JP3294901B2 - Rubber composition - Google Patents

Rubber composition

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Publication number
JP3294901B2
JP3294901B2 JP11870493A JP11870493A JP3294901B2 JP 3294901 B2 JP3294901 B2 JP 3294901B2 JP 11870493 A JP11870493 A JP 11870493A JP 11870493 A JP11870493 A JP 11870493A JP 3294901 B2 JP3294901 B2 JP 3294901B2
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Prior art keywords
rubber
total nitrogen
nitrogen content
weight
rubber composition
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JP11870493A
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JPH06329838A (en
Inventor
直哉 市川
祐一 日置
正治 林
俊明 榊
康之 田中
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住友ゴム工業株式会社
花王株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition containing natural rubber.

[0002]

2. Description of the Related Art Natural rubber is used in many fields from industrial goods such as tires, belts and rolls to sports goods such as tennis balls. Generally, compression, recovery, and elongation of a rubber product during use are repeated, energy loss is accumulated and heat is generated, and this heat promotes rubber fatigue and shortens the life of the rubber product. The greater the energy loss represented by the loss tangent tan δ, the greater the heat generation. For example, in the case of a tire, the rolling resistance is ta at 50 to 70 ° C.
It is empirically known that it depends on the magnitude of n δ,
When tan δ is large, not only heat generation is increased, but also rolling resistance is increased, and there is a problem that fuel efficiency of an automobile is deteriorated. A race or high-performance high grip tire is required to have a particularly large tan δ of the tread, while a tread of a fuel-saving tire is desirably a small tan δ as described above.

[0003] Natural rubber has better mechanical properties than synthetic rubber and has a small tan δ, and as described above, is widely used in applications such as tires, industrial goods, and sports goods. However, in recent years, the performance requirements for various rubber materials have become increasingly severe, and it has become necessary to further improve the performance of natural rubber having excellent heat generation and mechanical properties. That is, it has better mechanical properties, smaller heat generation, and the like. In the case of a rubber composition for a fuel-saving tire, good heat grip as well as low heat generation are required. The wet grip depends on the magnitude of tan δ at 0 ° C., and the larger the better, the better the wet grip.

[0004] Conventionally, in a rubber composition in which a natural rubber and a synthetic rubber are blended, an attempt has been made to improve heat generation by improving the synthetic rubber. In the field of tires, attempts have been made to improve the grip when wet as well as to improve the heat buildup. In addition, the properties of general rubber, such as tensile strength and tear resistance, are limited only by the improvement of synthetic rubber, and pure natural rubber compositions are completely improved except for those based on compounding agents such as reinforcing agents. No clues.

[0005] Furthermore, raw natural rubber (rubber used as a raw material) has a problem in that the processability and productivity during production are poor. Generally, the rubber product manufacturing process includes a kneading process in which various additives are added to raw rubber to knead the rubber, and a calendering or extruding process in which the kneaded rubber is formed into a sheet. In addition, the elasticity and plasticity of a rubber material greatly affect its workability and work efficiency. The elasticity and plasticity of an unvulcanized rubber material are usually represented by Mooney viscosity.The higher the Mooney viscosity, the higher the elasticity of the rubber and the lower the plasticity, and the lower the Mooney viscosity, the lower the elasticity of the rubber and the higher the plasticity. There is a tendency.

[0006] Raw natural rubber has a very high Mooney viscosity due to its high molecular weight, and therefore has high elasticity and low plasticity. For this reason, it is difficult to sufficiently mix the additives in the kneading step, and in the steps of calendering and extrusion, the torque is increased, the processing speed is reduced, and the productivity is reduced. When the torque is large, the energy is accumulated in the rubber and causes the rubber to generate heat, which may cause the rubber to burn.

Therefore, it is common practice to masticate prior to the kneading step. When the mastication is performed, the elasticity of the rubber is reduced, the plasticity is increased, and the processing operation after the kneading step becomes easy. Mastication is an operation in which a mechanical shear force is applied to rubber before adding an additive to loosen molecular agglomeration and cut molecular chains to lower the molecular weight (to make this reaction more likely to occur). Peptizers may be used). But,
There is a problem that the productivity is reduced by the addition of the mastication step.

