, the two casing sheet portions 23 and 27 are secured to each other over their peripheries, with the dispenser 1 disposed between them. This is shown in FIG. 4, in which only the casing portion 3 is shown, with the removable closure member 15 removed so as to unmask the dispensing orifice 12 formed by the body 10 of the dispenser 1 . As its name would suggest, the casing portion 3 literally encases the body 10 of the dispenser 1 while leaving its removable closure member accessible so that it can be removed easily, thereby unmasking the dispensing orifice 12 . It is thus possible to remove the casing portion 3 from the peripheral portion 4 by breaking the bridges of material 43 along the slots 44 . The two casing sheet portions 23 and 27 are secured together while holding the dispenser 1 captive between them.
Advantageously, it is also possible to fix the peripheral sheet portions 22 and 26 together along their peripheries 260 . It is thus possible to apply a suitable adhesive along the periphery 260 of the backing sheet 21 ; it is unnecessary to apply the adhesive along the line 215 along which the sheets 21 and 25 are connected together. Once folded over and applied against each other, the outer peripheries of the peripheral sheet portions 22 and 26 are fixed together. Thus, once the casing portion 3 has been removed from the peripheral portion 4 , the peripheral sheet portions 22 and 26 remain connected together. It is possible to omit sticking the sheet portions 22 and 26 together, since the sheets 21 and 25 are already fixed to each other at the casing portion 3 .
Although it contains the body 10 of the dispenser 1 , the casing portion 3 is substantially flat and plane. Actually, the casing sheet portions 23 and 27 are slightly curved or convex. The peripheral portion 4 is substantially plane and its sheet portions 22 and 26 are touching even outside the zone where they are stuck together. The dispenser assembly can thus be taken hold of by a suction-pad system at the casing portion 3 , and even more easily at the plane peripheral portion 4 . In addition, it is very easy to apply indications such as the trademark, the ingredients, and the instructions for use of the fluid on the casing portion 3 and on the peripheral portion 4 .
It should also be noted that the shape of the casing portion 3 is totally independent of the outside shape of the peripheral portion 4 : the casing portion 3 can be very stylized, while the portion 4 can be geometrically very simple, e.g. square or rectangular. The shape of the casing portion 3 is very simple to modify or to stylize by acting on the configuration of the cutouts 44 .
In the embodiment shown in the figures, the casing portion 3 occupies a central position, while the portion 4 extends all the way around the casing portion 3 . However, it is possible to consider other forms of embodiment in which the casing portion 3 opens out on an external side of the packaging 2 so that the portion 4 surrounds the casing portion 3 in part only. It is even possible to consider a dispenser assembly in which the slots 44 and the bridges of material 43 extend rectilinearly along a single line. But preferably, for reasons of appearance, the envelope portion 3 occupies a central position, with the portion 4 extending all the way around it. In addition, the casing portion 3 is thus exactly protected by the peripheral portion 4 .
With such packaging, it is easy to store it and to take hold of it, since the packaging is relatively flat, and even exactly flat at its peripheral portion 4 , and since it has an external shape that is geometrically simple.
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A fluid dispenser assembly having, a fluid dispenser ( 1 ) defining a substantially flat body ( 10 ) provided with a dispensing orifice ( 12 ) and with a removable closure member ( 15 ) masking the dispensing orifice, packaging ( 2 ) encasing the body ( 10 ) of the dispenser while leaving the removable closure member ( 15 ) accessible so that it can be removed from the body. The dispenser assembly being characterized in that the packaging ( 2 ) comprises a casing portion ( 3 ) containing the body ( 10 ) of the dispenser; and a substantially plane portion ( 4 ) connected to the casing portion ( 3 ) by zones of least resistance ( 43 ), so that the casing portion ( 3 ) can be separated from the plane portion ( 4 ).
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FIELD OF THE INVENTION
The present invention is directed generally to an ink fountain for use in a printing machine. More particularly, the present invention is directed to an ink fountain having a plurality of ink metering elements placed side by side in the ink fountain bottom. Most specifically, the present invention is directed to an ink fountain in which the ink metering elements are each pivotably adjustable about a pivot edge. The ink fountain bottom is provided with a longitudinal gap in which are carried a plurality of laterally placed ink metering elements. These elements are capable of pivotal movement within the gap about a pivot edge formed where a side wall of the gap and the fountain bottom intersect so that the ink metering slot formed between the ink metering elements and an ink roller is adjustable by pivotal movement of the ink metering elements. Each of the ink metering elements is secured to a pivotable arm which is caused to move by a crank arm that is carried in a slot in the arm. All the arms move in a similar fashion to provide a uniform ink metering slot along the length of the ink fountain roller.
DESCRIPTION OF THE PRIOR ART
Ink fountains for printing machines are generally well known in the art. Exemplary of such inking fountains is German Unexamined Published application No. 2,814,889 and corresponding U.S. Pat. No. 4,170,177 to Iida et al. This patent discloses an ink fountain roller which contacts printing ink in a reservoir. The patent further discloses a plurality of ink metering elements which are placed side by side in direct contact with each other. These ink metering elements are placed longitudinally along the axial length of, and spaced from the peripheral surface of, the ink fountain roller. These ink metering elements are pivotably mounted and supported in the ink fountain bottom and are rigidly secured to a pivotable arm. A controllable mechanism is provided to permit adjustment of an ink metering slot formed by the ink metering elements with the surface of the ink fountain roller.
A problem with ink fountains of this type is that the ink guiding surfaces of the ink fountain bottom and of the ink metering elements are always disposed at an angle of just greater than 90° which makes cleaning of the ink fountain quite difficult. A bottom plate of the ink fountain bottom removes printing ink from the ink guiding surfaces of the ink metering elements when the ink metering elements move in the "MORE INK" direction. As the metering elements move in this direction, it is the usual occurrence that ink particles get under the bottom plate. These ink particles can adversely effect the operation of the ink metering elements thereby making the adjustment of the ink metering slot difficult. As a result the slot is not uniform across its length and variations in thickness of the ink applied to the roller result.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an ink fountain for a printing machine.
Another object of the present invention is to provide an ink fountain having multiple side by side metering elements.
A further object of the present invention is to provide an ink fountain wherein each metering element is carried by a pivotable arm.
Yet another object of the present invention is to provide an ink fountain having an adjustable metering slot.
A still further object of the present invention is to provide an ink fountain having a longitudinal gap in the bottom of the ink fountain with the metering elements being pivotable in the gap.
As will be discussed in greater detail in the description of a preferred embodiment, as set forth hereinafter, the ink fountain in accordance with the present invention is comprised generally of a plurality of ink metering elements which are pivotably carried by spaced pivotable arms. The ink metering elements are placed side by side along the length of the ink roller and spaced from the surface of the roller to form a metering slot. A particular advantage of the present invention is that it permits the formation of an opening angle between the ink guiding surfaces of the ink metering elements and the ink fountain bottom of up to 180° so that the ink fountain can be thoroughly cleaned.
Another particular advantage of the ink fountain in accordance with the present invention is that is substantially reduces movement between the surfaces to be sealed against ink leakage of the ink metering elements and the ink fountain bottom so that ink leakage is substantially eliminated. Furthermore, the relative movement of the ink metering element and the ink fountain bottom does not cause any damage to the sealing means which prevent ink leakage.
BRIEF DESCRIPTION OF THE DRAWINGS
While the novel features of the ink fountain for use in a printing machine in accordance with the present invention are set forth with particularity in the appended claims, a full and complete understanding of the invention may be had by referring to the description of a preferred embodiment as set forth hereinafter and as may be seen in the accompanying drawings in which:
FIG. 1 is a schematic side view of the ink fountain in accordance with the present invention with the ink fountain bottom and ink roller being shown in section and with the lateral end plates removed for clarity; and
FIG. 2 is a schematic front view of the ink fountain of FIG. 1 with the lateral end plates being shown.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning initially to FIG. 1, there may be seen an ink fountain generally at 1 with an ink fountain bottom member 2 provided therein. An inner bottom surface 3 of ink fountain bottom member 2 is covered with printing ink, when the ink fountain is filled with printing ink. A ceramic-coated ink fountain roller 4, which is driven in a conventional manner, plunges into the ink fountain 1. Ink metering extensions 5 of ink metering elements 6 form a slot with ink fountain roller 4 through which the printing ink passes. The ink fountain bottom 2 extends as an extension of the bottom surface 3 past all of the ink metering elements 6, thus forming a tail piece 7 having a tail face 8. A longitudinal gap 9 is provided in the ink fountain bottom 2, extending down into bottom 2 from the inner bottom surface 3. This longitudinal gap 9 preferably has a rhombus-shaped cross section and extends axially parallel to an axis of rotation of the ink fountain roller 4 near the point of closest proximity of the ink fountain roller 4 to the ink fountain bottom 2. A left guiding surface portion 12 of the longitudinal gap 9 abuts the bottom surface 3 at an angle α, which is preferably less than 90°, but which can be as great as 90°. An edge formed by the abutment of the left guiding surface 12 and the bottom surface 3 serves as a pivoting edge or pivoting line 21 for the ink metering elements 6. A right guiding surface 11 extends parallel to the left guiding surface 12 of the longitudinal gap 9, and a base surface 10 of the longitudinal gap 9 extends parallel to, and at a depth "a" below the bottom surface 3, of the ink fountain bottom 2. Vertical openings 13 in the ink fountain bottom 2 end in the base surface 10 of the longitudinal gap 9, these vertical openings 13 being spaced along the entire length "b" of the ink fountain bottom, for example, 30 mm from each other. The cross section of each of the openings 13 is dimensioned so that a pivotable arm 17 which is rigidly secured to each ink metering element 6 that extends horizontally in gap 9, is moveable in opening 13. The pivotable arm 17 can move in a preselectable pivoting motion. It is provided for this purpose with an elongated hole 18 in its lower portion. A crank pin 19 which is driven by an electric motor engages this elongated hole 18. The pivotable arm 17 pivots about the point of intersection 21 of the guiding surface 12 with the bottom surface 3 of the ink fountain bottom 2. The pivoting edge 21 for the pivotable arm 17 is also the pivoting edge for each ink metering element 6 which is rigidly secured to the upper end of a corresponding arm 17. The inner bottom surface 3 of the ink fountain bottom 2 adjoins an ink guiding surface 22 of the ink metering elements 6, so that no groove or ridge which might impede the passage of ink over both surfaces 3 and 22 is formed. Ink guiding surface 22 extends initially in a straight direction, then turns into a concave curvature, which ends in an ink metering extension 5.
A vertical surface 24 of the ink metering element forms an angle β of approximately 90° with the ink guiding surface 22 of the ink metering element 6 and ends in a first carrier extension 26. This carrier extension 26 projects downwardly approximately 1 mm below a curved rear surface 27 of the ink metering element 6. A collar 28 at the upper end of the pivotable arm 17 is rigidly and permanently joined to the rear surface 27. The rear surface 27 also includes a second carrier extension 29. The first carrier extension 26 rests upon the base surface 10, whereas the second carrier extension 29 rests upon the right guiding surface 11 of the longitudinal gap 9. The carrier extensions 26, 29 each extend preferably over the entire length "c" of the ink metering element 6 and define an angle γ of approximately 80°. The carrier extensions 26, 29 may have a rectangular cross section while their front faces or carrier surfaces 14, 15 should be as narrow as possible. The carrier extensions 26, 29 may, however, be blade-shaped, or they may have a plane front or a curved front.
A borehole 20 is positioned coaxially with each opening 13 and extends into the side opposite the bottom surface 3 of the ink fountain 1. A plane borehole bottom 31 of each extension borehole 30 forms a surface of action for a conical compression spring 32, which is slipped over the pivotable arm 17. This compression spring 32 is held between the borehole bottom 31 and a bolt 33, which projects through the cross section of the pivotable arm 17 and which bolt 33 is rigidly secured to this arm 17. Both carrier extensions 26, 29 and thus the ink metering element 6 are pulled by the compression spring 32 towards the base surface 10 or the right guiding surface 11 of the longitudinal gap 9, respectively.
An elastic sealing membrane 34 which may be, for example, convex, is inserted between the borehole bottom 31 and the compression spring 32. This sealing membrane 34 has an aperture which sealingly engages the pivotable arm 17, sealing it completely. A sealing effect for the ink fountain bottom 2 is secured by pressing the edge of the sealing membrane 34 against the borehole bottom 31 by means of the compression spring 32. A narrow longitudinal groove 36, which extends the whole length "c" of the ink metering elements 6, is provided in a rear part 16 of each of the ink metering elements 6, above the second carrier extension 29, and receives a first lateral edge 38 of an elastic sealing strip 37 to seal the vertical openings 13 from the ink fountain roller 4. A second lateral edge 35 of the elastic sealing strip 37 is secured to the tail surface 8 of the ink fountain 2 thereby sealing this tail surface 8 of the ink fountain 2. The sealing strip 37 extends as a single element over the entire length "b" of the ink fountain bottom 2, and thus over all the ink metering elements 6 of the ink fountain 1, which are disposed side by side.
An axial groove 39 which extends along the entire length "c" of the ink metering elements 6 and parallel to the axis of rotation of ink fountain roller 4 is located in the vertical surface 24 of the ink metering elements 6 approximately 1 mm below the ink guiding surface 22. This groove 39 receives an elastic sealing cord 41 having, for example, a rectangular cross section. This sealing cord 41 extends without breaks over the length "b" of gap 9. It is of a suitable size so that in every operating position of the ink metering elements 6, the left guiding surface 12 of the longitudinal gap 9 is safely sealed to the vertical surface 24 of the ink metering element 6.
A lubricant chamber 43 which is defined and sealed by the sealing strip 37, a right side face 40 of the opening 13, the sealing membrane 34, a left side face 42 of the opening 13, the base surface 10, the left guiding surface 12, the sealing cord 41, the surfaces 24 and 27 of the ink metering element 6 facing the longitudinal gap 9, and by two lateral end plates 49 and 50, as seen in FIG. 2, extends over the length "b" of the gap 9, and is completely filled with a lubricating means, for example, grease. Printing ink or dirt is thus prevented from penetrating the lubricating means chamber 43 and cannot handicap the operation of the ink metering elements 6.
Each ink metering element 6 is provided with a through borehole 44 in its center. This borehole 44 ends on either front side 45, 46 of ink metering element 6, in a lubricating groove 47, 48 respectively. Every lubricating groove 47, 48 extends within the surface limits of the front sides 45, 46 and is approximately 10 mm long, 2 mm wide, and 0.5 mm deep. A grease nipple 20 is provided on the lateral end plate 49, through which grease can be forced into the boreholes 44 of the ink metering elements 6. An outlet nipple 25, which is capable of being closed and opened, is provided on the second lateral end plate 50, through which waste grease can be forced out. Since all the boreholes 44 of the ink metering elements are in connection with each other, it is possible to press grease through them in a way that the grease is pressed out between the front sides 45, 46 of adjacent ink metering elements 6, and thus dirt and ink pigments which may have accumulated between adjacent elements 6 are simultaneously pressed out.
In operation, the crank pins 19 are all caused to rotate by the electric drive motor (not shown), such motion causing the solid pivot arms 17 to pivot about pivot edge 21 whereby the ink metering elements 6, which are rigidly connected to pivotable arms 17, also pivot about pivot edge or line 21 to adjust the spacing between ink metering extension 5 and ink fountain roller 4. The ink in the ink fountain flows smoothly along the inner bottom surface 3 of ink fountain bottom 2 and along the curving ink guiding surface 22. The lubricating means chamber 43 is sealed by seal 41, by elastic sealing strip 37 and by elastic sealing membrane 34 so that no dirt or ink can get into the longitudinal gap 9. Thus the several ink metering elements 6 which are disposed side by side in gap 9 can operate smoothly and in uniformity to meter the ink applied to roller 4. Similarly, the lubricant which is forced through lubricant hole 44 in each metering element 6 and out through the lubricant grooves 47 and 48 keeps particles of dirt and ink from between end faces 45 and 46 of adjacent ink metering elements 6. Accordingly, the ink fountain in accordance with the present invention includes a plurality of individual ink metering elements which cooperate to uniformly meter ink on an ink roller. Furthermore, the ink fountain in accordance with the present invention allows the ink metering elements to operate smoothly and to remain dirt and ink free.
