Patent Application
20080177011
The present invention relates to a fibrous reinforcement for an air suspension to be used for air suspensions and the like in railroad cars, various types of industrial machinery, and automobiles (passenger cars, trucks, buses, and the like), and an air suspension reinforced by this fibrous reinforcement.
Examples of air suspensions to be used for suspensions in automobiles, suspensions of cabins in trucks, suspensions of seats for sitting, and the like includes those shown in
In an air suspension shown in
An air suspension shown in
The known rubber films 102 and 202 of the air suspension are reinforced by fiber cord layers (fiber cord woven fabrics) in which a large number of fiber cords formed from nylon or polyester are inclined relative to the circumferential direction of the rubber film main body and are arranged parallel to each other. Usually, two fiber cord layers are laminated while the first fiber cord layer and the second fiber cord layer are arranged in such a way that the fiber cord directions are inclined bilaterally symmetrically.
The nylon fiber exhibits excellent adhesion to the rubber. On the other hand, since the elongation is large, it is difficult to give sufficient pressure resistance to the rubber film. An aramid fiber is a reinforcing fiber having a small elongation. However, the aramid fiber exhibits poor adhesion to the rubber, and peeling between rubber/fiber easily occurs.
In order to improve the pressure resistance of the rubber film of the air suspension, sometimes, the number of the reinforcing fiber cord layers (the number of lamination of layers) is increased, the density of arrangement of the fiber cords is increased, or a high-strength cord, e.g., a carbon fiber cord, a steel cord, or a glass fiber cord, is used instead of the fiber cord. However, in the case where the number of lamination of the reinforcing fiber cord layers is increased, the film rigidity also increases and the deformation resistance increases. Consequently, fatigue is easily produced due to repetition of bending and the durability is impaired. In the case where the density of arrangement of the fiber cords is increased, it becomes impossible to ensure the rubber in a gap between the fiber cords and interlayer peeling easily occurs. In the case where the high-strength cord is used, the elongation for reinforcing the air suspension is insufficient, the bending resistance becomes poor, and the price becomes high.
Therefore, a technology for improving the pressure resistance, the bending resistance, the peeling resistance between rubber/fiber, the fatigue resistance, and the durability of the rubber film of the air suspension is desired regarding the common reinforcing fiber cord configuration.
It is an object of the present invention to provide a fibrous reinforcement for an air suspension effective for improving the pressure resistance, the bending resistance, the peeling resistance between rubber/fiber, the fatigue resistance, and the durability of a rubber film of the air suspension and an air suspension having the pressure resistance, the bending resistance, the peeling resistance between rubber/fiber, the fatigue resistance, and the durability improved significantly by using this fibrous reinforcement.
A fibrous reinforcement for an air suspension according to the present invention is characterized by including polyketone fibers.
An air suspension according to the present invention is characterized by including rubber reinforced by this fibrous reinforcement for an air suspension.
A fibrous reinforcement according to the present invention includes polyketone fibers.
The polyketone fiber exhibits excellent adhesion to the rubber and small elongation. Therefore, the pressure resistance, the bending resistance, the peeling resistance between rubber/fiber, the fatigue resistance, and the durability of a rubber film of an air suspension can be improved by using the polyketone fibers as the fibrous reinforcement.
The fibrous reinforcement according to the present invention may be formed substantially from a polyketone fiber cord. The fibrous reinforcement according to the present invention may be formed from a composite fiber cord containing polyketone, for example, a composite fiber cord of polyketone fibers and other fibers.
Preferably, the polyketone fiber constituting the fiber cord according to the present invention is produced from polyketone which is a raw material and which is represented by the following general formula (I):
in the general formula (I), R represents a bonding group derived from an ethylenic unsaturated compound and may be the same or different from one repeating unit to another.
The above-described polyketone is an alternating copolymer having a structure in which CO (carbonyl group) units and units derived from ethylenic unsaturated compounds are arranged in a molecule, that is, one olefin unit, e.g., an ethylene unit, is located adjacently to each CO unit in a polymer chain. This polyketone may be a copolymer of carbon monoxide and one type of specific ethylenic unsaturated compound or a copolymer of carbon monoxide and two or more types of ethylenic unsaturated compounds.