When a softening agent such as oil is blended, the Mooney viscosity decreases. However, since the softener is easily extracted from the rubber material even after vulcanization, if used in a large amount, it may bleed (bleed) onto the surface of the product after vulcanization, and may adversely affect the strength and the like. Depending on the application, it may not be used. It is known that natural rubber hardens during storage to increase the Mooney viscosity. To prevent this, a viscosity stabilized rubber (for example, SMR-CV) has been developed. However, this viscosity stabilized rubber contains hydroxylamine hydrochloride as an additive for stabilization,
Further, in some cases, it is necessary to add castor oil. Therefore, these chemicals may remain in the rubber product after vulcanization, adversely affecting the strength and the like, and may not be used depending on the application. In addition, since a step of adding these additives is added, there is a problem that productivity is reduced.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to further improve natural rubber which is superior in mechanical properties and heat generation as compared with synthetic rubber, that is, to achieve higher strength and tear resistance. It is an object of the present invention to provide a rubber composition which is large, has low heat build-up, has a low Mooney viscosity and is excellent in processability, does not require mastication, and has excellent productivity.

Another object of the present invention is to use this rubber composition as a material for a tire, to reduce rolling resistance, suppress heat build-up, and increase wet grip.

[0011]

Means for Solving the Problems and Actions In order to solve the above problems, the present inventors have conducted various studies on a new technology for modifying natural rubber. As a result, it is possible to remove the protein originally contained in natural rubber as much as possible at 50 to 70 ° C.
Tan δ at 0 ° C, improvement of tan δ at 0 ° C, high strength,
It has been found that it is effective in improving tear resistance and improving workability and productivity by lowering Mooney viscosity.

[0012] Natural rubbers subjected to a deproteinization treatment are known, and grade products such as crepe H, crepe G, crepe CD and the like are actually put on the market. These deproteinized natural rubbers are also actually used in rubber compositions. However, conventional deproteinized natural rubber has not obtained the above effects. When the present inventors examined the cause, it was found that the conventional deproteinized natural rubber was not yet sufficiently deproteinized.

It is generally said that the protein content of natural rubber can be represented by 6.3 times the total nitrogen content measured by the Kehldahl method. According to investigations by the present inventors, fresh natural rubber latex (field latex) has a total nitrogen content of about 0.5 to 0.5%.
0.8% by weight, commercial purified latex and raw rubber (smoked sheet rubber) have a total nitrogen content of about 0.3% by weight
That was all. Conventionally, the protein content of conventional deproteinized natural rubber is greatly reduced, but the total nitrogen content of crepe CD containing the least protein content is 0.11% by weight, and deproteinization is insufficient. Was.

Therefore, the present inventors have determined that the total nitrogen content is less than 0.1%.
Attempts to use highly deproteinized natural rubber to less than 1% by weight resulted in a
It succeeded in producing a rubber composition effective in reducing n δ, increasing tan δ at 0 ° C., increasing strength, improving tear resistance, and reducing Mooney viscosity, and completed the present invention. Was. That is, natural rubber highly deproteinized so as to have a total nitrogen content of 0.1% by weight or less has a smaller tan δ at 50 to 70 ° C. and a lower tan δ at 0 ° C. than ordinary natural rubber. δ is large, the strength is high, the tear resistance is large, and the Mooney viscosity is low.

