WO2003064518A1 - Rubber composition, vulcanizable rubber composition, and vulcanizate - Google Patents

Rubber composition, vulcanizable rubber composition, and vulcanizate Download PDF

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Publication number
WO2003064518A1
WO2003064518A1 PCT/JP2003/000933 JP0300933W WO03064518A1 WO 2003064518 A1 WO2003064518 A1 WO 2003064518A1 JP 0300933 W JP0300933 W JP 0300933W WO 03064518 A1 WO03064518 A1 WO 03064518A1
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Prior art keywords
rubber composition
weight
rubber
ethylenically unsaturated
parts
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PCT/JP2003/000933
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French (fr)
Japanese (ja)
Inventor
Akira Tsukada
Hirofumi Nomoto
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Zeon Corporation
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Publication of WO2003064518A1 publication Critical patent/WO2003064518A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber

Definitions

  • the present invention relates to a rubber composition used as a material for a rubber vulcanizate having excellent resistance to deterioration oil.
  • An object of the present invention is to provide a rubber vulcanizate which is excellent in oil resistance to deterioration and a rubber vulcanizate used as the material.
  • the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a nitrile group-containing copolymer rubber having a small iodine value and a large ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit content has a high ethylene content. Vulcanization by blending with a metal salt of a unsaturated unsaturated carboxylic acid to obtain a rubber vulcanizate that hardly changes in volume even when it comes into contact with degraded oil, hardens and hardly cracks The present inventors have completed the present invention based on this finding.
  • an iodine value of 20 or less, Per 100 parts by weight of a nitrile group-containing copolymer rubber (A) having an unsaturated unsaturated nitrile monomer unit content of 40 to 60% by weight, ⁇ ; -ethylenically unsaturated carboxylic acid metal salt (B) 3 to A rubber composition comprising 100 parts by weight is provided.
  • ⁇ , ⁇ — is based on 100 parts by weight of a nitrile group-containing copolymer rubber ( ⁇ ) having an iodine value of 20 or less and an ethylenically unsaturated nitrile monomer unit content of 40 to 60% by weight.
  • a vulcanizable rubber composition containing 3 to 100 parts by weight of a metal salt of an ethylenically unsaturated carboxylic acid (II) and 0.2 to 10 parts by weight of an organic peroxide vulcanizing agent.
  • a vulcanizate obtained by vulcanizing the above vulcanizable rubber composition.
  • the rubber composition of the present invention has an iodine value of 20 or less, an ⁇ , monoethylenically unsaturated nitrile monomer unit content of 40 to 60% by weight, and 100 parts by weight of a nitrile group-containing copolymer rubber ( ⁇ ).
  • ⁇ nitrile group-containing copolymer rubber
  • the nitrile group-containing copolymer rubber ( ⁇ ) used in the present invention is a rubber obtained by copolymerizing an a, S-ethylenically unsaturated nitrile-based monomer with another monomer.
  • the content of the unsaturated unsaturated nitrile monomer unit is 40 to 60% by weight, preferably 42 to 55% by weight. If the content of ⁇ , 8-ethylenically unsaturated nitrile monomer is too low, the oil resistance to deterioration is poor, and if it is too high, the cold resistance is poor.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and the like, with acrylonitrile being preferred.
  • the monomer to be copolymerized with the ⁇ , -ethylenically unsaturated nitrile monomer is a conjugated diene monomer, a non-conjugated dimeric monomer, ⁇ —Olefin and the like.
  • the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1-1.3-butadiene, and 1,3-pentadiene, and 1,3-butadiene is preferable.
  • the non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentadiene, 1.4-hexadiene, vinyl norportene, and dicyclopentadiene.
  • 1,4-pentadiene 1,4-pentadiene
  • 1.4-hexadiene vinyl norportene
  • dicyclopentadiene One-year-old ref Those having a number of 2 to 12 are preferred. Examples thereof include ethylene, propylene, 1-butene, 4-methyl-11-pentene, 11-hexene, and 1-octene.
  • the amount of the unit of the monomer copolymerized with the a, _ethylenically unsaturated nitrile monomer is based on the weight of the copolymer rubber (A). 60 wt%, and preferably from 45-58 weight 0 / o.
  • an aromatic vinyl monomer, a fluorine-containing vinyl monomer , alpha, chromatography ethylenically unsaturated monocarboxylic acids, alpha, - ethylenically unsaturated polycarboxylic acid or its anhydride, may be copolymerized and copolymerizable antioxidants.
  • Examples of the aromatic vinyl monomer include styrene, or-methylstyrene, vinyl pyridine and the like.
  • Examples of the fluorine-containing vinyl monomer include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene. And so on.
  • Examples of the ⁇ , / 3-ethylenically unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Examples of the ⁇ , monoethylenically unsaturated polycarboxylic acid include itaconic acid, fumaric acid, and maleic acid.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated polycarboxylic anhydride include itaconic anhydride and maleic anhydride.
  • Examples of the copolymerizable antioxidant include ⁇ _ (4-anilinophenyl) acrylamide, ⁇ — (4-anilinophenyl) methacrylamide, ⁇ — (4-anilinophenyl) cinnamamide, ⁇ — (4-anilinophenyl) croton Examples thereof include amide, 4-phenyl (4-vinylbenzyloxy) aniline, and 4-phenyl (4-vinylbenzyloxy) aniline.
  • the iodine value of the nitrile group-containing copolymer rubber (II) is 20 or less, preferably 15 or less, more preferably 10 or less. If the iodine value is too large, there is a problem that the oil resistance is deteriorated.
  • the nitrile group-containing copolymer rubber ( ⁇ ) can be prepared by copolymerization according to a conventional method. However, if the copolymer rubber is too large in iodine, ordinary hydrogenation treatment is carried out. It is preferable to saturate the unsaturated bond of the chain and adjust the iodine value to a small value.