Examples of ethylenic unsaturated compounds constituting R in the above-described formula (I) include unsaturated hydrocarbon compounds, e.g., ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, and styrene; unsaturated carboxylic acid or derivatives thereof, e.g., methyl acrylate, methyl methacrylate, vinyl acetate, and undecenic acid; and furthermore, undecenol; 6-chlorohexene; N-vinylpyrrolidone; and a diethyl ester of sulnyl phosphonic acid. These may be used alone or at least two types thereof may be used in combination. In particular, polyketone, in which an ethylenic unsaturated compound primarily containing ethylene is used, is preferable from the viewpoint of the dynamic characteristics, the heat resistance, and the like of the polymer.
In the case where ethylene and other ethylenic unsaturated compounds are used in combination as the ethylenic unsaturated compounds constituting the polyketone, it is preferable that ethylene is used in such a way as to constitute 80 percent by mole of the entire ethylenic unsaturated compounds. If this ratio is less than 80 percent by mole, the melting point of the resulting polymer becomes 200° C. or lower and, thereby, the heat resistance of the resulting polyketone fiber may become unsatisfactory. Preferably, the usage of ethylene is 90 percent by mole or more relative to the entire ethylenic unsaturated compounds from the viewpoint of the dynamic characteristics and the heat resistance of the polyketone fiber.
The above-described polyketone can be produced by known methods, for example, the methods described in EP Publication No. 121965 A, EP Publication No. 213671 A, and U.S. Pat. No. 3,914,391, the contents of which are hereby incorporated herein by reference.
Regarding the degree of polymerization of the above-described polyketone, preferably, the solution viscosity measured in m-cresol at 60° C. is within the range of 1.0 to 10.0 dL/g. If the solution viscosity is less than 1.0 dL/g, the dynamic strength of the resulting polyketone fiber may become unsatisfactory. Therefore, further preferably, the solution viscosity is 1.2 dL/g or more from the viewpoint of the dynamic strength of the polyketone fiber. On the other hand, if the solution viscosity exceeds 10.0 dL/g, the melting viscosity and the solution viscosity during formation of fibers may become too high and the spinnability may become poor. Therefore, further preferably, the solution viscosity is 5.0 dL/g or less from the viewpoint of the spinnability. It is particularly preferable that the solution viscosity is within the range of 1.3 to 4.0 dL/g in consideration of the dynamic strength, the spinnability, and the like of the fibers.
The above-described method for forming fibers of polyketone is not specifically limited. However, in general, a melt spinning method or a solution spinning method is adopted. In the case where the melt spinning method is adopted, desired fibers can be easily produced by the method described in, for example, Japanese Unexamined Patent Application Publication No. 1-124617, wherein a polymer is melt-spun usually at a temperature at least 20° C. higher than the melting point, and preferably about 40° C. higher than the melting point, and subsequently, a drawing treatment is performed usually at a temperature at least 10° C. lower than the melting point, and preferably about 40° C. lower than the melting point with a draw ratio of preferably at least 3 times, and further preferably with a draw ratio of at least 7 times.
On the other hand, in the case where the solution spinning is adopted, desired filaments can be produced by the method described in, for example, Japanese Unexamined Patent Application Publication No. 2-112413 incorporated herein by reference, wherein a polymer is dissolved into, for example, hexafluoroisopropanol, m-cresol, or the like at a concentration of 0.25 to 20 percent by mass, and preferably 0.5 to 10 percent by mass, fibers are formed by extrusion from a spinning nozzle, removal of the solvent and cleaning are performed in a bath of non-solvent, e.g., toluene, ethanol, isopropanol, n-hexane, isooctane, acetone, methyl ethyl ketone, or the like, preferably in an acetone bath to produce spun fibers, and furthermore, a drawing treatment is performed at a temperature within the range of (melting point−100° C.) to (melting point+10° C.), and preferably (melting point−50° C.) to (melting point). It is preferable that an antioxidant is added to this polyketone for the purpose of giving sufficient durability against heat, oxygen, and the like. If necessary, a delustering agent, a pigment, an antistatic agent, and the like can also be blended.