While an ink fountain for printing machines having means to maintain smooth operation of the ink metering elements in accordance with the present invention has been fully and completely described hereinabove, it will be obvious to one of ordinary skill in the art that a number of changes in, for example, the number of metering elements, the means for pivoting the arms, the securement means for the spring and the like may be made without departing from the true spirit and scope of the invention and that the invention is to be limited only by the following claims.
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An ink fountain for a printing machine is disclosed. A plurality of ink metering elements are placed side by side in a longitudinal gap in the bottom surface of an ink fountain with the gap being parallel to the axis of rotation of the ink roller. Each ink metering element includes an ink guiding surface which terminates in an ink metering extension that is adjustably spaced from the surface of the ink roller. Each of the ink metering elements is rigidly secured to a pivotable arm which extends through an opening in the ink fountain in a direction away from the inner bottom surface of the fountain. Pivoting of the arms causes the ink metering elements to pivot about a pivot line defined by the intersection of the inner bottom surface of the fountain bottom and a first edge of the longitudinal gap. Movement of the ink metering elements changes the space between the fountain roller and the ink metering extension thereby controlling the amount of ink carried out of the fountain by the ink fountain roller.
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TECHNICAL FIELD
[0001] The present application relates to the technical field of daily electronic products, and more particularly, relates to an atomization assembly and an electronic cigarette.
BACKGROUND
[0002] Electronic cigarettes are used for smoking cessation and substitute for traditional cigarettes. An electronic cigarette available in the market includes a battery assembly and an atomization assembly. The battery assembly includes a battery of which two ends are provided with a positive pole and a negative pole respectively, and a control board. The control board is further integrated with components including a gas flow sensor, a control circuit and the like. The atomization assembly includes heating wires and tobacco tar. When a smoking action is taking place, the control board controls the battery to supply power to the atomization assembly, thereby driving the heating wires to give out heat to further produce smoke.
[0003] Therefore, the battery of the electronic cigarette needs to supply power to the control board and the atomization assembly. In order to make the battery supply power to the control board and atomization assembly, the battery needs to be connected to the control board via wires by means of soldering in order to achieve an electrical connection between the battery and the control board. Besides, corresponding wires need to be soldered between the battery and the atomization assembly, in order to achieve a conduction therebetween.
[0004] However, in an existing electronic cigarette, during the assembly of the battery, the wires are soldered manually; therefore, the assembly thereof is inconvenient and time-consuming, which is bad for the automatic production of the electronic cigarette, and the efficiency is low.
[0005] Electronic cigarettes are used for smoking cessation and substitute for traditional cigarettes. An electronic cigarette available in the market includes a battery assembly and an atomization assembly. The battery assembly includes a battery and a control module, and the control module is further integrated with components including a gas flow sensor, a control circuit and the like. When smoking via a suction nozzle cover of the atomization assembly, the control module controls the battery to supply power to the atomization assembly, thereby driving the heating wires to give out heat to further produce smoke.
[0006] In the prior art, generally, the suction nozzle cover is directly mounted on an outer sleeve. However, various defects are inevitably occurred on surfaces of the suction nozzle cover and the outer sleeve; besides, deviations exist in shapes and dimensions respectively of the suction nozzle cover and the outer sleeve. Therefore, a gap will be inevitably formed at a junction between the suction nozzle cover and the outer sleeve. However, the suction nozzle cover does not have a sealing function, and thus the tobacco tar will leak out via the gap when pressure differences exist on two sides of the junction. In other cases, in the prior art, a movable sealing component is arranged or sleeved on the suction nozzle cover. However, since the sealing ring is movably mounted, frequently, the sealing ring is not arranged in place, thereby causing a leakage of tobacco tar, and thus the user experience is poor.
BRIEF SUMMARY
[0007] The objective of the present application is to provide an electronic cigarette of which the suction nozzle cover has a good sealing effect, aiming at the detects in the prior art that the suction nozzle cover of the electronic cigarette does not have the sealing function.
[0008] In accordance with one aspect of the present application, an atomization assembly is constructed, which is configured to be assembled with a battery assembly to form an electronic cigarette, wherein the atomization assembly comprises an outer sleeve and a suction nozzle cover inserted at one end of the outer sleeve; wherein a sealing component, which is fixedly connected to the suction nozzle cover, is protruded radially from a circumferential outer side wall of the suction nozzle cover, and the outer side wall is in contact with the outer sleeve, and a hardness of the sealing component is smaller than that of the suction nozzle cover.
[0009] In the atomization assembly of the present application, wherein the outer side wall of the suction nozzle cover is attached to an inner side wall of the outer sleeve; the sealing component extends from the outer side wall of the suction nozzle cover in a direction away from a central axis of the outer sleeve, and is further abutted against the inner side wall of the outer sleeve.
[0010] In the atomization assembly of the present application, wherein the sealing component is coaxially sleeved on the circumferential outer side wall of the suction nozzle cover, and the sealing component and the inner side wall of the outer sleeve form interference fit.
[0011] In the atomization assembly of the present application, wherein at least one groove adapted to the sealing component is defined on the circumferential outer side wall of the suction nozzle cover;
[0012] the sealing component is coaxially sleeved in the groove, and the sealing component and the inner wall of the outer sleeve form interference fit.
[0013] In the atomization assembly of the present application, wherein a plurality of grooves are provided; the plurality of grooves are parallel to each other, and are separately arranged on an outer wall of the connection portion; each of the grooves is coaxial with the suction nozzle cover.
[0014] In the atomization assembly of the present application, wherein the suction nozzle cover is fixed together with or integrated with the sealing component into one piece by means of double-shot molding or bonding; a cross-section of the sealing component is in shape of an “O”, a “V”, or a “Y”.
[0015] In the atomization assembly of the present application, wherein a vent pipe is defined in the outer sleeve; the vent pipe is communicated with air holes defined in the suction nozzle cover to form a smoke channel.
[0016] In the atomization assembly of the present application, wherein the suction nozzle cover is in shape of a hollow barrel adapted to the outer sleeve; the air holes are defined in the suction nozzle cover, and the air holes are second air holes.
[0017] In the atomization assembly of the present application, wherein the suction nozzle cover includes a cover body opposite to an opening end face of the outer sleeve, and a connection portion embedded in the outer sleeve.
[0018] In the atomization assembly of the present application, wherein the connection portion is in shape of a hollow cylinder adapted to the outer sleeve; a second air hole is defined in the connection portion;
[0019] the air holes further include a first air hole communicated with the second air hole; the first air hole is defined on an end face of the cover body, and a central axis of the first air hole is aligned with or deviated from a central axis of the outer sleeve;
[0020] a flange is formed by extending from an edge of the cover body in a radial direction of the cover body; the flange is abutted against a side edge on an opening end face of the outer sleeve.
[0021] In the atomization assembly of the present application, wherein a boss is formed by extending from a central portion on an end face of the cover body that faces to the vent pipe in an axis direction of the cover body; the boss is coaxial with the connection portion; a first air hole coaxial with the boss is further defined in a central portion of the boss.
[0022] In the present application, an electronic cigarette is further provided, which comprises an atomization assembly, the atomization assembly includes an outer sleeve and a suction nozzle cover inserted at one end of the outer sleeve; wherein a sealing component, which is fixedly connected to the suction nozzle cover, is protruded radially from a circumferential outer side wall of the suction nozzle cover, and the outer side wall is in contact with the outer sleeve, and a hardness of the sealing component is smaller than that of the suction nozzle cover.
[0023] In the electronic cigarette of the present application, wherein the outer side wall of the suction nozzle cover is attached to an inner side wall of the outer sleeve; the sealing component extends from the outer side wall of the suction nozzle cover in a direction away from a central axis of the outer sleeve, and is further abutted against the inner side wall of the outer sleeve.
[0024] In the electronic cigarette of the present application, wherein the sealing component is coaxially sleeved on the circumferential outer side wall of the suction nozzle cover, and the sealing component and the inner side wall of the outer sleeve form interference fit.
[0025] In the electronic cigarette of the present application, wherein at least one groove adapted to the sealing component is defined on the circumferential outer side wall of the suction nozzle cover;
[0026] the sealing component is coaxially sleeved in the groove, and the sealing component and the inner wall of the outer sleeve form interference fit.
[0027] In the electronic cigarette of the present application, wherein a plurality of grooves are provided; the plurality of grooves are parallel to each other, and are separately arranged on an outer wall of the connection portion; each of the grooves is coaxial with the suction nozzle cover.
[0028] In the electronic cigarette of the present application, wherein the suction nozzle cover is fixed together with or integrated with the sealing component into one piece by means of double-shot molding or bonding; a cross-section of the sealing component is in shape of an “O”, a “V”, or a “Y”.
[0029] In the electronic cigarette of the present application, wherein a vent pipe is defined in the outer sleeve; the vent pipe is communicated with air holes defined in the suction nozzle cover to form a smoke channel.
[0030] In the electronic cigarette of the present application, wherein the electronic cigarette further includes a battery assembly; the atomization assembly and the battery assembly are integrated with each other into one piece, or detachably connected to each other.
[0031] When implementing the electronic cigarette of the present application, the following advantageous can be achieved: the suction nozzle cover is fixed together with or integrated with the sealing component into one piece by means of double-shot molding, bonding or the like. In this way, the assembly of the suction nozzle cover is facilitated, and it is possible to avoid the leakage of the tobacco tar caused by not arranging the sealing component in place in the prior art. In this way, the suction nozzle cover has a sealing function, and a gap between the engagement surfaces of the suction nozzle cover and the outer sleeve is sealed, by which the leakage channel is cut off, and thus the leakage of the tobacco tar is prevented.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] The present application will be further described with reference to the accompanying drawings and embodiments in the following, in the accompanying drawings:
[0033] FIG. 1 is a schematic view of an atomization assembly provided in a first preferred embodiment of the present application;
[0034] FIG. 2 is a schematic view of a suction nozzle cover of the atomization assembly shown in FIG. 1 ;
[0035] FIG. 3 is a schematic view of the atomization assembly shown in FIG. 1 , in which case a sealing component is sleeved on the suction nozzle cover;
[0036] FIG. 4 is a schematic view of an atomization assembly provided in a second preferred embodiment of the present application;
[0037] FIG. 5 is a schematic view of a suction nozzle cover of the atomization assembly shown in FIG. 4 ;
[0038] FIG. 6 is a schematic view of an atomization assembly provided in a third preferred embodiment of the present application;
[0039] FIG. 7 is a schematic view of a suction nozzle cover of the atomization assembly shown in FIG. 6 ; and
[0040] FIG. 8 is a schematic view of an atomization assembly provided in a fourth preferred embodiment of the present application.
[0041] In figures:
[0000]
1 outer sleeve
11 vent pipe;
2 suction nozzle cover
20 cover body
21 connection portion;
22 flange
23 boss
24 first air hole;
25 second air hole
26 groove;
3 sealing component.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0042] In order to make the technical features, the propose and the technical effect of the present application more clearly, the specific implemental means of the present application will now be described in detail with reference to the accompanying drawings.
[0043] As shown in FIG. 1 , in a first preferred embodiment of the present application, an atomization assembly is provided, which is configured to be assembled with a battery assembly (not shown in the figures) to form an electronic cigarette. The atomization assembly includes an outer sleeve 1 , a suction nozzle cover 2 and a sealing component 3 . In this case, a hardness of the sealing component is smaller than that of the suction nozzle cover 2 . The outer sleeve 1 is substantially in shape of a hollow cylinder, and a vent pipe 11 or the like is defined inside the outer sleeve. The vent pipe 11 is communicated with air holes defined in the suction nozzle cover 2 to form a smoke channel.
[0044] As shown in FIG. 1 and combing with FIG. 2 , the suction nozzle cover 2 is substantially in shape of a hollow barrel, and the suction nozzle cover 2 is further embedded in one end of the outer sleeve 1 , the end is close to the vent pipe 11 . A sealing component 3 , which is fixedly connected to the suction nozzle cover 2 , is protruded radially from a circumferential outer side wall of the suction nozzle cover 2 in contact with the outer sleeve 1 . The outer side wall of the suction nozzle cover 2 is attached to an inner side wall of the outer sleeve 1 . The sealing component 3 extends from the outer side wall of the suction nozzle cover 2 in a direction away from a central axis of the outer sleeve 1 , and is further abutted against the inner side wall of the outer sleeve 1 .
[0045] As shown in FIG. 2 , the suction nozzle cover 2 includes a cover body 20 opposite to an opening end face of the outer sleeve 1 , and a connection portion 21 embedded in the outer sleeve 1 . The cover body 20 is integrated with the connection portion 21 .
[0046] The suction nozzle cover 2 further includes a flange 22 , a first air hole 24 , a second air hole 25 and a groove 26 . In this case, the connection portion 21 is arranged at an edge portion of one end face of the cover body 20 that faces towards the vent pipe 11 , and further extends along an axis direction of the cover body 20 . A cross-section of the connection portion 21 and a cross-section of the cover body 20 are of the same shape. The connection portion 21 is substantially in shape of a hollow barrel adapted to the outer sleeve 1 . The connection portion 21 is inserted into the outer sleeve 1 adapted thereto, such that the connection portion 21 is connected to the outer sleeve 1 by a plug connection. A second air hole 25 configured for the smoke to flow through is further defined in the connection portion 21 .
[0047] Furthermore, a flange 22 is formed by extending from an edge of the cover body 20 in a radial direction of the cover body 20 . When the connection portion 21 is inserted into the outer sleeve 1 adapted thereto, the flange 22 is abutted against a side edge of the opening end face of the outer sleeve 1 , and thus the suction nozzle cover 2 is effectively prevented from sliding into the outer sleeve 1 . A first air hole 24 is further defined in the cover body 20 . In this case, the first air hole 24 is a hole in shape of a cylinder, and an axis thereof is aligned with or deviated from the central axis of the outer sleeve 1 . In this embodiment, an axis of the first air hole 24 is preferably aligned with the central axis of the outer sleeve 1 . In this case, the vent pipe 11 , the second air hole 25 and the first air hole 24 are communicated with each other to form a smoke channel, in order to provide smoke for a user to suck in.
[0048] As shown in FIG. 3 combining with FIG. 2 , at least one groove 26 adapted to the sealing component 3 is defined on a circumferential outer side wall of the connection portion 21 , in order to reliably fix the sealing component 3 . When a plurality of grooves 26 are provided, the plurality of grooves 26 are parallel to each other, and are separately arranged on an outer wall of the connection portion 21 , and a central axis of each of the grooves 26 is aligned with a central axis of the connection portion 21 . The sealing component 3 is coaxially sleeved in the groove 26 ; besides, the sealing component 3 and the inner wall of the outer sleeve 1 form interference fit. A cross-section of the sealing component 3 is in various shapes. In this case, the cross-section of the sealing component 3 may be designed in a shape adapted to the groove 26 and the outer sleeve 1 , according to the structures of the groove 26 and the outer sleeve 1 . For example, the cross-section of the sealing component 3 in this case may be in shape of an “O”, a “V”, a “Y” or the like. It can be understood that, in other embodiments, it is also possible for the connection portion 21 to have no grooves 26 defined therein, and the sealing component 3 is directly coated on a whole peripheral face of the connection portion 21 .