Therefore, the first rubber composition of the present invention comprises:
Add a surfactant to natural rubber latex for cleaning
Subjected and the rubber component of the latex becomes isolated, with a total nitrogen content as an index of protein amount of 0.1 wt% or less
It is characterized by containing a certain deproteinized raw rubber and a vulcanizing agent or a crosslinking agent . Further, the second rubber of the present invention
The composition consists of a natural rubber latex with proteolytic enzymes or
Bacteria are added to degrade the protein and the
An index of protein mass, obtained by isolating the rubber content of latex,
With a total nitrogen content of less than 0.1% by weight
Containing raw rubber and vulcanizing or cross-linking agents
It is characterized by. The difference between the natural rubber used in the rubber composition of the present invention, which has been deproteinized until the total nitrogen content is 0.1% by weight or less, and conventionally known various deproteinized natural rubbers (crepe rubber) is as follows. It is clear from the following confirmation tests performed by the present inventors.

That is, various commercially available crepe rubbers are dried.
The dried product is dissolved in toluene, and this is infrared
The line spectra were measured.
0cm -1Absorption was observed. This absorption is due to the protein in the rubber.
Absorption caused by polypeptide binding.
Dried latex before deproteinization
Or RSS3 rubber.

On the other hand, the rubber composition of the present invention is used
The natural rubber deproteinized so that the total nitrogen content is 0.1% by weight or less has almost no absorption at the above-mentioned 3280 cm -1 , and especially the total nitrogen content is 0.02% by weight or less. The deproteinized natural rubber shows no absorption at 3280 cm -1 . This is because, as described later, the protein, that is, the polypeptide bond is degraded by treating the natural rubber with a protease and various surfactants.

The natural rubber used in the rubber composition of the present invention has a total nitrogen content in the rubber of 0.1% by weight as described above.
The protein is deproteinized until it becomes less, but as the protein is removed, the tan δ characteristics are improved (small at high temperature and large at low temperature), and processability and productivity are improved (decrease in Mooney viscosity). , High tear resistance and high tensile strength. Therefore, the lower the total nitrogen content in the rubber, the better, and within the above range, it is particularly preferably 0.05% by weight or less, more preferably 0.02% by weight or less.

The total nitrogen content used in the present invention is 0.1%.
Examples of natural rubber deproteinized to 1% by weight or less include “natural rubber vol. 6, No. 8, 274-281 (19)
74)), an improved deproteinized natural rubber (total nitrogen content: 0.06% by weight), etc.
In particular, those produced by the method proposed by the present applicant previously to decompose proteins by adding proteolytic enzymes or bacteria to latex, or by the method of repeatedly washing with a surfactant such as soap are preferred. Those which are used, particularly those produced by a method of treating them simultaneously or sequentially with a protease and a surfactant are more preferably used (Japanese Patent Application Nos. 4-208754 to 4-208754).
-208758). Washing with a surfactant may be performed by centrifugation or the like. After the above treatment, the rubber component is isolated by centrifuging the latex one or several times.

The protease used in the above treatment is not particularly limited, but may be of bacterial origin, of fungal origin,
Any yeast-derived protease may be used, but among them, a bacterial protease is preferably used. As the surfactant, for example, an anionic surfactant and / or a nonionic surfactant can be used. Examples of the anionic surfactant include carboxylic acid-based, sulfonic acid-based, sulfate-based, and phosphate-based surfactants.

The raw material latex may be fresh field latex obtained from a natural rubber tree or commercially available ammonia-treated latex. In particular, when the latter is used, natural rubber green strength (raw rubber) may be used. Strength) is improved, winding around a roll is improved, and there is also an effect that workability is further improved. The rubber composition of the present invention can use, as a main rubber component, a natural rubber which has been deproteinized so that the total nitrogen content is 0.1% by weight or less as described above, alone. To date, ordinary natural rubber that has not been deproteinized, commercially available deproteinized natural rubber having a total nitrogen content of more than 0.1% by weight, or various synthetic rubbers (styrene-butadiene rubber, butadiene rubber, etc.) Can also be used in combination with the deproteinized natural rubber.