  • the viscosity of the nitrile group-containing copolymer rubber ( ⁇ ) is preferably ML, +4 , (100 ° C). It is 10 to 300, more preferably 20 to 250, particularly preferably 30 to 200. If the Mooney viscosity is too low, the mechanical properties of the vulcanized product may be poor, and if it is too high, the processability may be poor.
  • alpha constituting the ⁇ one ethylenically unsaturated carboxylic acid metal salt (beta) alpha, the ⁇ - ethylenically unsaturated carboxylic acids, it is one that have at least monovalent free force Rupokishiru group , ⁇ , monoethylenically unsaturated monocarboxylic acid, a, monoethylenically unsaturated dicarboxylic acid, or, monoethylenically unsaturated dicarboxylic acid monoester, and the like.
  • the monoethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and 3-butenoic acid.
  • Examples of the or, ⁇ -ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, and itaconic acid. or,; 3-ethylenically unsaturated dicarboxylic acid monoesters include monomethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl itaconate, and the like.
  • an ester group-free or ⁇ -ethylenically unsaturated carboxylic acid is preferable, and a, a monoethylenically unsaturated monocarboxylic acid is more preferable.
  • methacrylic acid are particularly preferred.
  • the metal constituting the metal salt of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ( ⁇ ) is preferably zinc, magnesium, calcium, barium, titanium, chromium, iron, or cobalt from the viewpoint of the strength characteristics of carosulfide. , Nickel, aluminum, tin and lead, more preferably zinc, magnesium, calcium and aluminum, particularly preferably zinc.
  • the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid metal salt (B) can be used alone or in combination of one or more of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and a metal constituting the metal salt (B).
  • the ⁇ , -ethylenically unsaturated carboxylic acid and the metal or metal compound are added to the nitrile group-containing copolymer rubber ( ⁇ ) during the production of the rubber composition.
  • a metal salt ( ⁇ ) may be formed by reacting both in the nitrile group-containing copolymer rubber ( ⁇ ).
  • the metal salt ( ⁇ ) produced by such a method is preferable because it can be finely dispersed and easily dispersed.
  • the metal compound used to form the metal salt ( ⁇ ) include oxides, hydroxides, and carbonates of the above-mentioned metals. And zinc oxide and zinc carbonate are particularly preferred.
  • the metal salt ( ⁇ ) is preferably fine as long as it does not cause a handling problem, and the content of particles having a particle diameter of m or more is preferably 5% or less.
  • the metal salt (B) is compounded with the nitrile group-containing rubber (A)
  • the metal salt is used.
  • the metal salt (B) is formed with the nitrile group-containing rubber (A)
  • the metal salt is used.
  • the compound may be finely divided by a method of classifying the compound with an air classifier or a classifier with a sieve classifier.
  • the content of the metal salt of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ( ⁇ ) per 100 parts by weight of the nitrile group-containing copolymer rubber (A) is 3 to 100 parts by weight, preferably 10 to 80 parts by weight. It is more preferably 25 to 70 parts by weight. If the content of the ⁇ , monoethylenically unsaturated carboxylic acid metal salt (() is too small, the strength is poor, and if it is too large, kneading becomes difficult.
  • the rubber composition of the present invention may contain a compounding agent used for general rubber, for example, a reinforcing agent such as carbon black, silica, or short fiber, or a filler such as calcium carbonate, clay, talc, or galactic acid. Agents, plasticizers, pigments, antioxidants, tackifiers, processing aids, scorch inhibitors and the like. Further, a rubber or resin other than the nitrile group-containing copolymer rubber (II) may be contained within a range that does not substantially impair the effects of the present invention.
  • the method for preparing the rubber composition of the present invention is not particularly limited, and the components may be blended and kneaded according to a general method for preparing a rubber composition.
  • the vulcanizable rubber composition of the present invention comprises, in addition to the components of the rubber composition, an organic peroxide vulcanizing agent of 0.2 to 1 per 100 parts by weight of the nitrile group-containing copolymer rubber ( ⁇ ). It contains 0 parts by weight.
  • organic peroxide vulcanizing agent used in the present invention those used as a vulcanizing agent in the rubber industry are preferable, and examples thereof include dialkyl peroxides, disilver oxides, and carboxylic esters. Preferred are dialkyl baroxides.
  • dialkyl peroxides examples include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl veroxy) -13-hexine, 2,5-dimethyl 2,5- Di (t-butylperoxy) hexane, 1,3-bis (t-butylvinyloxyisopropyl) benzene, and the like.
  • diazyl peroxides examples include benzoyl peroxide, isobutyryl peroxide and the like.
  • peroxyesters examples include 2,5-dimethyl-2,5-bis (benzoylpropoxy) hexane, t-butylperoxyisopropyl ether and the like.
  • the organic peroxide vulcanizing agents can be used alone or in combination of two or more.
  • the amount of the organic peroxide vulcanizing agent to 100 parts by weight of the nitrile group-containing copolymer rubber (A) is 0.2 to 10 parts by weight, preferably 0.3 to 7 parts by weight, and particularly preferably 0 to 10 parts by weight. 5-5 parts by weight. If the amount of the organic peroxide vulcanizing agent is too small, the vulcanization density decreases and the compression set increases. If the amount of the organic peroxide vulcanizing agent is too large, the vulcanized product may have insufficient rubber elasticity.
  • a vulcanizing aid is usually used in combination.
  • the vulcanization aid it is preferable to use zinc oxide, magnesium oxide, triaryl cyanurate, trimethylolpropane trimethacrylate, N, N'-m-phenylenebismaleimide and the like.
  • the vulcanization aid may be dispersed in clay, calcium carbonate, silica or the like to improve the processability of the rubber composition.
  • the type and amount of the vulcanization aid are not particularly limited, and may be determined according to the use of the vulcanized product, the required performance, the type of the vulcanizing agent, the type of the vulcanization aid, and the like.
  • the method for preparing the vulcanizable rubber composition of the present invention is not particularly limited, and is the same as the method for preparing a general vulcanizable rubber composition.