[0049] During the practical producing process, the suction nozzle cover 2 is fixed together with or integrated with the sealing component 3 into one piece by means of double-shot molding, bonding or the like. In this way, the assembly of the suction nozzle cover 2 is simplified, and it is possible to avoid the leakage of the tobacco tar caused by not arranging the sealing component in place. When employing this structure, the suction nozzle cover 2 may be made from hard gel materials such as plastic, while the sealing component 3 may be made from soft gel materials such as silicon.
[0050] The atomization assembly provided in the first present embodiment of the present application is configured to be assembled with the battery assembly (not shown in figures) to form an electronic cigarette. It is possible for the atomization assembly to be integrated with the battery assembly, that is, the atomization assembly and the battery assembly share a same outer sleeve. However, in other embodiments, it is also possible for the atomization assembly to be detachably connected to the battery assembly. The battery assembly in this case belongs to prior art, and will not be described in detail here.
[0051] During the assembly process, the suction nozzle cover 2 sleeved with the sealing component 3 is inserted into the outer sleeve 1 , and the sealing component 3 and the outer sleeve 1 form interference fit. In this way, a gap is effectively avoided from being formed between the suction nozzle 2 and the outer sleeve 1 , and the tobacco tar is prevented from leaking out.
[0052] FIG. 4 shows an atomization assembly according to a second preferred embodiment of the present application, and the atomization assembly is configured to be assembled with a battery assembly to form an electronic cigarette. The differences between the atomization assembly in the second embodiment and that in the first embodiment lie in that, the structures of the cover bodies 20 are different.
[0053] As shown in FIG. 5 , a boss 23 coaxial with the outer sleeve 1 is formed on a central portion on an end face of the cover body 20 , the end face faces to the atomization assembly, and extends in an axis direction of the cover body 20 . The boss 23 is in shape of a cylinder, and is cooperated with the second air hole 25 described above to achieve a secondary condensation and recycle of the tobacco tar. A first air hole 24 coaxial with the boss 23 is further defined in a central portion of the boss 23 . The first air hole 24 is in shape of a cylinder. In this case, the vent pipe 11 , the second air hole 25 and the first air hole 24 are communicated with each other to form a smoke channel, in order to provide smoke for a user to suck in.
[0054] FIG. 6 shows an atomization assembly according to a third preferred embodiment of the present application, and the atomization assembly is configured to be assembled with a battery assembly to form an electronic cigarette. The differences between the atomization assembly in the third embodiment and that in the first embodiment lie in that, the structures of the connection portions 21 are different.
[0055] As shown in FIG. 6 and combing with FIG. 7 , the sealing component 3 is coaxially sleeved on a circumferential outer side wall of the connection portion 21 , and the sealing component 3 and an inner side wall of the outer sleeve 1 form interference fit. The connection portion 21 is fixed together with or integrated with the sealing component 3 into one piece by means of double-shot molding, bonding or the like.
[0056] FIG. 8 shows an atomization assembly according to a fourth preferred embodiment of the present application, and the atomization assembly is configured to be assembled with a battery assembly to form an electronic cigarette. The differences between the atomization assembly in the third embodiment and that in the first embodiment lie in that, the structures of the suction nozzle covers 2 are different.
[0057] As shown in FIG. 8 , the suction nozzle cover 2 is in shape of a hollow cylinder adapted to the outer sleeve 1 , and a second air hole 25 is defined in the suction nozzle cover 2 . The vent pipe 11 and the second air hole 25 are communicated with each other to form a smoke channel, in order to provide smoke for a user to suck in.
[0058] Although the present application is illustrated with the embodiments accompanying the drawings, however, it should be understood that, those skilled in the art may make many alternatives or equivalents, without going beyond the scope the claims intend to protect of the present application. Besides, many modifications may be made aiming at specific situation or materials, without going beyond the scope the claims intend to protect of the present application. Therefore, the present application is not limited to the specific embodiments disclosed herein, and the present application should include all the implementations fallen in the protection scope of the claims of the present application.
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An atomization assembly and electronic cigarette are provided. The atomization assembly is used for combining with a battery assembly to form an electronic cigarette. The atomization assembly comprises an outer sleeve ( 1 ), and a suction nozzle cover ( 2 ) inserted at one end of the outer sleeve ( 1 ). A sealing component ( 3 ), which is fixedly connected to the suction nozzle cover ( 2 ), is provided and protrudes radially from a circumferential outer side wall of the suction nozzle cover ( 2 ). The hardness of the sealing component ( 3 ) is smaller than that of the suction nozzle cover ( 2 ). The suction nozzle cover ( 2 ) is integrated with the sealing component ( 3 ) into one piece by double-shot molding, so that the suction nozzle cover ( 2 ) has a sealing function. A gap between the engagement surfaces of the suction nozzle cover ( 2 ) and the outer sleeve ( 1 ) is sealed, thereby preventing leakage.
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CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a divisional application of copending U.S. application Ser. No. 10/971,825, filed on Oct. 22, 2004.
FIELD OF THE INVENTION
The present invention relates, in general, to fluorescent marker molecules and, more specifically, to the preparation of highly fluorescent polyurethane compounds which are the reaction products of an isocyanate with fluorescent or non-fluorescent reactive polymers. These highly fluorescent polyurethane compounds provide unique markers for identifying the sources of component raw materials in fluids, fluid blends and solid compositions.
BACKGROUND OF THE INVENTION
Various colorants and dyes have been used to authenticate the composition and/or source of fluids and plastic articles. In some cases, it is preferable to use a marker or tag that is not detectable by the human eye so as to avoid interference with colored materials or to avoid detection of the additive. In such cases, it may be desirable to use marker compounds containing fluorophores that fluoresce or emit light in the ultraviolet or infrared region after excitation with an appropriate light source. For instance, U.S. Pat. Nos. 4,303,701 and 4,329,378 disclose methods for marking plastic lenses by impregnating them with fluorescent materials that do not respond to sunlight or normal visible light.
Luttermann et al., in U.S. Pat. No. 5,201,921 teach a process for identifying polyolefin plastics using lipophilic fluorescent dyes in concentrations suitable to minimize color distortions.
Markers are also becoming particularly important for protecting brand integrity for consumers. Such markers must be readily detectable at relatively low concentrations in the product. In the petroleum industry, markers are also useful for ensuring compliance with governmental regulations. For example, products such as diesel fuels, gasoline and heating oils often contain visible dyes or colorless fluorescent compounds that identify the intended use, tax status, or brand name of the product. Such markers are well known to those skilled in the art.
In addition, petroleum product markers must also fulfill other criteria such as being:
(1) soluble in hydrocarbon solvents; (2) resistant to leaching from the petroleum product by water or water that is strongly acidic or basic; (3) relatively chemically inert so as to avoid loss of color or fluorescence when in contact with other petroleum additives or water; and (4) free from interference from naturally occurring compounds already present in the petroleum product.
A number of artisans have attempted to provide acceptable fluorescent markers for use in the petroleum industry. For example, Smith, in U.S. Pat. No. 5,498,808, teaches the use of colorless fluorescent petroleum markers which are based on esterified derivatives of xanthene compounds such as fluorescein. One drawback to the markers of Smith is that fuels containing these markers must be treated with alkaline developing solutions to generate the visibly fluorescent chromophore. Other markers such as the phthalocyanine and naphthalocyanine dyes, disclosed in U.S. Pat. Nos. 5,804,447, 5,998,211 and 6,312,958, can be detected directly by their fluorescence in the near infrared (IR) region between 600 to 1,200 nm where naturally occurring components in the petroleum product will not interfere.
Carbamates or urethanes prepared with aromatic isocyanates are known to fluoresce in the ultraviolet region between 300 and 400 nm depending upon the substitution pattern of the isocyanate, solvent, and the alcohol used. Because petroleum compounds typically exhibit considerable background fluorescence at these wavelengths, urethanes have heretofore tended to be excluded from consideration as markers.
U.S. Pat. Nos. 3,844,965 and 4,897,087 disclose lubricating oil additives and ash less fuel detergents or dispersants which are said to be the reaction products of a polyether polyol and an aliphatic hydrocarbyl amine or polyamine with a polyisocyanate (i.e., polyether urethaneureas). Polyether urethane polyamines prepared from hydroxyalkylated polyamines, a polyisocyanate, and a polyether can be used as fuel additives with enhanced oxidative stability as taught by Blain et al. in U.S. Pat. No. 5,057,122. However no mention is made in any of these patents about the use of these compounds as fluorescent markers and no methods of enhancing their fluorescent response is discussed.
Polyether polyurethanes without active hydrogens have been used as plasticizers in U.S. Pat. Nos. 4,824,888, 5,525,654, and 6,403,702. These compounds are essentially diurethanes prepared by:
1) reaction of difunctional polypropylene glycol with a monoisocyanate or 2) reaction of a monofunctional monalkyl ether of polypropylene glycol with a diisocyanate.
Pantone et al., in U.S. Pat. No. 6,384,130, disclose another class of plasticizers that are the reaction products of an isocyanate-terminated prepolymer and a monofunctional alcohol. These compounds contain more than two urethane groups and the prepolymers may have a functionality greater than 2.0. The polyethers disclosed by Pantone et al. to make the polyurethanes do not contain fluorophores.
Reactive dyestuffs or colorants for plastics based on alkoxylated chromophores such as azo, triphenylmethane, and anthraquinone derivatives are disclosed in U.S. Pat. Nos. 4,284,729 and 4,846,846. The polyether derivatives provide non-migrating visible color to polyurethane articles by chemically reacting with isocyanates in the blend to become part of the polymer network. Again, no mention is made in any of these patents about the use of these compounds as fluorescent markers and no methods of enhancing or controlling their fluorescent response is discussed.
Thus, a need continues to exist in the art for colorless markers. It would be desirable if such markers had molecular structures that can be readily modified to provide fluorescence in the ultraviolet, visible, or near infrared (IR) region of the electromagnetic spectrum.
SUMMARY OF THE INVENTION
The present invention provides such markers in the form of highly fluorescent polymeric urethane or urea derivatives that fluoresce in the ultraviolet or near infrared region without being visible to the human eye at low concentrations in the fluid or article being marked. These highly fluorescent markers can be detected by techniques such as liquid or gel permeation chromatography coupled with appropriate detectors. The marker compounds are compatible with an extensive variety of materials, including petroleum products. The molecular weight and fluorescence emission wavelength of the compounds can be readily adjusted to provide a multitude of markers having unique fluorescence signatures. In addition, because the marker compounds are highly fluorescent, less of the particular compound is needed to provide an identifying signal.
These and other advantages and benefits of the present invention will be apparent from the Detailed Description of the Invention herein below.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described for purposes of illustration and not limitation. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, functionalities and so forth in the specification are to be understood as being modified in all instances by the term “about”. Equivalent weights and molecular weights given herein in Daltons (Da) are number average equivalent weights and number average molecular weights respectively, unless indicated otherwise.
The present invention provides a highly fluorescent compound containing the reaction product of at least one fluorophore-containing reactive polymer, optionally containing a polyamine unit of the formula NCH 2 CH 2 N and at least one unsubstituted or substituted aryl isocyanate or an unsubstituted or substituted aliphatic or cycloaliphatic isocyanate, at an isocyanate index of 100 or less, wherein the highly fluorescent compound emits fluorescence in the ultraviolet (UV), visible, or near infrared (IR) region.
The present invention further provides a process for producing a highly fluorescent compound involving reacting at least one fluorophore-containing reactive polymer, optionally containing a polyamine unit of the formula NCH 2 CH 2 N and at least one unsubstituted or substituted aryl isocyanate or an unsubstituted or substituted aliphatic or cycloaliphatic isocyanate, at an isocyanate index of 100 or less, wherein the highly fluorescent compound emits fluorescence in the ultraviolet (UV), visible, or near infrared (IR) region.
The present invention still further provides a process for marking one of a fluid, a fluid blend or a solid composition, involving adding to the one of a fluid, a fluid blend or a solid, the reaction product of at least one fluorophore-containing reactive polymer, optionally containing a polyamine unit of the formula NCH 2 CH 2 N and at least one unsubstituted or substituted aryl isocyanate or an unsubstituted or substituted aliphatic or cycloaliphatic isocyanate, at an isocyanate index of 100 or less, wherein the reaction product emits fluorescence in the ultraviolet (UV), visible, or near infrared (IR) region.
The present invention yet further provides a process for marking one of a fluid, a fluid blend or a solid composition, involving adding to the one of a fluid, a fluid blend or a solid, the reaction product of at least one non-fluorophore-containing reactive polymer, optionally containing a polyamine unit of the formula NCH 2 CH 2 N and at least one unsubstituted or substituted aryl isocyanate, at an isocyanate index of 100 or less, wherein the reaction product emits fluorescence in the ultraviolet (UV), visible, or near infrared (IR) region.
The highly fluorescent inventive polymeric urethane or urea derivatives fall into two classes depending upon the fluorescence characteristics of the active hydrogen compound and the type of isocyanate used.
Class I. The reaction product of a reactive polymer containing a fluorescent chromophore and an aromatic isocyanate, represented by the formula (I) below:
wherein
F represents a fluorophore;
P represents a polymeric moiety, optionally containing a polyamine unit of the formula NCH 2 CH 2 N;
X represents a reactive heteroatom chosen from O, N, and S;
n represents the number of reactive heteroatoms;
R 1 represents an unsubstituted or substituted aryl moiety; and
y represents the number of isocyanate groups.
Class II. The reaction product of a reactive polymer containing a fluorescent chromophore and an aliphatic or cycloaliphatic isocyanate, represented by the formula (II) below:
wherein,
F represents a fluorophore;
P represents a polymeric moiety, optionally containing a polyamine unit of the formula NCH 2 CH 2 N;
X represents a reactive heteroatom chosen from 0, N, and S;
n represents the number of reactive heteroatoms;
R 2 represents an unsubstituted or substituted aliphatic or cycloaliphatic moiety; and
y represents the number of isocyanate groups.
Also suitable as markers in the inventive methods are those polymeric urethane or urea derivatives which do not contain a fluorophore, but do contain an aromatic group in the isocyanate moiety, and are herein designated as Class III compounds.
Class III. The reaction product of a reactive polymer not containing a fluorescent chromophore and an aromatic isocyanate, represented by the formula (III) below:
wherein,
P represents a non-fluorophore-containing polymeric moiety, optionally containing a polyamine unit of the formula NCH 2 CH 2 N;
X represents a reactive heteroatom chosen from 0, N, and S;
n represents the number of reactive heteroatoms;
R 3 represents an unsubstituted or substituted aryl moiety; and represents the number of isocyanate groups.
y represents the number of isocyanate groups.
The highly fluorescent marker compounds of these three classes preferably have a molecular weight greater than 300 Da, more preferably between 1,000 and 50,000. The excitation wavelength to induce fluorescence is preferably greater than 210 nm and the emission wavelength is preferably greater than 290 nm. Surprisingly, the relative fluorescence of the marker compounds is greater than that expected from the simple addition of the fluorescence of the reactant fluorophores and, in some cases, may be up to seven times as much as expected. This allows for the use of greatly reduced amounts of the compounds as markers.
It is preferred that neither the reactive polymer nor the isocyanate absorb light in the visible region to the extent that any significant color is observed, but the reaction product may fluoresce in the ultraviolet below 400 nm, in the visible region, or in the near infrared above 700 nm. The highly fluorescent marker compounds are not intended to become chemically bound to the matrix in which they are used.