Other components constituting the rubber composition of the present invention together with the above rubber component include sulfur, organic sulfur compounds,
Vulcanizing or cross-linking agents such as organic peroxides, metal oxides, polyamines, polyisocyanates, modified phenolic resins;
Vulcanization accelerators such as aldehyde-amines, dithiocarbanates, guanidines, thiazoles, thiurams; vulcanization accelerators such as metal oxides and fatty acids; various antioxidants;
Reinforcing agents such as carbon black and white carbon; fillers; tackifiers; plasticizers; softeners; peptizers; coloring agents;

The rubber composition of the present invention can be used as a material of a product which is subjected to repeated compression and elongation. For example, industrial goods such as tires, rubber belts, rubber rolls, bladders, fenders and the like, and sports goods such as tennis balls, basketballs, soccer balls, volleyballs and the like can be mentioned. In tires, treads, sidewalls, plies, beads, etc., can be used as materials for all components that make up a rubber tire. Be blended.

The rubber composition of the present invention thus obtained is
As described in the following examples, tan δ at 50 to 70 ° C.
It is excellent in the effects of lowering the strength, increasing the strength, improving the tear resistance, and improving the productivity by lowering the Mooney viscosity.
Furthermore, when this material is used as a tire, it has the advantage that it has low heat build-up and excellent grip when wet.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments, but the configuration of the present invention is not limited to the following embodiments. Example 1 (Preparation of raw rubber) A 1% aqueous solution of a nonionic surfactant [trade name: Emulgen 810, manufactured by Kao Corporation] was added to a commercially available high ammonia latex [manufactured by Gasly of Malaysia] to reduce the rubber concentration to 8%. Adjusted and centrifuged at 11,000 rpm for 30 minutes.

Next, the creamy fraction produced by centrifugation is dispersed in a 1% aqueous solution of Emulgen 810 to adjust the rubber content to 8%.
Centrifugation was performed at a rotation speed of 11,000 rpm for 30 minutes. After this operation was repeated once, the obtained creamy fraction was dispersed in distilled water to prepare a deproteinized rubber latex having a solid rubber content of 60%.

Next, the deproteinized rubber latex is frozen,
After coagulation, moisture was removed and dried to obtain raw rubber. When the total nitrogen content in the obtained raw rubber was measured by the Kehldahl method, it was 0.04% by weight. (Production of rubber composition) For 100 parts by weight of the raw rubber,
The following components were blended and kneaded to produce a rubber composition.

Component weight part Furnace black (ISAF * 1 ) 50 Styrene 3 Zinc oxide (ZnO) 3 Antioxidant 13 1 Antioxidant RD (TMQ * 2 ) 1 Sulfur 1.5 Vulcanization accelerator NS 75 * 1: Intermediate super abrasion furnace black * 2: Polymer of 2,2,4-trimethyl-1,2-dihidroquinone Example 2 (Preparation of raw rubber) Commercially available high ammonia latex [solid rubber content, manufactured by Guthrie, Malaysia] 62.0%]
The mixture was diluted with a 0.12% aqueous sodium naphthenate solution to make the solid rubber content 10% by weight, and the pH was adjusted to 9.2 by adding sodium dihydrogen phosphate. And rubber content 10
g, proteolytic enzyme (Alcalase 2.0M)
Was added at a rate of 0.87 g, and the pH was readjusted to 9.2, followed by maintaining at 37 ° C. for 24 hours.

Next, the latex after the enzyme treatment is
Nonionic surfactant [Emulgen 8 (trade name, manufactured by Kao Corporation)
10] was added to adjust the rubber content to 8%, and the mixture was centrifuged at a rotation speed of 11,000 rpm for 30 minutes. Next, the creamy fraction produced by centrifugation was dispersed in a 1% aqueous solution of Emulgen 810 to adjust the rubber content to 8%.
Centrifugation was performed for 30 minutes at a rotation speed of 000 rpm. After this operation was repeated once, the obtained creamy fraction was dispersed in distilled water to prepare a deproteinized rubber latex having a solid rubber content of 60%.

Next, the deproteinized rubber latex is frozen,
After coagulation, moisture was removed and dried to obtain raw rubber. When the total nitrogen content in the obtained raw rubber was measured by the Kjeldahl method, it was 0.015% by weight. (Production of rubber composition) A rubber composition was produced in the same manner as in Example 1 except that 100 parts by weight of the raw rubber was used.