Preferably, the fiber cord substantially formed from the polyketone fiber is produced by performing first twisting of a plurality of polyketone fibers and further performing final twisting. Preferably, the final twisting coefficient thereof is 1,500 or more, in particular, within the range of 1,800 to 2,300. If the final twisting coefficient is less than 1,500, the bending fatigue resistance of the resulting rubber film becomes poor. If the final twisting coefficient is too large, the strength decreases, and the elongation and the creep increase. Therefore, it is preferable that the final twisting coefficient is 2,300 or less.
The final twisting coefficient is calculated, as described below, from the total fineness D (decitex: dtex) of the fibers constituting the cord and the number of final twists G (turns/10 cm).
Final twisting coefficient=G×√{square root over (D×0.9)} [Mathematical expression 1]
The number of first twists of this polyketone cord may be the same extent as the number of final twists, although they are not necessarily the same.
The total fineness of the polyketone fibers constituting the polyketone fiber cord is determined on the basis of a required strength force of the cord. For example, it is preferable that the total fineness is 1,800 to 5,010 decitex for the air suspension for a truck, a bus, or a railroad and is 400 to 1,500 decitex for the air suspension for a passenger car.
In the composite fiber cord including polyketone fibers and other fibers (hereafter referred to as “composite fiber cord of polyketone/other fiber”), preferably, the proportion of the total fineness of the polyketone fibers is 34% or more, in particular, 50% to 80% relative to the total fineness of the polyketone fibers and the other fibers constituting the cord. If the fineness of the polyketone fibers is smaller than this range, the effect of the present invention based on the use of the polyketone fibers cannot be exerted satisfactorily. Conversely, if the fineness is too large, the effect of combination with the other fibers cannot be exerted satisfactorily.
Preferably, the final twisting coefficient of the composite fiber cord of polyketone/other fiber is 1,500 or more, in particular, within the range of 1,800 to 2,300 for the same reason as the above-described reason for the polyketone fiber cord. If the final twisting coefficient is less than 1,500, the bending fatigue resistance of the resulting rubber film becomes poor. If the final twisting coefficient is too large, the strength decreases, and the elongation and the creep increase. Therefore, it is preferable that the final twisting coefficient is 2,300 or less.
The number of first twists of this composite fiber cord of polyketone/other fiber may not be the same as the number of final twists. It is preferable that the number of first twists is within the range of 0.5 to 1.5 times the number of final twists.
The total fineness of the polyketone fibers and the other fibers constituting the composite fiber cord of polyketone/other fiber is determined on the basis of a required strength force of the woven fabric. For example, it is preferable that the total fineness is 1,800 to 5,010 decitex for the air suspension for a truck, a bus, or a railroad and is 400 to 1,500 decitex for the air suspension for a passenger car.
Examples of the other fibers constituting the composite fiber woven fabric include nylon fibers and polyester fibers. One type of these other fibers may be used alone, or at least two types may be used in combination. In particular, it is preferable that the nylon fibers are used as the other fibers. The use of the nylon fibers in combination exerts the effects of increasing the elongation appropriately, improving the shock absorbing property, and facilitating the ride comfort.
In the present invention, 6,6-nylon, 6-nylon, 4,6-nylon, MXD6 nylon, or the like can be used as nylon constituting the nylon fibers. Preferably, 6,6-nylon is used.
In usual cases, the fiber cords are parallel arranged at a predetermined angle with respect to one direction of the rubber film. The number of disposition (density) of the polyketone fiber cords or the composite fiber cords of polyketone/other fiber is determined appropriately in accordance with the fineness thereof, characteristics required of the resulting rubber film, and the like. For example, preferably, the number of disposition is about 40 to 80 cords/5 cm for the air suspension for a truck, a bus, or a railroad and is about 90 to 150 cords/5 cm for the air suspension for a passenger car.
On the other hand, a rubber composition constituting the rubber film of the air suspension according to the present invention is not specifically limited. Common rubber compositions can be used, wherein a rubber component is the primary component and common additives are blended therein. Examples of the additives include a vulcanizing agent, an accelerator (vulcanization accelerator), a reinforcing agent, e.g., carbon and zinc oxide (zinc white), a plasticizer, e.g., aromatic oil, and if necessary, an age resistor, a mold release agent, a dispersing agent, a curing agent, a processing aid and extender, e.g., an adhesion regulator, and a colorant.