The chemical composition of the reactive polymer is not critical, but the reactive polymer should be soluble in the matrix in which it is to be used. Although polyesters are suitable, polyethers based on alkylene oxides or combinations of alkylene oxides such as ethylene oxide, propylene oxide, or butylenes oxide are preferred. The molecular weight of the reactive polymer should be such that the fluorescence intensity of its reaction product with an isocyanate allows detection of the compound at concentrations below 100 ppm. Preferably, the reactive polymer has a molecular weight in the range of 250 to 40,000 Da, more preferably in the range of 500 to 20,000 Da. Additionally, the functionality or number of active hydrogen atoms per molecule of reactive polymer may vary from 1 to 8. The chain length of the reactive polymer and the fluorophore may be chosen to adjust respectively the chromatographic behavior and fluorescent emission wavelength for the compound as desired. Reactive heteroatoms as used herein refers to oxygen, nitrogen or sulfur atoms of the reactive polymer which had reactive hydrogen atoms prior to reaction with the isocyanate in forming the highly fluorescent compound.
Fluorophores and methods of making them are known in the art. The fluorophore may be attached to the reactive polymer via any type of linking group such as an ester, amide, ether, etc., by means known to those skilled in the art.
In the case of the inventive Class I or the Class III compounds, the aromatic isocyanate may be mono or polyfunctional depending upon the desired molecular architecture of the reaction product. Suitable isocyanates include, but are not limited to, 4,4′-diphenylmethane diisocyanate (MOO, polymeric MOI (PMDI), toluene diisocyanate, allophanate-modified isocyanates, phenyl isocyanate, naphthalene isocyanate, naphthalene diisocyanate, isocyanate-terminated prepolymers and carbodiimide-modified isocyanates.
In the case of the inventive Class II compounds, suitable aliphatic or cycloaliphatic isocyanates include, but are not limited to, 1,6-hexamethylene-diisocyanate; isophorone diisocyanate; 2,4- and 2,6-hexahydrotoluenediisocyanate, as well as the corresponding isomeric mixtures; 4,4′-, 2,2′- and 2,4′-dicyclohexylmethanediisocyanate and 1,3 tetramethylene xylene diisocyanate.
As will be apparent to those skilled in the art, the inventive marker compounds may be made including various combinations of reactive polymers and isocyanates.
For the inventive marking methods, it is preferred that the highly fluorescent marker compounds be liquid and readily soluble in fluids. Therefore, those conditions which would produce high crosslink density or insoluble solids are preferably avoided, i.e., where n, in formulae (I), (II) or (III) is greater than one, a monofunctional isocyanate is preferred and where y is greater than one, a monofunctional polymer is preferred. If use of a diisocyanate is desired for n>1, a mixture of mono- and difunctional polymeric group is preferably used to control the molecular weight of the polyurethane product. The isocyanate index for reaction of the polymer with the isocyanate is less than or equal to 100 but a value of 100 is preferred.
The term “Isocyanate Index” (also commonly referred to as NCO index), is defined herein as the number of equivalents of isocyanate, divided by the total number of equivalents of isocyanate-reactive hydrogen containing materials, multiplied by 100, (i.e., NCO/(OH+NH)×100).
The fluorescence signature of the marker compounds may be adjusted by varying the chain length of the polymeric group, the presence or absence of fluorophore and the type of fluorophore. The highly fluorescent marker compounds may be added to the matrix to be marked in any amount depending upon the sensitivity of the detection system. The inventor herein contemplates that, with present technologies, detection may be effected at amounts of at least one part of the inventive compound per billion parts of matrix up to perhaps 100 parts per million. The matrix to be marked is virtually unlimited. Fluids, fluid blends and solid compositions (preferably before solidification has occurred) may be marked with the inventive compounds. The highly fluorescent marker compounds may be used to mark fluid blends, such as petroleum products including diesel fuel, gasoline and heating oil. Although less preferred because of a weaker signal, the inventor herein also contemplates the use of a fluorophore-containing polymer itself in the inventive marking methods.
EXAMPLES
The present invention is further illustrated, but is not to be limited, by the following examples.
Highly Fluorescent Marker Preparation Procedure
An apparatus was assembled from a three-liter resin kettle with a four-necked glass cover. A metal stirrer shaft with three Rushton turbines was inserted into the central neck. The other necks were fitted with a thermocouple, a nitrogen line, and a vacuum line. The resin kettle was inserted into a heating mantle jacket. The assembly was flushed with nitrogen for 15 minutes before charging 2,370 grams (1.483 equivalents) of polyether polyol to the resin kettle. The polyether was vacuum-stripped at 20-25 mm Hg while heating to 110° C. for two hours. The polyol was cooled to 60° C. before sufficient isocyanate was added to achieve the desired index. The mixture was heated for two to four hours at 125° C. under a nitrogen blanket. Consumption of the isocyanate was monitored by standard titration methods. The isocyanate index was varied from 90 to 100 and the amount of each reactant was dependent upon its active hydrogen content.
Fluorescence Analysis Method
High Performance Liquid Chromatography (HPLC) analyses of the highly fluorescent marker compounds were performed using a Model 1090M HPLC (Agilent Technologies) equipped with a Model 1046A Fluorescence detector. A five microliter aliquot of a 100 ppm solution of each marker compound was injected into the HPLC, which contained no analytical column and used unstabilized THF as mobile phase at a flow rate of 0.5 milliliters per minute. Because no analytical column was used, all components of each sample were unretained by the system and eluted together.
The fluorescent responses were monitored primarily at three specified wavelength combinations, namely: Excitation at 240 nm/Emission at 325 nm; Excitation at 240 nm/Emission at 310 nm; and Excitation at 230 nm/Emission at 310 nm. The photomultiplier tube (PMT) sensitivity was set at 8. Comparisons of marker compounds responses were based on peak area data.
Peak areas for the emission spectra of the marker compounds were compared to the peak area for a control to obtain the relative response ratio. The control was a polyether prepared by propoxylating nonylphenol. Although there was little difference in the response ratios when the excitation wavelength was 230 nm, various combinations of polymer fluorophores and aromatic isocyanates enhanced responses from two to nine times when excitation at 240 nm was used.
Table I details the composition of the highly fluorescent marker compounds and summarizes the results of fluorescence measurements performed at various combinations of excitation and emission wavelengths. The molecular weights listed correspond to the unreacted polymer.
TABLE I
Fluorescence in THF
Highly Fluorescent Marker Compound
Excitation 230 nm
Excitation 240 nm
Excitation 240 nm
Reactive Polymer
Isocyanate
Emission 310 nm
Emission 310 nm
Emission 325 nm
Ex. No.
Fluorophore
Funct.
MW
Funct.
Area
Ratio
Area
Ratio
Area
Ratio
C-1
nonylphenol
1
1,600
none
—
592
1.0
108
1.0
54
1.0
2
nonylphenol
1
1,600
4,4′-MDI
2
856
1.4
721
6.7
476
8.8
3
nonylphenol
1
1,600
phenyl isocyanate
1
789
1.3
211
2.0
105
1.9
4
Bisphenol A
2
3,000
phenyl isocyanate
1
1,023
1.7
344
3.2
185
3.4
5
Bisphenol A
2
3,000
1-napthyl isocyanate
1
704
1.2
200
1.9
493
9.1
6
none
1
1,600
phenyl isocyanate
1
165
0.3
126
1.2
62
1.1
7
none
1
1,600
4,4′-MDI
2
298
0.5
506
4.7
320
5.9
The foregoing examples of the present invention are offered for the purpose of illustration and not limitation. It will be apparent to those skilled in the art that the embodiments described herein may be modified or revised in various ways without departing from the spirit and scope of the invention. The scope of the invention is to be measured by the appended claims.
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The present invention provides highly fluorescent markers, made from a reactive polymer and an isocyanate, that fluoresce in the ultraviolet or near infrared region without being visible to the human eye at low concentrations in the fluid or article being marked. The molecular weight and fluorescence emission wavelength of these highly fluorescent marker compounds can be adjusted to provide a multitude of markers with unique fluorescence signatures.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a division of application Ser. No. 09/674,258, filed on Feb. 2, 2001; now U.S. Pat. No. 6,911,035 which is the 35 USC 371 national stage of PCT/NL99/00255, filed on Apr. 28, 1999, which designated the United States of America. The entire contents of both of these applications are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to suturing means for connecting a tubular vascular prosthesis to a blood vessel in the body.
The invention herein relates particularly, but not exclusively, to vascular prostheses intended to replace or support the natural vessel wall of particularly the aorta. Due to damage or other weakening of the wall thereof a dilation, a so-called aneurysm, can result locally herein. If timely action is not taken the vessel wall can eventually rupture at the location of such an aneurysm, resulting in internal bleeding and therewith a life-threatening situation. To avoid this the existing vessel wall is either replaced or covered with a suitable vascular prosthesis at the location of the aneurysm.
BACKGROUND OF THE INVENTION
A traditional method of arranging such a vascular prosthesis consists of opening the abdominal wall from the sternum to the pubis, whereafter an incision is made along the full length of the blood vessel at the location of the unhealthy part. A suitable vascular prosthesis in the form of a tubular body of circular knitted textile of a similar diameter and length is subsequently sutured to the healthy ends of the blood vessel with suture needle and thread. The affected vessel wall is then preferably placed round the vascular prosthesis and subsequently closed.
It will be apparent that the above specified method involves a major operation which in practice can require more than three hours. Even more important than the total duration of the operation however is that the blood flow in the vessel has to be interrupted for a relatively long time, of sometimes more than an hour. This involves a serious danger of complications both during the operation and thereafter. It will moreover be apparent that the stated size of the operation wound in this operating method also results in a relatively great discomfort for the patient and adversely affects his recovery. There is also the risk of a certain leakage through the suture, so-called false aneurysms, which may in such cases necessitate the operation being repeated.
In order to obviate these drawbacks an alternative operation technique has been developed, wherein a vascular prosthesis is arranged at the desired location endovascularly, i.e. via the vascular system itself. Such an endovascular prosthesis generally comprises a tubular body, the wall of which is formed by a metal scaffold which is resilient and capable of expanding in radial direction. The endo-prosthesis is arranged in compressed state on a tip of a catheter and manoeuvred with the catheter via a relatively small incision in the groin or another suitable place to the weakened part of the blood vessel for treating. Having arrived at the desired location, a temporary envelope is pulled off the prosthesis or a balloon incorporated in the prosthesis is expanded, whereby the prosthesis expands from the compressed to an expanded state, wherein the prosthesis lies resiliently against an inner wall of the blood vessel. Initially only the expansion force of the prosthesis holds the prosthesis in its place, but in the course of time bodily tissue will be deposited on the prosthesis whereby in the long term it will ideally be completely embedded in the wall of the blood vessel.
Such an endovascular method undeniably entails less discomfort for the patient than the classical operating method and the circulation of blood through the blood vessels also remains largely undisturbed. Nevertheless, this method also has drawbacks. Apart from the relatively high cost of this treatment there is the drawback that the suturing of the prosthesis to the blood vessel is effected initially solely by the radial spring force of the prosthesis. There is a therefore a real danger that the prosthesis can be entrained to a greater or lesser degree by the blood flow. This danger is acknowledged in an example of a known endovascular prosthesis which is described in the International patent application no. 97/39687, wherein for this purpose the proximal side of the prosthesis is provided with a ring of fine hooks to anchor the prosthesis in the vessel wall. Because it must be possible to introduce the entire unit endovascularly, the dimensions and therewith the anchoring of these hooks are inevitably limited.
There is however also the risk that the blood will be able to find its way between the wall of the blood vessel and the prosthesis and then still exert the original pressure on the vessel wall. Such a case is referred to as an endo-leak. To remedy such a complication an operation in the traditional manner will still have to be performed, whereby all advantages of an endovascular treatment method are nullified. In order to prevent this in the case of the above stated example of a known endovascular vascular prosthesis, tensioning straps are arranged at the location of both the proximal and the distal end of the vascular prosthesis, after it has been introduced, for better fixation of the whole round the vessel wall. Such a fixation is also described in the case of the endovascular vascular prosthesis known from the American U.S. Pat. No. 5,764,274. However, such tensioning straps cannot be introduced endovascularly so that a classical operation is still required for this purpose. The tensioning member of the applied tensioning straps moreover provides an undesirable irregularity in the body which may adversely affect the biocompatibility of the whole.
Finally, as a result of their necessarily fragile construction, endovascular prostheses have been found in practice to be of limited durability, whereby for the time being the quality of the prosthesis cannot be fully guaranteed in the long term.
SUMMARY OF THE INVENTION
The present invention has for its object to provide suturing means of the type stated in the preamble which allow a suturing technique which, compared to the traditional operation technique, entails only relatively minor surgery for the patient but which, compared to an endovascular method, enables a markedly more reliable suturing of the prosthesis to the vessel wall.
In order to achieve the intended objective, suturing means of the type stated in the preamble have the feature according to the invention that the suturing means comprise an internal, substantially annular body intended to be firmly connected to an outer end of the vascular prosthesis and to be received in the blood vessel, that the suturing means comprise an external annular body intended to lie clampingly on an outer wall of the blood vessel at least practically at the location of the internal annular body and that at least one of the two annular bodies is provided with suturing members which at least in connected situation thereof extend from the blood vessel substantially radially in the direction of a vessel wall and grip at least in the vessel wall so as to effect an adequate fixation of at least the internal annular body.
In order to arrange a vascular prosthesis it suffices, making use of such suturing means, to make only a small incision in or close to the affected part of the blood vessel where the vascular prosthesis will be sutured to healthy ends of the blood vessel to enable placing of the prosthesis into the vessel. Once the blood vessel has been sufficiently exposed and this incision made, the vascular prosthesis is introduced via the incision and optionally shortened to the required length. The internal annular body of the suturing means can herein already be incorporated in the prosthesis on an end thereof The vascular prosthesis is pressed sufficiently far into the blood vessel so that the end with the internal annular body of the suturing means eventually lies at the location of one of the healthy ends of the blood vessel on either side of the affected part thereof. The blood vessel is here accessible to the external annular body of the suturing means which is placed clampingly round the blood vessel at the position of the internal annular body to allow the suturing members to penetrate properly into at least the vessel wall and thus effect a reliable suturing and sealing of the prosthesis on the vessel wall. This procedure is repeated on the opposite side of the weakened vessel part with another end of the prosthesis, whereafter the vessel wall and abdomen are closed again.
It has been found in practice that the suturing means according to the invention, optionally making use of tools designed therefor such as for instance the devices which will be further described below, can be arranged within only a few seconds. The operation time, and particularly the necessary interruption of the natural blood flow through the vessel can thus be considerably limited when compared to the above specified traditional suturing method, which is of great importance particularly in the aftercare and recovery of the patient. Because at least the vessel wall is clamped between both annular bodies at the location of the suturing means, which thereby provide an effective sealing, the chance of an endo-leak is also drastically reduced, if not completely eliminated, by the suturing means according to the invention. Furthermore, the prosthesis is adequately fixed to the vessel wall by means of the internal annular body, whereby the danger of undesired shifting of the prosthesis in the blood vessel is likewise prevented, or at least greatly reduced. Because the annular body and the vascular prosthesis are introduced by classical means, no concessions have to made in their material and construction as in the case of an endovascular insertion technique. The internal annular body can therefore be relatively robust so as to be able to sufficiently counterbalance the forces exerted radially thereon by the external annular body and thus ensure an adequate fixation of the vascular prosthesis. For the prosthesis itself a traditional tubular body can be used per se, the long term durability thereof having by now been sufficiently tested, this in contrast to tubular bodies provided with stents, whether or not self-expanding, applied in endovascular treatment methods. The invention nevertheless requires only a small incision and the operating time, and more particularly the period of time for which the bloodstream is blocked, is considerably shorter than in the fully classical treatment method, which radically reduces the risk of mortality and other complications. The invention thus combines the advantages of both the known methods described above, i.e. relatively rapid and minimal surgery together with a reliable fixation and sealing of the prosthesis on the vessel wall, without the associated drawbacks.