  • the required components may be mixed using an internal mixer, an oven roll, or the like.
  • the kneading may be carried out at a temperature lower than the vulcanization starting temperature so that vulcanization does not occur during kneading.
  • the vulcanizate of the present invention is obtained by vulcanizing the above vulcanizable rubber composition.
  • the vulcanizable rubber composition may be heated. Generally, heating is performed after molding, or heating is performed simultaneously with molding.
  • the temperature during calosulphurization is preferably 100 to 200 ° C, more preferably 130 to 195 ° C, and particularly preferably 140 to 190 ° C. If the temperature is too low, the vulcanization time may be long and the vulcanization density may be low. If the temperature is too high, molding failure may occur.
  • the vulcanization time varies depending on the vulcanization method, vulcanization temperature, shape, etc., but is preferably 1 minute to 4 hours from the viewpoint of vulcanization density and production efficiency.
  • a heating method for vulcanization may be appropriately selected from methods used for vulcanization of rubber, such as press heating, steam heating, oven heating, and hot air heating.
  • the surface may be vulcanized but the inside may not be sufficiently vulcanized.
  • secondary vulcanization may be carried out while maintaining a high temperature normal state.
  • the physical properties of the rubber vulcanizate were measured by the following methods.
  • the prepared vulcanizable rubber composition was vulcanized at 170 ° C. for 20 minutes under a press pressure of 1 OM Pa to obtain a sheet having a thickness of 2 mm.
  • the sheet was punched out to prepare a test piece for a JIS K6251 bow I tension test.
  • the tensile strength (MPa) and elongation (%) of the vulcanized product were measured in accordance with JIS K6251, and the vulcanized product was vulcanized using a micro-size international rubber hardness tester in accordance with JIS K6253.
  • the hardness of the object IRHD micro
  • test specimens were immersed in 150 ° C test lubricating oil IRM902 oil for 168 hours, the volume before and after immersion was measured, and the volume change rate before immersion was expressed in%. Further, the hardness after immersion was measured in the same manner as in the measurement of the hardness of the above-mentioned normal physical properties, and the change from before immersion was measured. In the measurement of oil resistance, the smaller the absolute value of the volume change rate (%) and the change in hardness, the better the oil resistance. (3) Degradation oil resistance
  • Nitrile group-containing copolymer rubber A (Zetpol 1000L, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 7 or less, acrylonitrile unit content 44% by weight, Mooney viscosity ML 1 + 4 , ( 70) 100 parts, 100 parts, 15 parts of zinc methacrylate, 10 parts of zinc flower No.
  • a vulcanizable rubber composition was prepared.
  • This vulcanizable rubber composition was cured by pressing it at 170 ° C for 20 minutes at a pressure of 10 MPa to form a 2 mm thick sheet and punched out using a No. 3 dumbbell to prepare a test piece. did. Using this test piece, normal physical properties, oil resistance, and deterioration oil resistance were measured. Table 1 shows the results.
  • nitrile group-containing copolymer rubber B Zetpol 1010, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, oxygen value 10, acrylonitrile unit content 44 wt. %, Mooney viscosity ML 4, except for using (10 0 ° C) 85
  • the rubber composition was prepared as in example 1, and further vulcanized was measured the properties of the vulcanizate. Table 1 shows the results.
  • Comparative Example 1 A rubber composition was prepared and vulcanized in the same manner as in Example 1, except that zinc methacrylate was not blended and the amount of bonbon black was changed from 20 parts to 40 parts. Was measured. Table 1 shows the results.
  • nitrile group-containing copolymer rubber A nitrile group-containing copolymer rubber c (Zetpol 1020, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 24, acrylonitrile unit content 44 weight 0/0, arm one hundred twenty-one viscosity ML, +4, (10 0 ° C) 78) except for using the rubber composition was prepared as in example 1, and further vulcanized, the vulcanizate Were measured. Table 1 shows the results.
  • nitrile group-containing copolymer rubber d Zetpol
  • Example 2 2000, manufactured by Nippon Zeon Co., Ltd., using hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 4, acrylonitrile unit content 36% by weight, Mooney viscosity ML, +4 , (100 ° C) 85)
  • a rubber composition was prepared, and further subjected to force Q vulcanization, and the properties of the vulcanized product were measured.
  • Table 1 shows the results. table 1
  • the rubber vulcanizates of Comparative Example 1 containing no ⁇ , -ethylenically unsaturated carboxylic acid metal salt were prepared by changing the amount of carbon black and changing the hardness in the other Examples, ratio It was measured close to the comparative example, but the tensile strength and elongation were small, and in the measurement of the oil resistance to deterioration, the change in hardness was large and cracks were generated at small elongation.
  • the rubber vulcanizate of Comparative Example 2 using a nitrile group-containing copolymer rubber having an iodine value of more than 20 has a small elongation, and cracks occur at a small elongation in the measurement of deterioration resistance.
  • a, yS The rubber vulcanizate of Comparative Example 3 using a nitrile group-containing copolymer rubber having an ethylenically unsaturated nitrile monomer unit content of less than 40% by weight showed a volume change in oil resistance measurement.
  • the absolute value of the rate of change is large and the absolute value of the rate of change in volume is large in the measurement of deterioration oil resistance.
  • the vulcanizates of the present invention (Examples 1 and 2) hardly change in volume and hardness and hardly cause cracks in the measurement of deterioration oil resistance.
  • the rubber vulcanizates of the present invention exhibit excellent degradation oil resistance while substantially retaining the good physical properties and oil resistance of the nitrile group-containing copolymer rubber.
  • this rubber vulcanizate can be used for rubber parts that come into contact with lubricating oils such as automobiles, ships, and industrial machines, such as hoses, packings, and seals for automobile drive trains. Can be used.