For the rubber component, one type of natural rubber (NR), styrene butadiene rubber (SBR), butadiene rubber (BR), chlorosulfonated polyethylene rubber (CSM), chloroprene rubber (CR), ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), butyl rubber (IIR), acrylic rubber (ACM, ANM), ethylene acrylic rubber (AEM), hydrogenated nitrile rubber (HNBR), nitrile rubber (NBR), Hypalon (CSM), urethane rubber (U), and the like or blend rubber of at least two types thereof can be used.
For the purpose of reducing the vulcanization time by performing high temperature vulcanization, it is preferable that a rubber component containing at least one type of heat-resistant rubber is used. Examples of heat-resistant rubber include ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), butyl rubber (IIR), acrylic rubber (ACM), ethylene acrylic rubber (AEM), and hydrogenated nitrile rubber (HNBR).
However, the rubber component may be blend rubber of at least one type of the heat-resistant rubber and at least one type of versatile diene rubber, e.g., natural rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR), and chloroprene rubber (CR) or contain the above-described versatile diene rubber as a primary component depending on a vulcanization method.
In the case where the above-described heat-resistant rubber is contained as a primary component, it is preferable that the vulcanization is performed by using organic peroxides, resins, or amines as vulcanizing agents. Examples of the organic peroxides include dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, 1,3-bis(t-butylperoxy-isopropyl)benzene, and 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane. Examples of resins include alkylphenol.formaldehyde resins and brominated alkylphenol.formaldehyde resins. Examples of amines include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, diamines, e.g., diaminodiphenylmethane and hexamethylenediamine carbamate, and triethylenetetramine.
These vulcanizing agents other than sulfur may be used alone or at least two types may be used in combination.
If the usage of vulcanizing agent is too large, there is an increasing tendency toward embrittlement and the rubber becomes brittle. If the usage is too small, a cross-linking effect is reduced and a plastic property results, so that an appropriate rubber properties cannot be obtained. Therefore, it is preferable that the usage is specified to be 0.5 to 4.0 parts by weight relative to 100 parts by weight of rubber component.
In the case where the above-described versatile diene rubber is used as the rubber component, it is preferable that efficient vulcanization is performed by using a sulfur-containing compound, e.g., a thiuram based vulcanizing agent, or vulcanization is performed by using an organic vulcanizing agent, e.g., N,N′-m-phenylenedimaleimide, dicumyl peroxide, or 1,3-bis(t-butylperoxy-isopropyl)benzene.
The rubber film of the air suspension according to the present invention can be easily produced by a common molding vulcanization method while the above-described fiber cords according to the present invention are interposed between unvulcanized rubber formed from the above-described rubber composition.
In the case where the molding vulcanization is performed while the above-described reinforcing fiber cords according to the present invention are interposed between the unvulcanized rubber, if necessary, the reinforcing fiber cords may be impregnated with an adhesive. A common RFL solution (resorcin.formalin.latex) or the like can be used as this adhesive. Preferably, the amount of adhesion thereof is about 3.0% to 8.0% relative to the reinforcing fiber cord.
The dimension of the rubber film of the air suspension according to the present invention is not specifically limited. Usually, it is preferable that the thickness thereof is, for example, 4.0 to 7.0 mm, in particular, about 5 mm for the air suspension for a truck and a bus, 5.0 to 12.0 mm, in particular, about 10 mm for the air suspension for a railroad, and about 2 to 3 mm for the air suspension for a passenger car.
The rubber film of the air suspension according to the present invention can be produced as described below, for example. However, the following method for producing the rubber film is an example of the method for producing the rubber film according to the present invention. Therefore, the method is not limited to the following method.
(1) Method for Producing Rubber Film of Air Suspension for Passenger Car
A fiber woven fabric is produced by using the above-described fiber cords. In general, this fiber woven fabric is a cord fabric. Preferably, the thickness of the fiber cord to be used is about 0.2 to 0.4 mm. The thickness of the rubber film of the air suspension for a passenger car is specified to be about 2 to 3 mm, as described above. Therefore, if the thickness of the fiber cord is larger than this range, the thickness of the rubber film increases, the bending rigidity of the rubber film becomes high, and the durability and the ride comfort are adversely affected. If the thickness of the fiber cord is smaller than this range, satisfactory strength is not obtained. Since the polyketone fiber to be used in the present invention has high strength, even when the fiber cord is relatively thin, high strength can be obtained.