In a particular embodiment the suturing means according to the invention are characterized in that the suturing members, at least in the connected situation, extend radially from a first of the two annular bodies and are received in the other of the two annular bodies to thus effect a firm mutual connection while enclosing the wall of the vascular prosthesis and the vessel wall. In this embodiment the vessel wall and the vascular prosthesis are as it were clamped between both parts of the suturing means, wherein the suturing members provide a through mutual anchoring of the diverse parts. An exceptionally reliable suturing is thus obtained, which owing to the invention can be arranged in an extremely short time.
In a further embodiment the suturing means according to the invention are characterized in that the first annular body comprises a metal ring with lips which can be pressed radially outward and are provided with sharp protrusions which are capable of penetrating through the wall of the prosthesis, the wall of the blood vessel and into the material of the other of the two annular bodies. After the first annular body has been brought into position, the lips are pressed out with or without the use of a special accessory so that the sharp protrusions penetrate into the other annular body. The protrusions are herein preferably provided with one or more barbed hooks to ensure their fixation in the material of the other annular body.
A preferred embodiment of the suturing means according to the invention has the feature that the suturing members extend from the internal annular body and that the external annular body comprises at least a core of plastic for receiving the suturing members therein. Because the suturing members herein extend from the internal annular body and pass through the vessel wall to the outside to be received in the other annular body, the internal annular body can be relatively thin, whereby the natural blood flow is thereby disturbed as little as possible. In this respect an inner diameter is preferably chosen for the internal annular body which is equal to that of the original blood vessel and the blood vessel is slightly stretched to allow nesting of the annular body therein so that no turbulences or other disturbances whatsoever are caused in the blood flow. A visual inspection is thus further possible to establish that the normally sharp ends of the suturing member are actually lying in the other annular body and not outside it. Preferably applied herein is a tough or foamed plastic which allows for a relatively easy penetration of the suturing members and then firmly fixes the suturing members.
To enable a simple positioning of the external annular body round the blood vessel, a further particular embodiment of the suturing means according to the invention has the feature that the external annular body comprises a ring which is interrupted in at least one position and that at the location of the interruption closing means are provided to mutually connect adjacent ring parts. The blood vessel is herein inserted in the opened ring, whereafter the ring is closed using the closing means. The closing means for instance comprise a suturing member which extends from one of the two ends of the annular body and is capable of penetrating in fixing manner into the material of the other end. More particularly the closing means are adjustable so that the external body can be clamped and closed tightly round the internal one.
In a preferred embodiment the suturing means according to the invention have the feature that the external annular body comprises at least on a side facing the blood vessel a regular pattern of cams with which the body supports on the blood vessel, which cams leave mutually free interspaces extending over the full width of the body. Because in this embodiment at least one of the two annular bodies does not support on the blood vessel wall along its full surface but only with a regular pattern of cams between which channels remain clear, the blood vessel wall is prevented from being completely clamped off by the suturing means whereby the blood circulation therethrough could be endangered and the blood vessel wall could die off. The channels formed by the continuous interspaces effectively prevent this.
The prosthesis, preferably already provided with the internal annular body, is inserted into the blood vessel with a suitable tool. For adequate fixing herein of the internal annular body located inside the prosthesis a further particular embodiment of the suturing means according to the invention has the feature that the means also comprise a clamping ring which is intended to lie against an outer wall of the prosthesis at least practically at the position of the internal annular body and herein exert at least locally a radially inward directed force. More particularly the clamping ring herein comprises a crimp ring which can permanently decrease in diameter at increased temperature. After specified heating such a ring crimps around the prosthesis having therein the internal annular body of the suturing means, so that the prosthesis is clamped between the two. This ensures an adequate fixation of the internal body in the prosthesis.
In a further particular embodiment the suturing means according to the invention have the feature that the suturing members comprise protrusions which extend from the internal annular body on a side thereof directed toward the blood vessel wall and are capable, at least under the influence of a radially directed force, of penetrating at least partially the blood vessel wall to thus anchor the prosthesis therein. More particularly the suturing members herein comprise a regular pattern of crater-like openings, the walls of which form the protrusions. It is not necessary herein for the suturing members to penetrate completely through the vessel wall in order to penetrate for instance into an external annular body. An adequate gripping in the vessel wall will already suffice. This embodiment is herein based on the insight that in the bloodstream mainly axial forces will be exerted on the suture and not much in the way of radial forces, whereby an axial anchoring such as by means of the suturing members referred to here is in itself sufficient. The external annular body is able to provide the counterpressure possibly required herein at the moment the suturing members penetrate into the vessel wall. Furthermore, the external body will in this case also prevent the occurrence of possible endo-leaks, now that it can be placed tightly round the internal body while enclosing at least the vessel wall.
A further particular embodiment of the suturing means herein has the further feature according to the invention that the internal annular body has an inner diameter which is at least practically equal to an outer diameter of the vascular prosthesis and that the internal annular body is intended to lie against an outer wall of the vascular prosthesis. The internal annular body can be fixed by means of a suitable glue or otherwise on the outer wall of the vascular prosthesis, so that the protrusions do not have to be pressed through the prosthesis wall and can thereby be shorter. This reduces the chance of damage to the inner wall of the blood vessel during an operation, wherein a prosthesis provided with such an annular body is guided to the desired location via the blood vessel.
To further reduce this risk and also to enable insertion of the whole in simple manner in a blood vessel, a further embodiment has the feature herein that the internal annular body comprises a deformable ring which in a first contracted state has a diameter which falls within the diameter of the blood vessel and in a second expanded state is able to lie against an inner wall of the blood vessel. In the first contracted state the deformable ring, lying round the vascular prosthesis, can be inserted without difficulty into the blood vessel and manoeuvred to the desired position. There the ring is expanded to the full diameter so that the ring eventually lies against the vessel wall and the suturing members penetrate therein. This can be realized in a very short time and in particularly reliable manner making use of a special tool such as the device to be further described hereinbelow, so that here also the unavoidable disruption of the natural blood circulation during the operation is limited.
In a conventional operating method side vessels of a blood vessel are usually lost at the location of a vascular prosthesis arranged therein because such side vessels are closed off by the vascular prosthesis. The invention also provides, on the basis of the same principle as the above specified suturing means, branch means for connecting a side vessel of a main blood vessel to a vascular prosthesis arranged in the main blood vessel, which branch means make it possible to preserve a possible side vessel. According to the invention such branch means comprise a flange-shaped internal body intended to lie against an inner wall of the vascular prosthesis, which flange-shaped body carries on its side directed toward the vascular prosthesis a hollow stem open on both sides as well as at least one suturing member, both of which are able to penetrate through the wall of the vascular prosthesis, and comprise a flange-shaped external body intended to lie round the side vessel against an outer wall of the main blood vessel at the position of the internal body, which external body is provided with a bore for receiving the side vessel and the stem therein, wherein at least in mutually connected state the suturing member is received in the external flange-shaped body, thus forming a firm mutual connection, and the stem is received in the side vessel, thus forming an open connection between the main blood vessel and the side vessel. The internal body is herein pressed through the prosthesis wall as a kind of thumbtack with the stem and the at least one suturing member, wherein the stem is carried into the side vessel. The at least one suturing member penetrates adjacently of the side vessel through not only the prosthesis but also the vessel wall. The external body is placed round the side vessel and pressed firmly together with the internal body so that the suturing member penetrates in the material of the external body and thus effects a firm connection. In this manner the hollow stem provides an open communication between the prosthesis in the main blood vessel and the side vessel, which latter is thus preserved.
In a preferred embodiment of the branch means the stem tapers to a point at its free end in order to facilitate penetration thereof through the prosthesis wall. Although for the mutual connection of the two flange-shaped bodies a single suturing member will optionally suffice, a preferred embodiment of the branch means has the feature that the internal body comprises at least two suturing members which are disposed around the stem. For the purpose of simple positioning of the external body a further preferred embodiment of the branch means according to the invention has the feature that the external disc-like body comprises a channel which provides access to the bore from a peripheral edge. The side vessel can herein be inserted in the bore in simple manner via the channel.
The invention also relates to a device for inserting and suturing a flexible tubular vascular prosthesis in the body, which prosthesis is provided on a free end with an annular body which lies against a wall thereof, comprising a flexible infeed line, which infeed line is provided on one end with a fixation member intended for receiving thereon the vascular prosthesis with the internal annular body, which fixation member is able when energized to exert a radially outward directed force on the annular element.
The prosthesis is pushed into the affected blood vessel making use of such a device using the flexible infeed line, wherein the fixation member holds the prosthesis precisely in place. At the intended location the fixation member is energized to thus press the prosthesis with the annular body radially outward. The prosthesis with the annular element is thus pressed from the inside against the vessel wall, which herein preferably receives a counterpressure from outside in the form of a second annular body forming part of the suturing means according to the invention and arranged round the blood vessel at that position. Owing to the action of said force the suturing members provided on at least one of the two annular bodies will be able to adequately penetrate at least the vessel wall and thus achieve a reliable fixation of the vascular prosthesis.
In a particular embodiment the device according to the invention has the feature that the annular body comprises a metal ring with suturing members which can be pressed radially outward and that the fixation member is able to exert a radially outward directed force on at least the suturing members of the annular body. In this embodiment the radial force is not so much exerted on the annular body as a whole but more specifically on the outward pressable suturing members which thereby penetrate into or even through the vessel wall.
A further particular embodiment has the feature herein that the suturing members comprise lips with sharp ends which are retracted and can be pressed radially outward and that the fixation member comprises a rotatable disc for receiving the annular body thereon, which disc is provided with recesses for receiving the lips of the annular body therein. In this embodiment the suturing members are formed by outward pressable lips which are initially directed inward and therefore lie at least partially retracted in the ring. The retracted lips herein fall into the recesses of the disc and will be forced radially outward when the disc is rotated and the lips are herein driven out of the recesses. Such a retracted positioning facilitates insertion of the prosthesis provided with the annular body and prevents unintentional damage to the vessel wall during transport to the suturing location. At the intended location the lips are forced out of the respective recesses by appropriate rotation of the disc. All lips will thus penetrate with their sharp end at least almost simultaneously at least into the vessel wall to effect the desired suturing.
In order to prevent the annular body co-rotating under the influence of the rotation of the disc, a further particular embodiment of the device according to the invention has the feature that the fixation member comprises two discs which are rotatable in opposing directions and are mutually adjacent and which together receive the annular body thereon, which discs are both provided with recesses for receiving therein lips of the annular body which are retracted in opposing directions and which can be pressed radially outward. By thus performing two rotations in opposing directions in the fixation member which act upon the internal annular body, at least practically no net force is exerted thereon so that possible co-rotation of the annular body is prevented. This is particularly important if the suturing members of the annular body have to be received at a precisely determined location in for instance a second annular body which has been arranged externally round the vessel wall.
In a further particular embodiment the device according to the invention has the feature that the fixation member comprises an inflatable body which in a first at least partially evacuated state can be received in the prosthesis with the annular body and in a second filled state takes on a cylindrical form coaxially with the prosthesis, an external diameter of which is at least practically equal to an internal diameter of the vascular prosthesis. Such a fixation member has a relatively simple mechanical construction and is found in practice to have sufficient expansion force to press the vascular prosthesis with the annular body sufficiently firmly from the inside against the vessel wall to thus enable suturing members to at least penetrate adequately therein.
In order to avoid overloading of the vessel wall herein and retain full control over the expansion behaviour of the inflatable body, a preferred embodiment thereof has the feature according to the invention that in the second state the inflatable body is at least practically non-stretch and herein maintains an internal pressure in the order of magnitude of several tens of atmospheres. In inflated form such a fixation member behaves as a rigid and practically non-compressible body which is thereby highly suitable for absorbing and compensating possible counterpressure on the suturing members. In evacuated state such a fixation member is in contrast flexible and yielding, whereby together with or without a prosthesis arranged thereon it allows of exceptionally easy manoeuvring via the blood vessel to the desired location.
A further embodiment of the device according to the invention has the feature that the device comprises a second fixation member intended for fixing a second annular body, which second annular body is intended for lying against an outer wall of a blood vessel and that monitoring means are provided for indicating the mutual position of both fixation members. The second annular body is placed round the blood vessel with the second fixation member at a location which corresponds precisely with that of the first internally arranged annular body on the first fixation member. To enable adequate control of this relative position, the monitoring means provide an accurate indication of the mutual position of both fixation members and therewith of both annular bodies. A precise alignment of the respective positions of both annular bodies can thus be realized in simple manner. The suturing members of at least one of the two bodies can subsequently be driven into at least the vessel wall to thus ensure an adequate enclosing and anchoring of the vascular prosthesis on the vessel wall.
The invention further relates to a vascular prosthesis comprising a flexible tubular body intended to be connected to a blood vessel with a first and a second end respectively at a first and a second location.
In order to enable such a vascular prosthesis making use of the suturing members and device according to the invention to be arranged in the body of a patient in a short time, such a vascular prosthesis according to the invention has the feature that the tubular body comprises an opening in a wall thereof between the first and second end. This opening provides a passage for the suturing means and device according to the invention for realizing therewith said connections at the first and second location. After the first end of the prosthesis has been sutured, the second or further end of the prosthesis can be fixed in similar manner from the inside via the opening in the prosthesis. Following this operation the opening in the prosthesis is closed and the vessel wall sutured at this location, whereafter the bloodstream can resume its natural flow. To facilitate closing of the prosthesis a preferred embodiment thereof has the feature according to the invention that the tubular body comprises an externally directed collar around the opening. In such an embodiment only the collar has to be closed to close the prosthesis adequately. For this purpose a lace can for instance be provided in the collar with which the collar can be laced up, although such a collar can also be closed extremely quickly in other manner, such as for instance by means of stapling.
A further vascular prosthesis comprising a flexible tubular body, at least a first end of which is intended for connecting to a blood vessel has the feature according to the invention that the tubular body is provided on at least the first end with an internal annular body of the suturing means according to the invention. A first particular embodiment of such a prosthesis according to the invention, wherein the internal annular body lies against an inner wall of the tubular body, has the feature herein that a clamping ring lies clampingly on an outer wall of the tubular body at the location of the internal annular body. A second particular embodiment of such a prosthesis according to the invention has the feature herein that the internal annular body lies on an outer wall of the tubular body via a suitable glue connection. Such prostheses are ready for immediate use at least on the relevant end and can be supplied including the relevant parts of the suturing means in a sterilized packaging, which saves (preparation) time during the operation.
A further preferred embodiment of the vascular prosthesis according to the invention has the feature that a second end of the tubular body is provided with coupling means which are capable of a liquid-tight coupling to a free end of a second flexible tubular body. More particularly this preferred embodiment according to the invention is characterized in that the coupling means comprise a rigid, tubular coupling element which is firmly connected on a first side to the second end of the tubular body and comprises on a second part a taper intended for clampingly receiving thereon the free end of the second tubular body. A rapid coupling can thus be established extremely rapidly between both tubular bodies wherein the free end of the second tubular body simply has to be pushed onto the taper. In order to secure this connection a further particular embodiment of the vascular prosthesis according to the invention is characterized in that the coupling element is provided at the location of the taper with at least one external, tangentially running rib which extends over at least a part of the periphery of the taper and more particularly in that the coupling element comprises at the location of the taper at least two external ribs which leave a certain mutual interspace, which interspace is intended for receiving a clamping ring at that position which fixedly clamps the end of the second tubular body onto the taper. The free end of the second tubular body is pushed over this rib or ribs onto the taper, whereafter the rib and optionally the clamping ring keeps the second tubular body from sliding off unintentionally.