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Abstract

A rubber composition which comprises 100 parts by weight of a nitrile copolymer rubber (A) having an iodine value of 20 or lower and a content of α,ß-ethylenically unsaturated nitrile monomer units of 40 to 60 wt.% and 3 to 100 parts by weight of a metal salt of an α,ß-ethylenically unsaturated carboxylic acid (B). Also provided is a vulcanizable rubber composition comprising this rubber composition and incorporated therein 0.2 to 10 parts by weight of an organic-peroxide vulcanizing agent (C). The vulcanizable composition gives a rubber vulcanizate having excellent resistance to deteriorating oils.

Description

明細書 ゴム組成物、加硫性ゴム組成物および加硫物 技術分野  Description Rubber composition, vulcanizable rubber composition and vulcanizate
本発明は、耐劣化油性に優れたコ'ム加硫物の材料となるゴム組成物に関す る。 背景技術  The present invention relates to a rubber composition used as a material for a rubber vulcanizate having excellent resistance to deterioration oil. Background art
近年、 自動車においては、エンジンの高出力化、 FF化、排ガス対策などによつ て、エンジンルームの熱的環境条件は過酷化している。一方、 自動車用潤滑油で は、 ロングライフ化、低燃費化などが進められている。その結果、潤滑油は、高温 条件下で長期間交換されることなく使用できることが求められている。し力、し、潤滑 油は空気との接触により酸化が進行し、その結果、劣化油が生成する。  In recent years, thermal environmental conditions in the engine room have become severer due to the increase in engine output, the use of FFs, and measures against exhaust gas. On the other hand, for lubricants for automobiles, longer life and lower fuel consumption are being promoted. As a result, it is required that lubricating oil can be used under high temperature conditions without being replaced for a long time. The lubricating oil is oxidized by contact with air, resulting in the generation of degraded oil.
ゴム部品は、劣化油との接触により硬化するという問題が指摘され、また、ァク リロ二トリル一ブタジエン共重合ゴムを水素添加したゴムでは硬化の程度が小さい ことが知られている（豊田合成技報告、 Vo l . 26、 No . 2、第 5 1〜 56頁（1 984 ) )。 し力、し、耐劣化油性により優れたゴム加硫物が求められている。 発明の開示  It has been pointed out that rubber parts are hardened by contact with degraded oil, and it is known that the degree of hardening is low with hydrogenated acrylonitrile-butadiene copolymer rubber (Toyoda Gosei Technical Report, Vol. 26, No. 2, pp. 51-56 (1 984)). Rubber vulcanizates that are more excellent in elasticity and resistance to deterioration oil are required. Disclosure of the invention
本発明の目的は、耐劣化油性に優れたコ 'ム加硫物とその材料となるゴム組成 物を提供することにある。  An object of the present invention is to provide a rubber vulcanizate which is excellent in oil resistance to deterioration and a rubber vulcanizate used as the material.
本発明者らは、上記目的を達成すべく鋭意検討した結果、ヨウ素価が小さく、 α , β—エチレン性不飽和二トリル単量体単位含有量の大きな二トリル基含有共 重合体ゴムにエチレン性不飽和カルボン酸の金属塩とを配合して加硫させることに より、 劣化油と接触しても体積が変化し難ぐ硬化し難 クラックの発生し難いゴ ム加硫物が得られることを見出し、この知見に基づいて、本発明を完成させるに至 つた。  The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a nitrile group-containing copolymer rubber having a small iodine value and a large α, β-ethylenically unsaturated nitrile monomer unit content has a high ethylene content. Vulcanization by blending with a metal salt of a unsaturated unsaturated carboxylic acid to obtain a rubber vulcanizate that hardly changes in volume even when it comes into contact with degraded oil, hardens and hardly cracks The present inventors have completed the present invention based on this finding.
力、くして本発明によれば、第一の発明として、ヨウ素価 20以下、 ， ーェチレ ン性不飽和二トリル単量体単位含有量 40~60重量％の二トリル基含有共重合 ゴム（A) 100重量部に対し、 ο;， ーエチレン性不飽和カルボン酸金属塩（B)3〜 100重量部を含有してなるゴム組成物が提供される。 According to the present invention, as a first invention, an iodine value of 20 or less, Per 100 parts by weight of a nitrile group-containing copolymer rubber (A) having an unsaturated unsaturated nitrile monomer unit content of 40 to 60% by weight, ο; -ethylenically unsaturated carboxylic acid metal salt (B) 3 to A rubber composition comprising 100 parts by weight is provided.
第二の発明として、ヨウ素価 20以下、 ーエチレン性不飽和二トリル単量 体単位含有量 40〜60重量％の二トリル基含有共重合ゴム（Α) 100重量部に対 し、 α , ^—エチレン性不飽和カルボン酸金属塩（Β)3〜100重量部および有機 過酸化物加硫剤 0. 2〜 10重量部を含有する加硫性ゴム組成物が提供される。  As a second invention, α, ^ — is based on 100 parts by weight of a nitrile group-containing copolymer rubber (Α) having an iodine value of 20 or less and an ethylenically unsaturated nitrile monomer unit content of 40 to 60% by weight. Provided is a vulcanizable rubber composition containing 3 to 100 parts by weight of a metal salt of an ethylenically unsaturated carboxylic acid (II) and 0.2 to 10 parts by weight of an organic peroxide vulcanizing agent.
さらに第三の発明として、上記加硫性ゴム組成物を加硫してなる加硫物が提 供される。 発明を実施するための最良の形態  Further, as a third invention, there is provided a vulcanizate obtained by vulcanizing the above vulcanizable rubber composition. BEST MODE FOR CARRYING OUT THE INVENTION
本発明のゴム組成物は、ヨウ素価 20以下、 α, 一エチレン性不飽和二トリル 単量体単位含有量 40~60重量％の二トリル基含有共重合ゴム（Α) 100重量部 に対し、 ひ ， 一エチレン性不飽和カルボン酸金属塩（Β)3〜100重量部を含有し てなる。  The rubber composition of the present invention has an iodine value of 20 or less, an α, monoethylenically unsaturated nitrile monomer unit content of 40 to 60% by weight, and 100 parts by weight of a nitrile group-containing copolymer rubber (Α). (1) It contains 3 to 100 parts by weight of a metal salt of a monoethylenically unsaturated carboxylic acid (II).