Example 3 Same as Example 1 except that 100 parts by weight of a raw rubber having a total nitrogen content of 0.09% by weight, which was produced in the same manner as (Preparation of raw rubber) in Example 1, was used. To produce a rubber composition. Example 4 In the same manner as in Example 1 except that 100 parts by weight of a raw rubber having a total nitrogen content of 0.009% by weight and produced in the same manner as (Preparation of raw rubber) in Example 2 was used, A rubber composition was manufactured.

Example 5 Same as Example 1 except that 100 parts by weight of a raw rubber having a total nitrogen content of 0.02% by weight, which was produced in the same manner as (Preparation of raw rubber) in Example 2, was used. To produce a rubber composition. Comparative Example 1 A rubber composition was produced in the same manner as in Example 1, except that 100 parts by weight of pale crepe belonging to the cleanest class among commercially available solid rubbers was used without deproteinization. Total nitrogen content of solid rubber is 0.46% by weight
Met.

Comparative Example 2 Same as Example 1 except that 100 parts by weight of a raw rubber having a total nitrogen content of 0.11% by weight was produced in the same manner as (Preparation of raw rubber) in Example 1. To produce a rubber composition. Comparative Examples 3-5 The total nitrogen content used in Example 2 was 0.015% by weight.
The rubber compositions of Comparative Examples 3 to 5 were produced in the same manner as in Example 2 except that 100 parts by weight of each of the following raw rubbers was used instead of 100 parts by weight of raw rubber.

Comparative Example 3: High ammonia latex air-dried Comparative Example 4: SMR-CV (Standard Malaysian Rubber-
CV) Comparative Example 5: Natural rubber (RSS No. 3) prepared by adding a peptizing agent and masticating Tensile strength test The rubber compositions prepared in the above Examples and Comparative Examples were each subjected to 140 ° C. for 20 minutes. After press vulcanization under the conditions, JI
SK 6301 “Vulcanized rubber physical test method”
The initial tensile strength T B [MPa] and elongation E B (%) were determined according to the test method described in the section “Tensile test”. After the cured sample was allowed to stand at 100 ° C. for 48 hours, the same measurement was performed to determine the tensile strength T B [MPa] and the elongation E B (%) after aging.

Tear Strength Test Each of the rubber compositions prepared in each of the Examples and Comparative Examples was
After press vulcanization at 40 ° C for 20 minutes, JIS
According to the test method described in Section 9 “Tear Test” of K 6301 “Vulcanized Rubber Physical Test Method”, the tear strength T R
[KN / m] was determined.

Measurement of loss tangent tan δ The rubber compositions prepared in each of Examples and Comparative Examples were
After press vulcanization under conditions of 40 ° C. and 20 minutes, JIS K
The loss tangent tan δ was measured according to the test method described in 6394 “Test Method for Dynamic Properties of Vulcanized Rubber”. The measurement conditions were a frequency of 10 Hz, a temperature of 70 ° C. and 0 ° C.

Measurement of Mooney Viscosity and Scorch Time The Mooney viscosity ML 1 + 4 (130 ° C.) of the rubber composition prepared in each of the examples and comparative examples was measured according to JIS K 6300 “Physical test method for unvulcanized rubber”. It was measured in accordance with the test method described in the section 4 “Mooney viscosity test”. Scorch time (min) is 5 points, 10 points and 90
The machine automatically read the time until the point goes up.

Hardness Measurement The rubber compositions prepared in each of the Examples and Comparative Examples were respectively
After press vulcanization at 40 ° C for 20 minutes, JIS
The initial spring-type hardness H S was determined in accordance with the test method described in Section 5 “Hardness Test” of K 6301 “Vulcanized Rubber Physical Test Method”. In addition, the sample after vulcanization
After standing at 48 ° C. for 48 hours, the same measurement was performed to determine the spring hardness H S after aging.