A prosthesis provided with such coupling means can be sutured on the first end to a healthy end of the blood vessel in the above described manner, while the second end provides the option of a liquid-tight rapid coupling to another, possibly similar vascular prosthesis. It is hereby unnecessary to perform a second or further suturing from the inside of one and the same prosthesis, and the sutures can be placed independently of each other and the different free ends can be mutually connected by means of the coupling means described here. Not only can additional time be gained in practice due to such a rapid coupling, but the possibility is also provided of a modular construction of a vascular prosthesis system of mutually connectable prosthesis elements, to which prosthesis system the invention therefore also relates. In addition to single prosthesis elements with only a main leg which is arranged on either side between healthy ends of the affected blood vessel, this vascular prosthesis system for instance also comprises more complex elements which are adapted in respect of design to specific surgery.
A particular embodiment of the vascular prosthesis according to the invention provides as such a module which is specifically suitable for realizing a so-called end-to-side anastomosis. This particular embodiment of the vascular prosthesis has the feature that the tubular body comprises a main leg, between opposite ends of which at least one side leg extends, and that at least one of the free ends of the tubular body carries either an internal annular body associated with the suturing means according to the invention or coupling means of the above specified type. More particularly this embodiment has the feature that the main leg is provided on either side with such an internal annular body. In this embodiment the main leg can be fully inserted into a healthy blood vessel and fixedly sutured therein on either side in the above described manner. The at least one side leg of the prosthesis then provides a branch of this blood vessel and can be sutured, either directly or via the above specified coupling means and a further vascular prosthesis, to an end of a further blood vessel, thus realizing an end-to-side anastomosis.
Another particular embodiment of the vascular prosthesis according to the invention is characterized in that the tubular body comprises a primary leg with a first free end and a second end which divides into at least two secondary legs and that at least one of the free ends of the tubular body carries either an internal annular body associated with the suturing means according to the invention or coupling means of the above specified type. This embodiment is eminently suitable and thereby provides appropriate modular elements of the prosthesis system according to the invention for the purpose of a so-called end-to-end anastomosis, particularly one close to the bifurcation, wherein a healthy end of a blood vessel must be connected to usually two other healthy ends of blood vessels.
For the complete replacement or support of a bifurcation of the chest or stomach aorta, a particularly practical embodiment of the vascular prosthesis herein has in this respect the feature according to the invention that the primary leg is provided on the first end with an internal annular body and that the secondary legs each carry coupling means on their free end. The primary leg is herein sutured to a healthy end of the aorta, while the secondary legs are coupled to healthy ends of the arteries branching therefrom via single prostheses which can each be individually shortened to the desired length.
Suitable for a more general end-to-end anastomosis and smaller bifurcations is a further particular embodiment of the vascular prosthesis according to the invention which is characterized in that at least the secondary legs are each provided at their free end with an internal annular body. These secondary legs can be sutured according to the invention directly to the branches of a blood vessel which is itself coupled to the primary leg either directly or via a further vascular prosthesis according to the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be further elucidated and explained on the basis of a number of embodiments and an associated drawing which further illustrate the invention but do not in any way limit the invention in its range and scope. In the drawing:
FIGS. 1A-1C show a perspective view of a first embodiment of the suturing means according to the invention;
FIG. 2 shows a longitudinal section of a first embodiment of the device and a vascular prosthesis according to the invention;
FIGS. 3A-3B show two cross-sections of the device of FIG. 2 in successive stages of operation;
FIGS. 4A-4C show different cross-sections of an embodiment of branch means according to the invention;
FIGS. 5A-5B show in perspective view a second embodiment of suturing means and a vascular prosthesis according to the invention;
FIGS. 6A-6B show a perspective view of a second embodiment of a device according to the invention;
FIG. 7 is a perspective view of a further embodiment of a vascular prosthesis according to the invention which forms a vascular prosthesis module forming part of an embodiment of a vascular prosthesis system according to the invention;
FIGS. 8A-8B show a detail drawing in cross-section of a rapid coupling with an embodiment of the vascular prosthesis according to the invention; and
FIGS. 9-12 show a perspective view of further embodiments of a vascular prosthesis according to the invention which each form a vascular prosthesis module forming part of the embodiment of the vascular prosthesis system according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
The figures are purely schematic and not drawn to scale. Some dimensions in particular are (highly) exaggerated for the sake of clarity. Corresponding components are designated as far as possible in the figures with the same reference numerals.
The suturing means of FIGS. 1A-1B comprise an internal annular body 10 , see FIG. 1A , in the form of a closed ring of high-grade steel or another biocompatible metal or metal alloy. Arranged in the wall of the ring at regular positions are notches 11 which provide space for suturing members 12 . The suturing members here comprise a regular pattern of lips 12 with sharp protrusions 13 . The lips are initially retracted radially but in the shown situation are pressed radially outward, in which case lips 12 are able to penetrate through the vascular prosthesis and the vessel wall, which will be further elucidated hereinbelow.
The suturing means further comprise an external annular body 20 , see FIG. 1B , in the form of a ring with at least a core of plastic. In this embodiment the ring is wholly manufactured from a plastic and with a sufficient thickness such that ring 20 can receive suturing members 12 therein in clamping and snapping manner, so that a reliable gripping and mutual connection is effected. Other than the internal body, external ring 20 does not comprise an integral unit but ring 20 has an interruption 21 where closing means are provided to hold together adjacent ring parts. The closing means here comprise a snap member 22 which snaps precisely into a complementary bore 23 in the adjacent ring part, this being shown in more detail in the indicated circle. If desired, more of such snap members can be provided so that ring 20 is adjustable and can be adapted to the actual dimensions of the blood vessel. Ring 20 can thus be opened and closed manually. Ring 20 comprises on its inner side a regular pattern of cams 24 , whereby ring 20 is able to support on an outer wall of a blood vessel while leaving clear interspaces 25 . The interspaces 25 extend over the full width of ring 20 and thus provide continuous channels which ensure sufficient blood circulation through the vessel wall to prevent undesired dying off thereof.
The suturing means of this embodiment further comprise a clamping ring 30 , see FIG. 1C . The clamping ring here comprises a crimp ring manufactured from a suitable crimp foil of plastic and is therefore no more than an extremely thin band which is nevertheless capable of exerting a substantial radially inward directed force when it is permanently reduced in diameter at increased temperature.
In order to suture a vascular prosthesis to a blood vessel in the body making use of such suturing means, an incision is made therein at the position of or close to the affected part to be replaced or supported after the blood vessel has been exposed over a sufficient length, wherein a length of no more than a few centimetres usually suffices. Via this incision the vascular prosthesis is inserted into the blood vessel, for instance using the embodiment of the device according to the invention shown in FIG. 2 .
The device shown in FIG. 2 comprises a hollow, flexible infeed line 101 which is provided at one end with a fixation member 102 which is intended for receiving the vascular prosthesis thereon. Vascular prosthesis 40 is herein provided on a free end with the above described internal annular body 10 which lies against an inner wall of prosthesis 40 . The above specified crimp ring 30 holds prosthesis 40 and internal ring 10 firmly together. The retracted suturing members 12 of internal ring 10 fall into corresponding recesses in a rotatable disc 103 , 104 forming part of fixation member 10 , see also FIGS. 3A and 3B . In this embodiment the fixation member comprises two such discs 103 , 104 which rotate in mutually opposing directions, driven herein by separate drive shafts 105 respectively 106 which are guided thereto via the hollow infeed line. Owing to this retracted position of the suturing members the whole of prosthesis 40 , inner ring 10 and crimp ring 30 are properly fixed on fixation member 102 .
Lying on fixation member 102 the prosthesis 40 is guided with infeed line 101 into the weakened or at least affected blood vessel 50 via a relatively small incision 51 arranged herein which must be just large enough to enable passage of fixation member 102 . At the intended location the above specified external annular body 20 is placed round blood vessel 50 . The device can optionally be provided herein with a second fixation member to thereby fix this external annular body 20 onto vessel wall 50 , wherein monitoring means are moreover optionally provided which indicate the mutual position of both fixation members so as thus to be certain that both annular bodies 10 , 20 lie opposite one another in sufficiently precise manner.
In this situation both discs 103 , 104 in the first fixation member are rotated a small turn in opposite directions from outside using shafts 105 , 106 so that the initially retracted suturing members 12 of the internal ring are driven out of the recesses of the discs. The radially outward directed force exerted therein on internal ring 10 , or at least on suturing members 12 thereof, ensures that suturing members 12 are raised and penetrate through prosthesis 40 , crimp ring 30 and vessel wall 50 and are thus received in the material of external ring 20 , see also FIGS. 3A and 3B which show the situation respectively before and after this rotation. Barbed hooks 14 on sharp ends 13 of the suturing members herein ensure an effective connection practically free of play to outer ring 20 . Each of the suturing members 12 on inner ring 10 thus penetrates at the same moment into outer ring 20 whereby an extremely reliable connection is established to the outer ring. The rotation is preferably performed by means of a pistol-like mechanism on the end of drive shafts 105 , 106 whereby the rotation, and therewith the suturing of the vascular prosthesis, can be performed extremely accurately in a fraction of a second. The opposing rotation direction of the two discs herein ensures that at least practically no net tangential force is exerted on the internal ring and the vascular prosthesis, so that these remain accurately in place.
Once the operation has been thus performed on this side of the vascular prosthesis, it is repeated on the opposite side. In order herein to provide passage to infeed line 101 with fixation member 102 the vascular prosthesis is itself also provided according to the invention with an opening 41 between both ends. As soon as the second suture has also been made in similar manner, fixation member 102 is removed and this opening 41 in vascular prosthesis 40 is closed. So as to simplify this, the vascular prosthesis according to the invention comprises an externally directed collar 42 which can be simply closed by stapling or closed in a short time using a lace or the like. Finally, the incision 51 made in the vessel wall is sutured, whereafter the bloodstream can resume its natural flow. The patient is now ready for further post-treatment, wherein inter alia the skin is closed, and subsequent recovery from the operation. As a result of the invention the entire operation all in all requires markedly less time than a more conventional operating technique wherein a suture is placed manually to stitch the prosthesis and the blood vessel together, wherein particularly the necessary interruption of the blood flow can be considerably shorter owing to the invention. The clamping enclosure of vessel wall 50 between internal ring 10 and external ring 20 moreover reduces the chance of so-called false aneurysms or endo-leaks which in some cases of said conventional surgical respectively endovascular operating techniques may afterward completely negate the result of the operation.
In a conventional operation technique small side vessels of the blood vessel will normally be closed off by the prosthesis whereby the circulation to the organs supplied thereby will be obstructed and these organs can become inactive in the course of time or can even die off. The invention does however provide a possibility of preserving the circulation via such side vessels in the form of branch means based on the same suturing principles as the above specified suturing means. A number of embodiments thereof is shown in FIGS. 4A-4D .
The branch means drawn in FIG. 4A comprise a flange-shaped internal body 60 , see FIG. 4C , which is intended for lying against an inner wall of main blood vessel 50 , as shown in FIG. 4A . Body 60 is manufactured from a high-grade biocompatible material, for instance a high-grade form-retaining plastic, steel or other metal or metal alloy, and can optionally be embodied slightly curved to allow flange 61 to connect better onto the radius of blood vessel 50 . On one of its two sides the body 60 carries a hollow stem 62 open at both ends which is able to penetrate through prosthesis 40 . Stem 62 in this case tapers slightly on its outer end and thus forms a mandrel facilitating various aspects. Four suturing members 63 stand on the flange around mandrel 62 .
The branch means further comprise an external flange-shaped external body 70 , see also FIG. 4C , which lies on the outside of main blood vessel 50 against the vessel wall thereof. External body 70 is manufactured from a plastic which allows a penetration of suturing members 63 therein. The external body comprise a through-bore 71 , in which side vessel 52 is received via a radially running channel 72 .
In order to make a branch the internal body 60 is pierced through the prosthesis wall from inside, wherein both suturing members moreover penetrate straight through the vessel wall and are pressed into the external body. The barbed hooks on the ends of the suturing members herein ensure a strong suturing in the material of external body 70 so that a reliable connection is established. Hollow stem 62 herein penetrates into side vessel 52 and thus makes an open connection between main blood vessel 50 having prosthesis 40 therein on the one side and side vessel 52 on the other. Via this connection a proper blood circulation through the side vessel is ensured, whereby the circulation to the organs supplied thereby can be fully retained. In similar manner possible other side vessels can if desired also be very quickly connected to the prosthesis.
An alternative embodiment of such branch means is shown in FIG. 4B . In this case stem 62 of first body 60 does not taper, but retains the same inner diameter over its entire length to limit the blood flow as little as possible. A separate mandrel 65 is used to force a perforation in prosthesis wall 40 for stem 62 . In preference the body 60 is herein already situated on the mandrel, which is removed afterward. This embodiment of the branch means is further the same as that in FIG. 4A , i.e. the fixation is here also brought about by an anchoring in external body 70 .
The embodiment of the branch means shown in FIG. 4D provides fixation in a different way. In this case the stem 62 of internal body 60 comprises at least on its outer end a number of separate fingers which allow a radial movement. On one end thereof are situated one or more suturing members, in this case in the form of barbed hooks 66 , which are able to penetrate the vessel wall of the side vessel. For instance using mandrel 65 said fingers are driven apart after the body is positioned. If desired, mandrel 65 can be specifically designed for this purpose, for instance with a local, gradual thickening which drives the fingers apart as mandrel 65 is pulled out of stem 62 . An anchoring can thus be realized in side vessel 52 , which renders unnecessary a further anchoring in main vessel 50 as in the embodiments of FIGS. 4A and 4B . A significant advantage here is that the vessel wall does not have to be fully perforated and that an in principle foreign external body 70 such as used in the other embodiments can be omitted.
A second embodiment of the suturing means and vascular prosthesis according to the invention is shown in FIGS. 5A and 5B . In this embodiment vascular prosthesis 40 is already provided on the end which has to be connected to the blood vessel with an internal annular body 10 with suturing members 12 forming part of the suturing means. Other than in the first embodiment of the suturing means, the internal annular body here lies on an outer wall of vascular prosthesis 40 and suturing members 12 here penetrate only partially into the vessel wall instead of right through it into an external annular body. In this embodiment annular body 10 has for this purpose an inner diameter which is practically equal to an external diameter of vascular prosthesis 40 and is fixed thereon via a glue connection.
The suturing members are formed by a regular pattern of crater-like openings 14 in the wall of internal body 10 , the relatively sharp walls 15 of which form protrusions which are capable of entering the vessel wall under the influence of a radially outward directed force action to thus anchor in the vessel wall the body with the vascular prosthesis fixed thereon. The biocompatible materials for the diverse components are here also carefully chosen, wherein for the internal body high-grade steel is used in which openings 14 are punched. The punched edge unavoidably occurring herein forms the wall 15 of the thus obtained crater-like shape of opening 14 .
To facilitate insertion of vascular prosthesis 40 with ring 10 thereon, a relatively thin wall thickness is used here, whereby ring 10 is deformable and can be crimped to about 60% of its original diameter, see FIG. 5B . The flexible vascular prosthesis co-deforms herein. In this situation the whole unit is inserted and expanded at the intended location using for instance a second embodiment of a device according to the invention. This device is shown in FIGS. 6A and 6B and comprises an expandable fixation member in the form of an inflatable balloon 200 which in evacuated state can be received in crimped ring 10 and vascular prosthesis 40 . In this situation the whole unit is inserted into the blood vessel for treating via an incision arranged for this purpose in the vessel wall. Once prosthesis 40 is situated at the correct location a suitable medium, either a gas or a liquid, is admitted into balloon 200 via a thin flexible infeed line 201 , so that it expands together with the vascular prosthesis 40 and ring 10 lying thereon. For this purpose the infeed line 201 is provided on one end with coupling means 202 , see FIG. 6B , wherewith a connection can be made in simple manner to means for supplying the medium under pressure.