As described above, the fiber woven fabric is impregnated with the common adhesive, e.g., the RFL solution, if necessary.
Two fiber woven fabrics described above are used, and both surfaces of each fiber woven fabric are coated with adhesive rubber of CR base or the like. Two coated goods are laminated in such a way that the warp directions of the cord fabrics intersect at a predetermined intersection angle and bilateral symmetry is established in the warp direction. Furthermore, cover rubber of CR base or the like is laminated on both surfaces of the resulting laminated sheet and heat-vulcanization is performed at a predetermined condition. The above-described adhesive rubber has a thickness of about 0.2 to 0.25 mm, and the cover rubber has a thickness of about 0.6 to 0.8 mm.
(2) Method for Producing Rubber Film of Air Suspension for Truck, Bus, or Railroad
A fiber woven fabric is produced by using the above-described fiber cords. In general, this fiber woven fabric is a cord fabric. The thickness of the fiber cord to be used is not specifically limited. However, about 0.5 to 1.2 mm is preferable. The thickness of the rubber film of the air suspension for a truck, a bus, or a railroad is specified to be about 5 to 10 mm, as described above. Therefore, it is preferable that the thickness of the fiber cord is specified to be within the above-described range from the viewpoint of the bending rigidity, the strength, and the like of the rubber film
As described above, the fiber woven fabric is impregnated with the common adhesive, e.g., the RFL solution, if necessary.
Two fiber woven fabrics described above are used, and both surfaces of each fiber woven fabric are coated with adhesive rubber of NR/SBR base or the like. Two coated goods are laminated in such a way that the warp directions of the cord fabrics intersect at a predetermined intersection angle and bilateral symmetry is established in the warp direction. Furthermore, cover rubber of NR/SBR base or the like is laminated on both surfaces of the resulting laminated sheet and heat-vulcanization is performed at a predetermined condition. The above-described adhesive rubber has a thickness of about 0.25 to 0.35 mm, and the cover rubber has a thickness of about 2 to 4 mm.
The present invention will be specifically described below with reference to the examples and the comparative examples.
In the following description, the polyketone fibers to be used were produced by forming fibers from polyketone represented by the above-described general formula (1) where R was ethylene, the polyketone having a degree of polymerization suitable for exhibiting a solution viscosity measured in m-cresol at 60° C. of 4.0 dL/g. The 6,6-nylon fiber was used as the nylon fibers.
Regarding cord fabrics including cords shown in Table 1 with the number of disposition (density) shown in Table 1, the properties were evaluated by the following methods. The results are shown in Table 2.
<Properties of Dipped Goods>
The cord fabric was dipped in an adhesive solution (RFL solution (resorcin.formalin.latex)), so that the adhesive solution (solid matter) was adhered thereto by 6%. The resulting cord fabric was evaluated by the following methods i) to iii).
i) Strength Force and Elongation
Regarding one cord, the measurement was performed on the basis of JIS L1017 at a distance between grips of 25 cm and a tensile speed of 30 cm/min.
ii) Heat Shrinkage
On the basis of JIS L1017 (method B), heating was performed at a temperature of 180° C. for 0.5 hours, cooling was performed for 30 minutes and, thereafter, the value of heat shrinkage was measured.
iii) Tenacity (g/d)
The value of strength force in the unit of N measured in the item i) was converted to a value in the unit of g, and the resulting value was divided by a total denier number of the cord (0.9 denier=1.0 dt (decitex) so as to determine the tenacity.
<Properties after Vulcanization>
Regarding the samples produced as described in the following items [1] and [2], the measurements were performed as described in the following items iv) to ix).