Measurement of Abrasion Amount The rubber compositions prepared in each of Examples and Comparative Examples were
After press vulcanization at 40 ° C. for 20 minutes, the AKRON abrasion after 500 rotations and 500 rotations of this test using an Akron abrasion tester according to the method specified in BS standard 903 part A9 C method. [Cc] was measured.

Table 1 shows the above results. From the above results,
Tables 1 and 2 show the values of the total nitrogen content of the raw rubbers used in the rubber compositions of the respective Examples and Comparative Examples measured by the Kehldahl method.

[0041]

[Table 1]

[0042]

[Table 2]

As is clear from the results shown in Tables 1 and 2, all of Examples 1 to 5 having the constitution of the present invention have a Mooney compared to Comparative Examples 1 to 5 using other conventional raw rubbers. Since the viscosity was low and the Mooney viscosity was lower than that of Comparative Example 5 in which mastication was performed once, it was found that workability was improved as mastication was unnecessary, and that productivity was excellent.
Example 1 in which the total nitrogen content was 0.1% by weight or less
5 Both, total nitrogen content of a high strength T B tensile compared to Comparative Example 1-5 in which more than 0.1 wt%, yet it has been found that tear resistance is large.

[0044] Any Further Examples 1 to 5 also, small decrease and increase the amount of spring type hardness H S elongation E B due to aging, From this, it was confirmed that those not easily aged. In addition, since the results of the abrasion tests of Examples 1 to 5 were almost the same as those of the conventional ones, it was found that they were sufficiently usable as tire rubber.

Examples 1 to 5 are all comparative examples 1 to 5.
Since tan δ at 70 ° C. was smaller than that of No. 5, it was also found that a rubber tire having low energy loss and low rolling resistance could be manufactured. In addition, since Examples 1 to 5 all have equal or higher tan δ at 0 ° C. than Comparative Examples 1 to 5, it was also found that a rubber tire having good wet grip was obtained.

Further, when the results of the respective examples were compared and examined, it was confirmed that the lower the total nitrogen content was, the more desirable results were obtained.

[0047]

As described above, the rubber composition of the present invention has a composition at 50-70 ° C.
Low tan δ, excellent in reducing heat generation and rolling resistance, high strength, high tear resistance, and lower Mooney viscosity than masticated, good workability, no need for mastication, and high productivity It has outstanding characteristics that have never been seen before. Further, when this material is used as a tire material, there is a characteristic that heat generation is small, rolling resistance is reduced, and a wet grip is excellent.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoya Ichikawa 41-1, Shimizu, Uozumi-cho, Akashi-shi, Hyogo Prefecture Inventor Masaharu Hayashi 133-5 Enohara, Wakayama City, Wakayama Prefecture (56) References JP-A-6-256404 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08L 7/00-7 / 02 C08C 1/00-19/44

Claims (5)

    (57) [Claims]
  1. (1) A surfactant is added to natural rubber latex.
    Wash and isolate the latex rubber.
    Comprising Te, total nitrogen content as an indicator of protein mass 0.1
    A rubber composition comprising: deproteinized raw rubber that is not more than weight%; and a vulcanizing agent or a crosslinking agent .
  2. 2. The method of claim 1 wherein the natural rubber latex contains proteolytic enzymes or
    Is used to treat the protein by adding bacteria
    Deproteinization comprising isolated rubber component of the latex, the total nitrogen content as an indicator of protein amount is 0.1 wt% or less
    A rubber composition comprising: a raw rubber; and a vulcanizing agent or a crosslinking agent .
  3. Wherein the claim 1 or 2 A rubber composition according total nitrogen content of 0.05 wt% or less.
  4. Wherein said claim 1 or 2 A rubber composition according total nitrogen content of 0.02 wt% or less.
  5. 5. Any of claims 1-4, which is a material for tires
    The rubber composition of crab according.
JP11870493A 1993-05-20 1993-05-20 Rubber composition Expired - Lifetime JP3294901B2 (en)

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