Admitting of the medium is continued until ring 10 has assumed at least its original shape and protrudes with craters 12 into vessel wall 50 . Balloon 200 now has a cylindrical shape with an outer diameter which at least practically corresponds with the internal diameter of the vascular prosthesis 40 . Because a balloon wall is used here which is at least practically non-stretch, the vessel wall is prevented from being loaded too much should too much air accidentally be admitted. In practice a pressure in the order of several tens of atmospheres prevails in balloon 200 , whereby the balloon behaves as a rigid, non-compressible body which gives sufficient counterpressure to arrange an external annular body round the blood vessel in the above stated manner so that a reliable, leakage proof connection is created between prosthesis 40 and the blood vessel. The medium is then released from balloon 200 again so that it crimps and can be removed easily, whereafter the incision can be closed and the normal blood flow restarted. The patient is now ready for usual after-care.
Further embodiments of a vascular prosthesis according to the invention are shown in FIGS. 7 to 12 . These embodiments form together with the above described embodiments modules of a more extensive embodiment of a vascular prosthesis system according to the invention.
The vascular prosthesis of FIG. 7 was also shown in FIG. 6B and comprises a flexible tubular body with a main leg 45 between the free ends of which at least one and in this case two side legs 46 extend. The free ends of the main leg are herein provided with an internal annular body 10 forming part of the suturing means of the type of FIGS. 5A and 5B which lies on an outer wall of the prosthesis. Both side legs are provided on their ends with coupling means 90 , 91 which are capable of an at least practically liquid-tight rapid coupling to a free end of a second flexible tubular body 80 of a second vascular prosthesis.
The coupling means are shown in cross-section in more detail in FIGS. 8A and 8B and comprise per side leg 46 a cylindrical coupling element 90 which is firmly connected by means of a suitable glue connection to the relevant side leg. On a free end the coupling element 90 comprises a slightly conically tapering taper 91 for receiving thereon the free end of the second vascular prosthesis 80 . The coupling element here has an internal diameter practically equal to that of vascular prostheses 40 , 80 so that the blood flow thereof encounters hardly any obstacle.
A mutual connection of both prostheses can be effected simply, rapidly and reliably by sliding the free end of the second vascular prosthesis 80 over taper 91 such that it is clamped fast. Thus achieved is the coupling of FIG. 8B which has already been found extremely reliable in practice. However, in order to further ensure the connection a crimp ring can optionally be placed round the end of the second vascular prosthesis 80 at the position of taper 91 and can be crimped thereon at increased temperature. The shear resistance of the second vascular prosthesis can be further increased by also providing the taper with one or more tangentially running ribs or an otherwise wrinkled or rough surface. In all cases the advantage of a liquid-tight rapid coupling between the two vascular prostheses 40 , 80 is retained.
The modular embodiment of the vascular prosthesis shown in FIG. 7 is extremely suitable for a double end-to-end anastomosis wherein an incision is made in a main blood vessel for introducing therein of the main leg 45 of the prosthesis. Main leg 45 is subsequently sutured in the main blood vessel as described with reference to FIGS. 6A and 6B , and clamped by means of two external annular bodies 20 . Side legs 46 can then each be coupled to an end of a further blood vessel. For this purpose use is made of intermediate prostheses, for instance of the type shown in FIG. 9 . These prostheses each comprise a free end and an internal annular body 10 on the other end for suturing to a blood vessel end and form a further module of the prosthesis system. Once both intermediate prostheses, after optionally being shortened to a desired length, are connected to the blood vessel end, the free end is pushed over coupling element 70 to thus complete a double end-to-side anastomosis. The prosthesis of FIG. 9 can otherwise also be deployed per se for a simple end-to-end anastomosis wherein the one end is connected to a first blood vessel end and the free end, with or without interposing of a comparable prosthesis provided with coupling means, is coupled to a second end of the blood vessel. In a variation of this prosthesis (module), the free end is provided with coupling means, which enables a linear extension of free-ending vascular prostheses.
For a multiple end-to-end anastomosis use can advantageously be made of the vascular prosthesis according to the invention shown in FIG. 10 which forms a further module in the prosthesis system. This prosthesis comprises a main leg 45 having on one side a free end which can be coupled to coupling means of another module and on the other side an internal annular body 10 forming part of the suturing means according to an embodiment of the invention. Connected to the main leg between both ends is a side leg 46 which likewise carries such an internal annular body 10 on its end. By means of these bodies 10 the prosthesis can be sutured to respective ends of a first and second blood vessel, while the free end provides the option of either direct suturing to a second end of the first blood vessel or coupling to an intermediate prosthesis which is sutured to this second end and provided on a free end with coupling means according to the invention.
A single end-to-side anastomosis in a blood vessel 50 is shown in FIG. 11 . Use is made for this purpose of a further embodiment of the vascular prosthesis according to the invention which forms a corresponding further module in the prosthesis system. This prosthesis is sutured in and on a blood vessel in similar manner to the prosthesis of FIG. 7 and herein provides a single side leg 46 between both ends of the main leg 45 received in blood vessel 50 . The free end of side leg 46 can for instance be coupled with the above stated variation of the prosthesis of FIG. 9 to an end of a further blood vessel.
For support or even complete by-pass of a bifurcation use can advantageously be made of the vascular prosthesis according to the invention shown in FIG. 12 which thereby forms a further module within the prosthesis system according to the invention. This vascular prosthesis comprises a tubular body with a primary leg 47 which divides at one end into two secondary legs 48 . Making use of this module an aorta-bifemoral bypass can be performed in relatively simple manner. Primary leg 47 of the prosthesis is herein sutured with suturing means 10 to the aorta abdominalis. From the two secondary legs 48 an end-to-end respectively end-to-side anastomosis to the arteria femoralis can then be made with interposing of two prostheses of the type shown either in FIG. 9 or in FIG. 11 . If desired, these second prostheses can herein each be individually shortened to a desired length and coupled with the above described rapid coupling to the first vascular prosthesis. Such a prosthesis can also be deployed very practically for a bypass at a higher location between the aorta abdominalis and the arteria iliaca communis, as it can in the case of any other bifurcation.
Although the invention has been further described above solely with reference to a single embodiment, it will be apparent to all that the invention is in no way limited to the given examples. On the contrary, many variations and embodiments are possible for the average skilled person within the scope of the invention. The vascular prosthesis system can thus be extended with additional prosthesis modules, each for a specific operation or for a similar type of surgery but with other dimensions and/or couplings.
Many variations of the shown suturing means are also possible for an average skilled person without having to depart from the scope of the invention. Different types of suturing member can thus be applied and the internal and external annular bodies can also be manufactured from other materials and can be designed or embodied differently. More particularly the annular bodies can for instance be provided with perforations to enhance the acceptance and accommodation thereof in the body. For insertion and clamping of the prosthesis according to the invention alternative devices can also be used instead of the described device and balloon, for instance a device with outward scissoring parts which can be forced apart from a distance.
The invention generally provides a completely new surgical procedure in respect of the processing of vascular prostheses which draws much less heavily on the condition of the patient than the more conventional surgery.
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Suturing elements for connecting a vascular prosthesis to a blood vessel include an internal, substantially annular body intended to be received in the blood vessel in addition to an external annular body intended to lie clampingly on an outer wall of the blood vessel at least practically at the location of the internal annular body. At least one of the two annular bodies is provided with suturing members which grip in the vessel wall so as to effect an adequate fixation of at least the internal annular body. The device for use with such suturing elements and a vascular prosthesis which is provided on at least one of its outer ends with at least a part of such suturing elements are disclosed. Different embodiments of such prostheses together form a modular vascular prosthesis system. A side vessel of a thus supported blood vessel can be preserved using branch elements.
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BACKGROUND OF THE INVENTION
1) Field of the Invention
This invention relates, in general, to novel quinoline polymers, chelates thereof, and their preparation and use. In one aspect this invention is directed to quinoline polymers which are produced by reacting 2-aminomethyl-8-hydroxyquinolines and diisocyanates and reacting the resultant polymeric product with a metal salt. In another aspect, this invention is directed to methods of preparing quinoline polymers and their chelates with transition metal ions, and their use in application areas which exploit the fluorescence or radioactivity of such chelates. The chelates of this invention are particularly useful in in vivo therapeutic applications utilizing radioactivity, or fluorescent labeling utilizing incident light. In a further aspect, the invention is directed to chelates of quinoline polymers with radioactive metal ions and their use in the topical treatment of rheumatoid arthritis and cancer.
2) Background of the Related Art
It is known that chelating agents such as ethylendiaminetetraacetic acid (EDTA), 1,3-diketones, thiosemicarbazides, and aminothiols, among others, form chelates with metal ions. However, few of the known chelates exhibit fluorescence and few have been shown to form water insoluble chelates, making the latter suitable for topical treatments utilizing radioactivity.
Accordingly, one or more of the following objects will be achieved by the practice of the present invention. It is an object of this invention to provide quinoline polymers produced from 2-aminomethyl -8-hydroxyquinolines and diisocyanates which are capable of forming chelates with transition metal ions. Another object of this invention is to provide novel polymer chelates which will exhibit distinct fluorescence excitation and emission spectra corresponding to that of the specific metal ion which is chelated and wherein the chelates themselves are stable. It is a further object of the present invention to provide quinoline polymers which can be used for the preparation of chelates of radioactive metal ions. A still further object of this invention, is to provide stable polymeric chelates of radionuclides which are water insoluble, and are useful for the topical treatment of rheumatoidal arthritis and cancer. These and other objects will readily become apparent to those skilled in the art in the light of the teachings contained herein.
SUMMARY OF THE INVENTION
In its broad aspect, this invention is directed to polymers produced from 2-amino-8-hydroxyquinolines and diisocyanates, certain metal chelates of these polymers with transition metal ions, and to processes for their preparation and use. The present invention is particularly directed to the chelates of quinoline polymers with readioactive metals, which are water insoluble and well suited for topical treatment of of rheumatoidal arthritis in joints (synovial cavity), and cancer. Chelates of the quinoline polymers with rare earth metal ions will exhibit fluorescence upon exposure to incident light. Such chelates have application in fluorescent labeling, while chelates with radioactive metals have therapeutic applications. The complexes of quinoline polymers with radionuclides, for example, can be localized in in vivo areas wherein radioactivity confers therapeutic benefits.
DETAILED DESCRIPTION OF THE INVENTION
The quinoline polymers employed in the present invention have the following recurring units: ##STR1## wherein n is an integer having a value of up to 10,000, preferably up to 500, and more preferably from 10 to 250; m is zero or an integer with a value of from 1 to 10,000, preferably from 1 to 500 and more preferably from 1 to 250; R represents a divalent group containing up to 20 carbon atoms and includes substituted and unsubstituted alkylene, arylene, aralkylene, alkarylene, alkylenearylene, or divalent alicyclic or heterocyclic groups; R' represents a divalent group containing up to 20 carbon atoms, and includes alkylene, arylene, aralkylene, alkarylene, alkylenearylene, or divalent alicyclic or heterocyclic groups and R 1 , R 2 , R 3 and R 4 represent hydrogen, OH, F, Cl, Br, I, NO 2 , NO, COOH, SO 3 H, NH 2 , NHNH 2 , arylazo, heteroarylazo or a substituted or unsubstituted alkyl, aryl or heteroaryl group of up to 20 carbon atoms.
The terms "alicyclic" and "heterocyclic" as used throughout the specification and appended claims refers to monocyclic and polycyclic groups composed of hydrogen and up to 20 carbon atoms, more preferably up to 12, and which may also contain one or more heteroatoms such as oxygen, nitrogen or sulfur. Preferred are those groups containing up to 6 ring atoms.
The term "substituted" as used throughout the specification and appended claims refers to substituents such as lower alkyl or aryl of up to about 12 carbon atoms, halogen, hydroxyl, nitro, and the like.
The quinoline polymers of the present invention were synthesized by allowing 2-aminomethyl-8-hydroxyquinolines of the general formula: ##STR2## to react with diisocyanates of the general formula:
0═C═N--R--N═C═O
wherein R, R 1 , R 2 , R 3 and R 4 are as indicated above.
Examples of the quinolines which may be employed include 2-aminomethyl-4,8-dihydroxyquinoline, 2-aminomethyl-4,8-dihydroxy-5-phenylazoquinoline, and the like.
The diisocyanates which can be employed include, for example, polymethylenediisocyanates such as tetramethylenediisocyanate and hexamethylenediisocyanate, and aromatic diisocyanates such as 2,4-toluenediisocyanate, mixtures of 2,4-and 2,6-toluenediisocyanates (80/20:2,4/2,6); p,p'-diphenylenediisocyanate, p,p'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthlene diisocyanate, 1,5-tetrahydronaphthlene diisocyanate, and other polyisocyanates such as 4,4'-diphenylmethanediisocyanate, p-phenylenediisocyanates, 1,5-tetrahydronaphthalenediisocyanate and 4,4'-dicyclohexylmethanediisocyanate.
The solvents which may be employed include tetrahydrofuran, toluene, dimethylformamide, dimethylsulfoxide, acetone, pyridine, methylenechloride and dioxane with pyridine being the preferred solvent.
The temperature of the reaction ranges from about 0° to 150° C., with the preferred temperature being 80° C.
In general, it is preferred to employ stoichiometric equivalent amounts of the 2-amino-methyl-8-hydroxyquinoline and the diisocyanate although proportions of the quinoline and the diisocyanate may range from about 0.75:1 to 1.25:1.
An indirect route for the synthesis of quinoline copolymers involves the preparation of the 2-ureadomethyl-8-carbamatoquinolines bearing terminal isocyanato groups, as in the formula: ##STR3## wherein R1-R 4 are as previously described. The bisisocyanatoquinoline is then allowed to react with diamine compounds of the formula:
H.sub.2 N--R'--NH.sub.2
to provide quinoline copolymers of the general formula: ##STR4## wherein R, R', R 1 -R 4 , n and m are as previously defined.
As indicated above, the quinoline polymers of the present invention complex with metal ions to form novel chelates. The choice of the particular metal ion will depend, of course, on the intended use of the chelate. That is, whether such use is in vitro or in vivo as well as the ability of the particular metal ion to form the chelate compound with the quinoline polymer of the invention.
Suitable metal ions include, but are not limited to, transition metal ions having atomic numbers of 21 to 29 and 40 to 83 and ions derived from the elements of the lanthanide series.
For nuclear therapy, one can use radioactive ions derived from elements such as copper. yttrium, rhenium, holmium, cesium and the like.
For fluorescence, one can utilize the elements of the lanthanide series such as europium, terbium, lanthanum and the like.
Preparation of the chelates of the quinoline polymers and the metal ions is effected in the conventional manner for the preparation of chelation of compounds. In practice, this can be accomplished by combining the quinoline polymer with an appropriate metal ion salt in an inert liquid medium. It is preferable to use a solvent in which both reaction partners are soluble. As shown in the examples, the quinoline polymer and the metal salts were mixed in an inert liquid, such as dimethylsulfoxide, and stirred at room temperature. The quinoline polymers of this invention are receptive to chelation, and thus may be advantageously utilized in any of the general technologies: radioisotopes for therapy and fluorescence in in vivo diagnostics, for example.
The following examples are illustrative of the best mode presently contemplated for the practice of this invention.
EXAMPLE 1
Polymer of 2-Aminomethyl-4,8-dihydroxyquinoline and 1,6-Diisocyanatohexane
A mixture of 238 milligrams (1.237 mmol) of 2-amino-4,8-dihydroxyquinoline and 0.2 milliliters (1.237 mmol) of 1,6-dissocyanatohexane in five milliliters of anydrous pyridine was stirred at 80° C. for four hours and at ambient temperature for 18 hours. Methanol (10 milliliters) was added and the solvents were removed by a rotary evaporator. The product was washed with methanol. 100 milligrams of the colorless solid polymer were obtained.