本発明に用いる二トリル基含有共重合ゴム（Α)は、 a, S—エチレン性不飽和 二トリル系単量体を他の単量体と共重合して得られるゴムであり、 a, ーエチレン 性不飽和二トリル単量体単位含有量が 40〜 60重量％、好ましくは 42〜55重 量％のものである。 α, 8—エチレン性不飽和二トリル単量体含有量が少なすぎる と耐劣化油性に劣り、逆に多すぎると耐寒性に劣る。 α, β 一エチレン性不飽和二 トリル系単量体としては、例えば、アクリロニトリル、メタクリロニトリル、 α—クロロア クリロニトリルなどが挙げられ、アクリロニトリルが好ましい。 The nitrile group-containing copolymer rubber (Α) used in the present invention is a rubber obtained by copolymerizing an a, S-ethylenically unsaturated nitrile-based monomer with another monomer. The content of the unsaturated unsaturated nitrile monomer unit is 40 to 60% by weight, preferably 42 to 55% by weight. If the content of α, 8-ethylenically unsaturated nitrile monomer is too low, the oil resistance to deterioration is poor, and if it is too high, the cold resistance is poor. Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and the like, with acrylonitrile being preferred.
二トリル基含有共重合ゴム（Α)において、 α， ーエチレン性不飽和二トリル系 単量体と共重合させる単量体としては、共役ジェン系単量体、非共役ジェン系単 量体、 α—ォレフィンなどが例示される。共役ジェン系単量体としては、例えば、 1 , 3—ブタジエン、イソプレン、 2, 3—ジメチル一 1. 3—ブタジエン、 1 , 3—ペンタジェン などが挙げられ、 1 , 3—ブタジエンが好ましい。非共役ジェン系単量体は、好ましく は炭素数が 5 ~12のものであり、 1 , 4—ペンタジェン、 1. 4—へキサジェン、ビニル ノルポルネン、ジシクロペンタジェンなどが例示される。 一才レフインとしては、炭素 数が 2~ 12のものが好まし《エチレン、プロピレン、 1ーブテン、 4—メチル一 1一べ ンテン、 1一へキセン、 1—ォクテンなどが例示される。 In the nitrile group-containing copolymer rubber (Α), the monomer to be copolymerized with the α, -ethylenically unsaturated nitrile monomer is a conjugated diene monomer, a non-conjugated dimeric monomer, α —Olefin and the like. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1-1.3-butadiene, and 1,3-pentadiene, and 1,3-butadiene is preferable. The non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentadiene, 1.4-hexadiene, vinyl norportene, and dicyclopentadiene. One-year-old ref Those having a number of 2 to 12 are preferred. Examples thereof include ethylene, propylene, 1-butene, 4-methyl-11-pentene, 11-hexene, and 1-octene.
二トリル基含有共重合ゴム（A)中の、 a, _エチレン性不飽和二トリル単量 体と共重合される単量体の単位の量は、共重合ゴム（A)重量に基づき、 40〜60 重量％、好ましくは 45〜58重量0 /oのものである。 In the nitrile group-containing copolymer rubber (A), the amount of the unit of the monomer copolymerized with the a, _ethylenically unsaturated nitrile monomer is based on the weight of the copolymer rubber (A). 60 wt%, and preferably from 45-58 weight 0 / o.
さらに、 α, )3—エチレン性不飽和二トリル単量体と共重合される単量体として、 上記の単量体に加えて、芳香族ビニル系単量体、フッ素含有ビニル系単量体、 α , ーエチレン性不飽和モノカルボン酸、 α, —エチレン性不飽和多価カルボン酸 またはその無水物、共重合性の老化防止剤などを共重合してもよい。 Further, as the monomer copolymerized with the α,) 3-ethylenically unsaturated nitrile monomer, in addition to the above monomers, an aromatic vinyl monomer, a fluorine-containing vinyl monomer , alpha, chromatography ethylenically unsaturated monocarboxylic acids, alpha, - ethylenically unsaturated polycarboxylic acid or its anhydride, may be copolymerized and copolymerizable antioxidants.
芳香族ビニル系単量体としては、例えば、スチレン、 or—メチルスチレン、ビニル ピリジンなどが挙げられる。フッ素含有ビニル系単量体としては、例えば、フルォロ ェチルビニルエーテル、フルォロプロピルビニルェ一テル、 o—トリフルォロメチルスチ レン、ペンタフルォロ安息香酸ビニル、ジフルォロエチレン、亍トラフルォロエチレンな どが挙げられる。 α, /3—エチレン性不飽和モノカルボン酸としては、例えば、ァクリ ル酸、メタクリル酸などが挙げられる。 α, 一エチレン性不飽和多価カルボン酸と しては、例えば、ィタコン酸、フマル酸、マレイン酸などが挙げられる。 α, β—ェチレ ン性不飽和多価カルボン酸無水物としては、例えば、無水ィタコン酸、無水マレイ ン酸などが挙げられる。共重合性の老化防止剤としては、例えば、 Ν_(4—ァニリ ノフエニル）アクリルアミド、 Ν— (4—ァニリノフエニル）メタクリルアミド、 Ν— (4—ァニ リノフエニル）シンナムアミド、 Ν— (4—ァニリノフエニル）クロトンアミド、 Ν—フエニル 一 4一（3—ビニルベンジルォキシ）ァニリン、 Ν—フエニル一 4一（4—ビニルベンジル ォキシ）ァニリンなどが挙げられる。  Examples of the aromatic vinyl monomer include styrene, or-methylstyrene, vinyl pyridine and the like. Examples of the fluorine-containing vinyl monomer include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene. And so on. Examples of the α, / 3-ethylenically unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Examples of the α, monoethylenically unsaturated polycarboxylic acid include itaconic acid, fumaric acid, and maleic acid. Examples of the α, β-ethylenically unsaturated polycarboxylic anhydride include itaconic anhydride and maleic anhydride. Examples of the copolymerizable antioxidant include Ν_ (4-anilinophenyl) acrylamide, Ν— (4-anilinophenyl) methacrylamide, Ν— (4-anilinophenyl) cinnamamide, Ν— (4-anilinophenyl) croton Examples thereof include amide, 4-phenyl (4-vinylbenzyloxy) aniline, and 4-phenyl (4-vinylbenzyloxy) aniline.