[1] Method for Producing Rubber Film Sample of Air Suspension for Passenger Car
Two cord fabrics of fiber cords were used after being subjected to an adhesion treatment with the RFL solution. Both surfaces of each cord fabric were coated with adhesive rubber of CR base having a thickness of 0.2 mm. Two coated goods were laminated in such a way that the warp directions of the cord fabrics intersected at a predetermined intersection angle and bilateral symmetry was established in the warp direction. Furthermore, cover rubber of CR base having a thickness of 0.6 mm was laminated on each of the two surfaces of the resulting laminated sheet and vulcanization was performed under the condition of 170° C. and 0.75 MPa for 15 minutes.
[2] Method for Producing Rubber Film Sample of Air Suspension for Truck, Bus, or Railroad
Two cord fabrics of fiber cords were used after being subjected to an adhesion treatment with the RFL solution. Both surfaces of each cord fabric were coated with adhesive rubber of NR/SBR base having a thickness of 0.3 mm. Two coated goods were laminated in such a way that the warp directions of the cord fabrics intersected at a predetermined intersection angle and bilateral symmetry was established in the warp direction. Furthermore, cover rubber of NR/SBR base having a thickness of 2.5 mm was laminated on each of the two surfaces of the resulting laminated sheet and vulcanization was performed under the condition of 155° C. and 1.5 MPa for 20 minutes.
iv) Strength Force
The reinforcing fiber cord was taken out of the vulcanized sample, and the strength force was measured in a manner similar to the above-described method for measuring the strength force of the dipped goods.
v) Strength Maintenance Ratio after Bending (%)
Two coated goods produced as in the above-described items [1] and [2] were laminated in such a way that the warp directions of the cord fabrics were directed in the longitudinal direction of the sample. The resulting vulcanized sample in the shape of a slip having a width of 25 mm±0.5 mm was looped over a pulley, and a bending test was performed under the following condition. After the bending test, the reinforcing fiber cord in the innermost layer during the bending test was taken out, the strength force was measured in a manner similar to the above-described method for measuring the strength force of the dipped goods, and the maintenance ratio thereof (strength after bending test÷strength before bending test×100) was calculated.
pulley diameter: 75 mm
load: 10% of strength force at break
the number of bending: 200,000 times
vi) Adhesion (Peeling Test)
Two coated goods produced as in the above-described items [1] and [2] were laminated in such a way that the warp directions of the cord fabrics became parallel to each other, so that a laminated sheet in the shape of a slip having a width of 25 mm±0.5 mm and a length of 100 mm was produced. Regarding this sample, a peeling test was performed based on JIS K6256-1999 at a rate of 50 mm/min. The adhesion force (N/25 mm width) was determined from the force required for peeling at this time.
vii) Separation Resistance (for Passenger Car)
A piston was actuated under the following condition, and the number of reciprocation of the piston until an irregularity, e.g., leakage of air, bulging due to entrance of air between the rubber fiber cords, or peeling between the rubber fiber cords, occurred.
inner pressure: 1.2 MPa
effective diameter of air suspension: 95 mm
amplitude of piston: ±40 mm
viii) Durability (for Truck, Bus, and Railroad)
A piston was actuated under the following condition, and the number of reciprocation of the piston until an irregularity, e.g., leakage of air or cracking of surface rubber, occurred.
inner pressure: 1.0 MPa
effective diameter of air suspension: 200 mm
amplitude of piston: ±50 mm
ix) Pressure Resistance
A maximum pressure until breakage occurred was measured on the basis of JIS D4101.
As is clear from Tables 1 and 2, according to the present invention, the air suspension exhibiting excellent pressure resistance, bending resistance, peeling resistance between rubber/fiber, fatigue resistance, and durability is provided by the reinforcing effect of the polyketone fiber.
The present invention has been described in detail with reference to specific forms. However, it is apparent to those skilled in the art that various modifications could be made without departing from the spirit or scope of the present invention.
The present invention contains subject matters related to Japanese patent application (Japanese Patent Application No. 2005-228358) filed on Aug. 5, 2005 and Japanese patent application (Japanese Patent Application No. 2005-319697) filed on Nov. 2, 2005, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-228358 | Aug 2005 | JP | national |
| 2005-319697 | Nov 2005 | JP | national |
This is a continuation application of PCT/JP2006/314559 filed on Jul. 24, 2006.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2006/314559 | Jul 2006 | US |
| Child | 12023081 | US |