EXAMPLE 2
2-Ureadomethyl-4-hydroxy-8-carbamatoquinoline Chemical Structure: ##STR5##
A mixture of 160 miligrams (0.84 mmol) of 2-aminomethyl 4,8-dihydroxyquinoline and 1.0 milliliters of 1,6-diisocyanatohexane in 2.5 milliliters of anhydrous pyridine was stirred at ambient temperature for four days. The solvent was removed under high vacuo and the produce washed several times with hexane to remove the excess diisocyanate. 600 milligrams of the product was obtained. TLC on silica gel plate, using 20% methanol-methylene chloride, showed one spot, R f 0.84; infrared spectrum showed strong band at 2280 cm -1 (--N═C═O ).
EXAMPLE 3
Quinoline-pyridine Copolymer
The product of Example 2 was redissolved in five milliliters of anhydrous pyridine, To this was added 74 millgrams of 2,6-diaminopyridine and the mixture was stirred at amient temperature for 18 hours. The reaction mixture was then stirred at 100° C. for two hours and allowd to cool to room temperature. The solvent was removed in a rotary evaporator and the produce was washed with methanol. 420 milligrams of the copolymer was obtained.
EXAMPLE 4
Labeling of Quinoline Polymer with Ytrium-90
5 milligrams of quinoline polymer prepared as in Example 1 were dissolved in 1 ml of dimethylsulfoxide. To this was then added 1 mCi of yttrium-90 acetate, and to the stirrred solution 1 ml of 0.01M tris uffer (pH 7) was added in order to precipitate the particles. After 30 minutes of incubation at ambient temperature, the particles were filtered using a membrane with a molecular weight cut off of 30,000 Daltons, and washed three times with the same buffer. The biodistribution study in rabbits was performed by resuspending these labeled particles in saline, injecting the suspended material into the synovial cavity, and analyzing the readioactivity uptake by various organs over various time periods postinjection.
EXAMPLE 5
Labeling of Quioline Polymer with Indium-111
2 Mg of quinoline polymer, prepared according to Example 1, were dissolved in 1 ml of dimethylsulfoxide, To this was added 0.3 mCi of indium-111 tropolone, the rest of the procedure is the same as that for the labeling yttrium-90 detailed in Example 4. The indium-111 labeled particles were resuspended in saline and used for i. v. administration in animals as in Example 4.
Although the invention has been illustrated by the preceding examples, it is not to be construed as being limited to the materials employed therein, but rather, the invention is directed to the generic area as hereinbefore disclosed. Various modifications and embodiments thereof can be made without departing from the spirit or scope thereof.
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Quinoline polymers are provided which are conveniently prepared by the reaction of 2-amino-8-hydroxyquinolines and diisocyanates. The resulting polymeric compounds are then chelated with certain metal ions to provide chelates having utility in biological areas or in areas where the properties of the particular metal ion chelate can be utilized.
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TECHNICAL FIELD
The present invention relates to roof ditch molding used to cover the roof ditch of motor vehicles, and more particularly to an end formed roof ditch molding in which the Class A finish of the roof ditch molding is continuous, inclusive of the two end caps thereof.
BACKGROUND OF THE INVENTION
In the automotive arts, it is a well known practice to attach the roof panel to each of the left and right body side panels via a respective roof ditch. In this regard, a sealant or sealer tape is used to seal the overlapping metal edges of the roof and respective body side panels, wherein the roof ditch is thereupon covered by a cosmetic roof ditch molding. See, for example, U.S. Pat. Nos. 7,004,535 and 6,030,701.
A roof ditch and associated roof ditch molding of interest is utilized by General Motors Corporation of Detroit, Mich. with respect to its 2006 Chevrolet Impala, of which various aspects are exemplified at FIGS. 1 through 5 .
As shown at FIG. 1 , a roof ditch 10 runs longitudinally along each of the left and right joinders of the roof panel 12 with the left and right body side panels 14 , 16 . As best seen at FIGS. 2 and 3 , the roof ditch 10 is configured as a slot, having at its floor the overlap of a roof edge 12 a with a respective body panel edge (left body side panel edge 14 a being shown by way of example in FIGS. 2 and 3 ). A sealer tape 18 is located at the floor to seal the overlap of the edges. A roof ditch molding 20 is placed into each roof ditch above the sealer tape 18 to provide a cosmetic match between the roof panel and the left and right body side panels.
The roof ditch moldings 20 are each composed of a plastic extruded central molding member 20 a and a pair of separately plastic injection molded end caps 20 b , 20 c (see FIG. 1 , as well as FIG. 4 , whereat only end cap 20 b is shown). The central molding member 20 a has a T-shaped cross-section defined by a head 22 and a beam 24 , having preferably a metal insert 25 for stiffening. The visible portion of the head 22 a has a Class A finish which cosmetically matches the finish of the roof panel 12 and right and left body side panels 15 , 16 . At the lower extremity of the beam 24 is a pair of wings 26 which are periodically present along the length of the beam to provide securement by flexed conformance to the roof ditch at locations P 1 and P 2 (see FIG. 2 ). In order to prevent end peeling of the roof ditch molding from the roof ditch, each end portion of the beam is modified to remove the wings and provide thereat a plunger 28 which interferingly couples to a spring bracket 30 which is, itself, anchored in the roof ditch at the sealer tape 18 (see FIG. 3 ).
FIG. 5 is a block diagram 50 indicating the steps of manufacture of the prior art roof ditch molding 10 .
At execution Block 52 , the central molding member 20 is extruded, inclusive of the head 22 , the beam 24 and the wings 26 , wherein the wings may be composed of a more flexible material than the central molding member.
At execution Block 54 , the wings are routered away at the end portions of both ends of the beam (see 24 a in FIG. 4 ) and at selected periodic locations along the beam so that discrete sections of wings are present between the end portions.
At execution Block 56 , a surface prep 32 (see FIG. 3 ) is applied to the beam 24 at the end portions, the end portions are then placed in an injection molding machine, and the plungers 28 are then formed as a plastic injection mold onto the beam.
Finally, at execution Block 58 each end cap 20 d is separately injection molded onto the respective ends of the central molding member by placement of a section of each end portion of the central molding member into an injection molding machine (the result is shown best at FIG. 4 ).
While the roof ditch molding 20 serves its purpose quite well, there is difficulty encountered with respect to providing a seamless look to the Class A finish 22 a of the head 22 and the Class A finish 20 d of the end caps 20 a , 20 b , particularly in view of the line of interfacial demarcation 34 as between the extruded central molding member and the injection molded end caps. Further, while the injection molding of the plungers creates heat to the Class B side, this heat can cause untoward deformation of the Class A side of the head.
Accordingly, what remains needed in the art is some way to make a Class A finish seamlessly extending between the central molding member and the end caps of a roof ditch molding.
SUMMARY OF THE INVENTION
The present invention is a roof ditch molding having a Class A finish extending between the central molding member and the end caps thereof, effected by the end caps being integrally formed of the head of the central molding member.
The end formed roof ditch molding according to the present invention includes a plastic extruded central molding member inclusive of a beam, a head and wings at the lowermost extremity of the beam, wherein end portions of the beam have the wings removed and an end section of each end portion has the beam removed, and wherein at each end section the head is contoured to assume an end cap shape and is provided with a notch. Each end portion is then placed into a plastic injection molding machine whereat the end section thereof is folded at the notch and a shot of plastic deposited adjacent the notch as a brace for retention of the fold angle and stiffening of its now fully formed end cap. Only one end section may have the integral, end formed end cap in situations in which the roof ditch molding requires an end cap at only one end thereof.
It is an additional aspect of the present invention that the beam be extruded to include a pair of nibs (one on either side of the beam) disposed between the head and the wings. A metal insert may be provided in the head or beam during the extrusion process. In this regard, the periodic removal of the wings at the end portions of the beam provides for the nibs to interferingly engage the spring brackets of the roof ditch.
In operation of the end formed roof ditch molding according to the present invention, because the end caps are integrally formed of the head of the central molding member, the Class A finish is seamlessly continuous from end cap to end cap, and the cosmetic appearance of the end formed roof ditch molding is flawless.
Accordingly, it is an object of the present invention to provide an end formed roof ditch molding in which the end caps are integrally formed of the head of the central molding member thereof, whereby the Class A finish is continuous from end cap to end cap so that the cosmetic appearance of the end formed roof ditch molding is flawless.
This and additional objects, features and advantages of the present invention will become clearer from the following specification of a preferred embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of a moor vehicle with roof ditches and prior art roof ditch moldings therefor.
FIG. 2 is a sectional view taken along line 2 - 2 of FIG. 1 .
FIG. 3 is a sectional view taken along line 3 - 3 of FIG. 1 .
FIG. 4 is a truncated, perspective view of a portion of the prior art roof ditch molding of FIG. 1 .
FIG. 5 is a block diagram of the steps of manufacture of the prior art roof ditch molding of FIG. 1 .
FIG. 6 is a top plan view of a moor vehicle with roof ditches and end formed roof ditch moldings therefor according to the present invention.
FIG. 7 is a sectional view taken along line 7 - 7 of FIG. 6 .
FIG. 8 is a sectional view taken along line 8 - 8 of FIG. 7 .
FIG. 9 is a truncated, bottom perspective view of a end formed roof ditch molding according to the present invention, shown at an intermediate state of manufacture.
FIG. 10 is a truncated, side perspective view of a final manufactured end formed roof ditch molding of FIG. 6 .
FIG. 11 is a sectional view seen along line 11 - 11 of FIG. 10 .
FIG. 12 is a block diagram of the steps of manufacture of the end formed roof ditch molding of FIG. 6 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the Drawing, FIGS. 6 through 11 depict various views of, and FIG. 12 depicts the manufacturing steps for, an end formed roof ditch molding 100 according to the present invention.
Referring firstly to FIG. 6 , a roof ditch 102 runs longitudinally along each of the left and right joinders of the roof panel 104 with the left and right body side panels 106 , 108 . The roof ditch 102 is configured generally in a conventional manner as discussed hereinabove with respect to FIGS. 1 through 3 , being in the general form of a slot having its floor defined by the overlap of a respective roof panel edge 104 a with a respective body panel edge (left body panel edge 106 a being shown in FIGS. 7 and 8 merely be way of example). A sealer tape 110 is conventionally located at the floor of the roof ditch 102 in order to provide a seal of the overlapped roof and side panel edges.
As shown best at FIGS. 7 and 8 , the end formed roof ditch molding 100 according to the present invention is placed into each roof ditch 102 above the sealer tape 110 to provide a flawless cosmetic match between the roof panel and the left and right body side panels. The end formed roof ditch moldings 100 are each composed of a plastic extruded central molding member 112 , wherein it will be described hereinbelow how the end caps 114 a , 114 b are integrally formed thereof (see FIG. 6 , as well as FIG. 10 whereat only end cap 114 a is shown).
The central molding member 112 has a T-shaped cross-section defined by a head 116 and a beam 118 . Preferably a metal insert 120 for stiffening is provided during the extrusion process. A pair of nibs 122 a , 122 b , one nib disposed on each side of the beam 118 , are also provided during the extrusion process. At the lower extremity of the beam 118 is a pair of wings 124 also provided during the extrusion process, which may be formed of a material more flexible that that of the beam and the head. The wings 124 are periodically present along the length of the beam 118 to provide securement to the roof ditch by flexed conformance at locations P 1 ′ and P 2 ′ (see comparison between unflexed state of the wings at FIG. 11 to the flexed state of the wings in the roof ditch at FIG. 7 ).
The visible portion of the head has a Class A finish 116 a , and end caps 114 a , 114 b also have a Class A finish 114 c , wherein the Class A finish is flawlessly continuous with respect to the head and end caps. This feature is made possible because the end caps are integral with the head. The Class A finish of both the head and the end caps cosmetically matches the Class A finish 105 of both the roof and right and left body side panels.
In order to prevent end peeling of the end formed roof ditch molding 100 from the roof ditch 102 , each end section (see 126 at FIG. 10 ) of the beam 118 is modified to remove the wings 124 , whereby the nibs 122 a , 122 b are then thereat the lowest extremity of the beam. The nibs 122 a , 122 b interferingly couple to a spring bracket 128 secured in the roof ditch at the sealer tape 110 (see FIG. 8 ), obviating the above mentioned plunger and all its associated manufacturing steps
FIG. 12 is a block diagram 200 indicating the steps of manufacture of the end formed roof ditch molding 100 , wherein a mid-stage of the manufacture is shown at FIG. 9 , and a finished stage of the manufacture is shown at FIGS. 10 and 11 .
At execution Block 202 , the central molding member 112 is plastic extruded, inclusive of the head 116 , beam 118 , nibs 122 a , 122 b , wings 124 and insert 120 (if present), wherein the wings may be composed of a more flexible material than the central molding member, and wherein as the extrusion proceeds, the wings are sliced off at the end portions of the beam, as for example by a blade positioned appropriately near the extrusion location of the plastic extrusion machine, whereby the removal of the wings results in the nibs becoming locally thereat at the lowest extremity of the beam.
At execution Block 204 , at the end section 130 of the head 116 (see FIG. 9 ), the beam 118 is removed, an end cap contour C is provided, and a fold notch 132 provided, these three operations all being preferably provided by a grinding operation. The end result of execution Block 204 is shown at FIG. 9
Finally, at execution Block 206 a selected part of the end portion 126 of the central molding member is placed into a plastic injection molding machine, wherein the end section 130 is bent at the fold notch 132 to the predetermined angle with respect to the head, and a shot of plastic is injected at the fold notch to provide a brace 134 which affixes the orientation of the completed respective end cap 114 a , 114 b , (see FIG. 6 , and in particular see the end cap 114 a shown at FIG. 10 ).
As can be understood from FIG. 10 , since the head and the end caps are an integrally formed single piece, there is no interfacial demarcation therebetween, and that since the head and the end caps have continuously the same Class A finish, the cosmetic appearance of the end formed roof ditch molding 100 is flawless, being far superior to the prior art roof ditch molding which has an interfacial demarcation and differing manufactures of the head and the end caps.
It is to be understood that the inclusion of the pair of nibs with the central molding member provides an “I-beam” cross-section thereof (i.e., of the head, the beam and the pair of nibs) which improves the bending strength of the roof ditch molding according to the present invention as compared to the prior art roof ditch molding having an absence of nibs. This improved bending strength improves the final appearance and is based upon a right balance of the nib dimensions and the wing geometry with respect to the rest of the part, as shown at FIG. 11 . Further, since there is no injection molding step to add a plunger, as is required in the prior art, there is an improved surface appearance to the Class A side of the head whereat the Class A finish is located.
It is to be further understood that while it is most preferred to include both the nibs and at least one integral, end formed end cap in the most preferred embodiment of the present invention, other embodiments of the present invention can be derived therefrom, namely: 1) the extrusion process of the head and beam can include the nibs whether or not the end caps are formed integrally with the head, and 2) the end caps can be made integrally with the head whether or not the nibs are part of the extrusion of the head and beam.
To those skilled in the art to which this invention appertains, the above described preferred embodiment may be subject to change or modification. Such change or modification can be carried out without departing from the scope of the invention, which is intended to be limited only by the scope of the appended claims.
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A roof ditch molding having a Class A finish seamlessly including the end caps thereof. An extruded central molding member includes a beam and a head, wherein the end sections have the beam removed and the head is contoured and provided with a notch. The end sections are then placed into a plastic injection molding machine whereat the head is folded at the notch a shot of plastic deposited adjacent the notch for retention of the fold angle and stiffening of the now formed end caps. A pair of nibs provide engagement with spring clips at the ends of the roof ditch.
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