二トリル基含有共重合ゴム（Α)のヨウ素価は、 20以下、好ましくは 15以下、よ リ好ましくは 10以下である。ヨウ素価が大きすぎると耐劣化油性に劣るという問題 を生じる。二トリル基含有共重合ゴム（Α)は、常法に従って共重合することによリ調 製できるが、共重合ゴムのヨウ素が大きすぎる場合には、通常の水素添加処理を 行なうことにより、主鎖の不飽和結合を飽和させ、ヨウ素価を小さく調整して用いれ ぱよい。  The iodine value of the nitrile group-containing copolymer rubber (II) is 20 or less, preferably 15 or less, more preferably 10 or less. If the iodine value is too large, there is a problem that the oil resistance is deteriorated. The nitrile group-containing copolymer rubber (Α) can be prepared by copolymerization according to a conventional method. However, if the copolymer rubber is too large in iodine, ordinary hydrogenation treatment is carried out. It is preferable to saturate the unsaturated bond of the chain and adjust the iodine value to a small value.
二トリル基含有共重合ゴム（Α)のム一二一粘度 ML, +4, ( 100°C)は、好ましくは 1 0〜 300、より好ましくは 20 ~ 250、特に好ましくは 30 ~ 200である。ム一ニー粘 度が小さすぎると加硫物の機械的物性が劣る場合があり、逆に大きすぎると加工 性に劣る場合がある。 The viscosity of the nitrile group-containing copolymer rubber (Α) is preferably ML, +4 , (100 ° C). It is 10 to 300, more preferably 20 to 250, particularly preferably 30 to 200. If the Mooney viscosity is too low, the mechanical properties of the vulcanized product may be poor, and if it is too high, the processability may be poor.
本発明に用いる α , β一エチレン性不飽和カルボン酸金属塩（Β )を構成する α , β—エチレン性不飽和カルボン酸は、少なくとも 1価のフリーの力ルポキシル基を有 するものであって、 α , 一エチレン性不飽和モノカルポン酸、 a , 一エチレン性 不飽和ジカルボン酸、 or , ーエチレン性不飽和ジカルボン酸モノエステルなどが 例示される。 ， 一エチレン性不飽和モノカルボン酸としては、アクリル酸、メタク リル酸、クロトン酸、 3—ブテン酸などが挙げられる。 or , β一エチレン性不飽和ジカ ルボン酸としては、マレイン酸、フマル酸、ィタコン酸などが挙げられる。 or , ;3—ェ チレン性不飽和ジカルボン酸モノエステルとしては、マレイン酸モノメチル、マレイン 酸モノエチル、ィタコン酸モノメチル、ィタコン酸モノェチルなどが挙げられる。これら の中で、コ'ム加硫物の強度特性の点からエステル基をもたない or , β—エチレン性 不飽和カルボン酸が好ましく、 a , 一エチレン性不飽和モノカルボン酸がより好ま しく、メタクリル酸が特に好ましい。 Used in the present invention alpha, constituting the β one ethylenically unsaturated carboxylic acid metal salt (beta) alpha, the β- ethylenically unsaturated carboxylic acids, it is one that have at least monovalent free force Rupokishiru group , Α, monoethylenically unsaturated monocarboxylic acid, a, monoethylenically unsaturated dicarboxylic acid, or, monoethylenically unsaturated dicarboxylic acid monoester, and the like. Examples of the monoethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and 3-butenoic acid. Examples of the or, β-ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, and itaconic acid. or,; 3-ethylenically unsaturated dicarboxylic acid monoesters include monomethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl itaconate, and the like. Among these, from the viewpoint of the strength characteristics of the rubber vulcanizate, an ester group-free or β-ethylenically unsaturated carboxylic acid is preferable, and a, a monoethylenically unsaturated monocarboxylic acid is more preferable. And methacrylic acid are particularly preferred.
α , β—エチレン性不飽和カルボン酸金属塩（Β )を構成する金属としては、カロ 硫物の強度特性の点から、好ましくは、亜鉛、マグネシウム、カルシウム、バリウム、 チタン、クロム、鉄、コバルト、ニッケル、アルミニウム、錫、鉛が挙げられ、より好まし くは亜鉛、マグネシウム、カルシウムおよびアルミニウムが挙げられ、特に好ましくは 亜鉛である。  The metal constituting the metal salt of α, β-ethylenically unsaturated carboxylic acid (Β) is preferably zinc, magnesium, calcium, barium, titanium, chromium, iron, or cobalt from the viewpoint of the strength characteristics of carosulfide. , Nickel, aluminum, tin and lead, more preferably zinc, magnesium, calcium and aluminum, particularly preferably zinc.
a , ーエチレン性不飽和カルボン酸金属塩（B )は、それを構成する α , β —ェ チレン性不飽和カルボン酸および金属、それぞれ、 1種または 2種以上を組合わせ 用いることができる。  The α, β-ethylenically unsaturated carboxylic acid metal salt (B) can be used alone or in combination of one or more of α, β-ethylenically unsaturated carboxylic acid and a metal constituting the metal salt (B).
， β—エチレン性不飽和カルボン酸金属塩（Β )は、ゴム組成物の製造時に、 二トリル基含有共重合ゴム（Α)に、 α , ーエチレン性不飽和カルボン酸と前記金 属または金属化合物とを配合して、二トリル基含有共重合ゴム（Α)中で両者を反 応させて、金属塩（Β )を生成させたものであってもよい。このような方法で生成され た金属塩（Β )は、細かくなリ、分散させ易く好ましい。金属塩（Β )を生成させるのに 用いられる金属化合物としては、前記金属の酸化物、水酸化物、炭酸塩などが挙 げられ、特に酸化亜鉛、炭酸亜鉛が好ましい。 The α, -ethylenically unsaturated carboxylic acid and the metal or metal compound are added to the nitrile group-containing copolymer rubber (酸) during the production of the rubber composition. And a metal salt (Β) may be formed by reacting both in the nitrile group-containing copolymer rubber (Α). The metal salt (Β) produced by such a method is preferable because it can be finely dispersed and easily dispersed. Examples of the metal compound used to form the metal salt (Β) include oxides, hydroxides, and carbonates of the above-mentioned metals. And zinc oxide and zinc carbonate are particularly preferred.
二トリル基含有共重合ゴム（A)中に α , β一エチレン性不飽和カルボン酸と金 属または金属化合物とを配合して α， β一エチレン性不飽和カルボン酸金属塩 ( Β )を生成させる場合には、 α , 8—エチレン性不飽和カルボン酸 1モルに対して、 金属または金属化合物を金属量として 0. 5〜3. 2モル、好ましくは 0. 7〜2. 5モ ル配合して反応させる。金属または金属化合物量が少なすぎても多すぎても、 α , β—エチレン性不飽和カルボン酸が金属または金属化合物と反応し難くなる。ただ し、金属化合物として、酸化亜鉛、炭酸亜鉛、水酸化亜鉛などを用いる場合は、 それら単独でもゴムの配合剤として加硫促進剤として機能するので、上記範囲の 上限を超えても、配合組成によっては問題を生じない場合がある。  Mixing α, β-ethylenically unsaturated carboxylic acid and metal or metal compound in nitrile group-containing copolymer rubber (A) to form metal salt of α, β-ethylenically unsaturated carboxylic acid (Β) In this case, 0.5 to 3.2 moles, preferably 0.7 to 2.5 moles, of a metal or a metal compound as a metal amount per 1 mole of the α, 8-ethylenically unsaturated carboxylic acid is used. And react. If the amount of the metal or the metal compound is too small or too large, the α, β-ethylenically unsaturated carboxylic acid hardly reacts with the metal or the metal compound. However, when zinc oxide, zinc carbonate, zinc hydroxide, or the like is used as the metal compound, the compound alone functions as a vulcanization accelerator as a rubber compounding agent. Depending on the case, no problem may occur.
金属塩（Β )は、取り扱いの問題を生じない限り、細かなものが好ましく、粒子径 m以上の粒子の含有量を 5 %以下としたものが好ましい。そのためには、金 属塩（B )を二トリル基含有ゴム（A )に配合する場合には金属塩を、金属塩（B )を 二トリル基含有ゴム（A)で生成する場合には金属化合物を、風力分級装置で分 級する、ふるい分級装置で分級するなどの方法によって、細かくすればよい。  The metal salt (Β) is preferably fine as long as it does not cause a handling problem, and the content of particles having a particle diameter of m or more is preferably 5% or less. For this purpose, when the metal salt (B) is compounded with the nitrile group-containing rubber (A), the metal salt is used. When the metal salt (B) is formed with the nitrile group-containing rubber (A), the metal salt is used. The compound may be finely divided by a method of classifying the compound with an air classifier or a classifier with a sieve classifier.
二トリル基含有共重合ゴム（A) 1 00重量部に対する α , β—エチレン性不飽和 カルボン酸金属塩（Β )の含有量は、 3〜1 00重量部、好ましくは 1 0〜80重量部、 より好ましくは 25 ~ 70重量部である。 α , 一エチレン性不飽和カルボン酸金属 塩（ Β)の含有量が少なすぎると強度が劣り、逆に多すぎると混練が困難になる。  The content of the metal salt of α, β-ethylenically unsaturated carboxylic acid (Β) per 100 parts by weight of the nitrile group-containing copolymer rubber (A) is 3 to 100 parts by weight, preferably 10 to 80 parts by weight. It is more preferably 25 to 70 parts by weight. If the content of the α, monoethylenically unsaturated carboxylic acid metal salt (（) is too small, the strength is poor, and if it is too large, kneading becomes difficult.
本発明のゴム組成物には、一般的なゴムに使用される配合剤、例えば、カーボ ンブラック、シリカ、短繊維などの補強剤、炭酸カルシウム、クレー、タルク、ゲイ酸力 ルシゥ厶などの充填剤、可塑剤、顔料、老化防止剤、粘着付与剤、加工助剤、ス コーチ防止剤などを含有してもよい。また、二トリル基含有共重合ゴム（Α)以外の ゴムや樹脂を本発明の効果を実質的に阻害しない範囲で含有せしめてもよい。  The rubber composition of the present invention may contain a compounding agent used for general rubber, for example, a reinforcing agent such as carbon black, silica, or short fiber, or a filler such as calcium carbonate, clay, talc, or galactic acid. Agents, plasticizers, pigments, antioxidants, tackifiers, processing aids, scorch inhibitors and the like. Further, a rubber or resin other than the nitrile group-containing copolymer rubber (II) may be contained within a range that does not substantially impair the effects of the present invention.
本発明のゴム組成物の調製方法は特に限定されず、一般的なゴム組成物の 調製方法に従って、各成分を配合し、混練すればよい。  The method for preparing the rubber composition of the present invention is not particularly limited, and the components may be blended and kneaded according to a general method for preparing a rubber composition.
本発明の加硫性ゴム組成物は、上記ゴム組成物の各成分の他に、二トリル基 含有共重合ゴム（Α) 1 00重量部当たり、有機過酸化物加硫剤 0. 2〜1 0重量部 を含有するものである。 本発明で用いる有機過酸化物加硫剤としては、ゴム工業分野で加硫剤として 使用されているものが好ましく、例えば、ジアルキルパーオキサイド類、ジァシルバー オキサイド類、パ一ォキシエステル類などが挙げられ、好ましくはジアルキルバーオ キサイド類である。ジアルキルパーオキサイド類としては、例えば、ジクミルパーォキ サイド、ジ一 tーブチルバ一オキサイド、 2 , 5—ジメチルー 2 , 5—ジ（t—ブチルバーオ キシ）一 3—へキシン、 2 , 5—ジメチルー 2 , 5—ジ（t—ブチルパーォキシ）へキサン、 1 , 3—ビス（t—ブチルバ一ォキシイソプロピル）ベンゼンなどが挙げられる。ジァシル パーオキサイド類として、例えば、ベンゾィルバ一オキサイド、イソプチリルパーォキ サイドなどが挙げられる。パーォキシエステル類としては、例えば、 2 , 5—ジメチルー 2 , 5—ビス（ベンゾィルパ一ォキシ）へキサン、 t—ブチルパーォキシイソプロピル力一 ポネートなど）などが挙げられる。有機過酸化物加硫剤は、単独で、または 2種以 上を組合わせて用いることができる。 The vulcanizable rubber composition of the present invention comprises, in addition to the components of the rubber composition, an organic peroxide vulcanizing agent of 0.2 to 1 per 100 parts by weight of the nitrile group-containing copolymer rubber (共). It contains 0 parts by weight. As the organic peroxide vulcanizing agent used in the present invention, those used as a vulcanizing agent in the rubber industry are preferable, and examples thereof include dialkyl peroxides, disilver oxides, and carboxylic esters. Preferred are dialkyl baroxides. Examples of the dialkyl peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl veroxy) -13-hexine, 2,5-dimethyl 2,5- Di (t-butylperoxy) hexane, 1,3-bis (t-butylvinyloxyisopropyl) benzene, and the like. Examples of the diazyl peroxides include benzoyl peroxide, isobutyryl peroxide and the like. Examples of the peroxyesters include 2,5-dimethyl-2,5-bis (benzoylpropoxy) hexane, t-butylperoxyisopropyl ether and the like. The organic peroxide vulcanizing agents can be used alone or in combination of two or more.
二トリル基含有共重合ゴム（A) 1 00重量部に対する有機過酸化物加硫剤の 配合量は、 0. 2〜1 0重量部、好ましくは 0. 3〜7重量部、特に好ましくは 0. 5 - 5 重量部である。有機過酸化物加硫剤の配合量が少なすぎると、加硫密度が低下 し、圧縮永久ひずみが大きくなる。有機過酸化物加硫剤の配合量が多すぎると、 加硫物のゴム弾性が不十分となる場合がある。  The amount of the organic peroxide vulcanizing agent to 100 parts by weight of the nitrile group-containing copolymer rubber (A) is 0.2 to 10 parts by weight, preferably 0.3 to 7 parts by weight, and particularly preferably 0 to 10 parts by weight. 5-5 parts by weight. If the amount of the organic peroxide vulcanizing agent is too small, the vulcanization density decreases and the compression set increases. If the amount of the organic peroxide vulcanizing agent is too large, the vulcanized product may have insufficient rubber elasticity.
有機過酸化物加硫剤を使用する場合は、通常、加硫助剤を併用する。加硫 助剤としては、酸化亜鉛、酸化マグネシウム、 トリァリルシアヌレ一ト、 トリメチロール プロパントリメタクリレート、 N , N '—m—フエ二レンビスマレイミドなどを用いることが 好ましい。加硫助剤は、クレー、炭酸カルシウム、シリカなどに分散させ、ゴム組成 物の加工性を改良したものを使用してもよい。加硫助剤の種類および配合量は特 に限定されず、加硫物の用途、要求性能、加硫剤の種類、加硫助剤の種類など に応じて決めればよい。  When an organic peroxide vulcanizing agent is used, a vulcanizing aid is usually used in combination. As the vulcanization aid, it is preferable to use zinc oxide, magnesium oxide, triaryl cyanurate, trimethylolpropane trimethacrylate, N, N'-m-phenylenebismaleimide and the like. The vulcanization aid may be dispersed in clay, calcium carbonate, silica or the like to improve the processability of the rubber composition. The type and amount of the vulcanization aid are not particularly limited, and may be determined according to the use of the vulcanized product, the required performance, the type of the vulcanizing agent, the type of the vulcanization aid, and the like.
本発明の加硫性ゴム組成物を調製する方法は、格別限定されることはなく、一 般の加硫性ゴム組成物の調製方法と同じである。例えば、密閉式混合機、オーブ ンロールなどを用いて所要成分を混合すればよい。ただし、加硫剤、加硫助剤など の配合以降は、混練中に加硫が起こらないように、加硫開始温度未満に維持して 混練すればよい。 本発明の加硫物は、前述の加硫性ゴム組成物を加硫したものである。ゴム組 成物を加硫するには、加硫性ゴム組成物を加熱すればよい。一般的には、成形し た後に加熱するか、成形と同時に加熱する。 The method for preparing the vulcanizable rubber composition of the present invention is not particularly limited, and is the same as the method for preparing a general vulcanizable rubber composition. For example, the required components may be mixed using an internal mixer, an oven roll, or the like. However, after the compounding of the vulcanizing agent and the vulcanization aid, the kneading may be carried out at a temperature lower than the vulcanization starting temperature so that vulcanization does not occur during kneading. The vulcanizate of the present invention is obtained by vulcanizing the above vulcanizable rubber composition. To vulcanize the rubber composition, the vulcanizable rubber composition may be heated. Generally, heating is performed after molding, or heating is performed simultaneously with molding.
カロ硫時の温度は、好ましくは 100~200°C、より好ましくは 130〜195°C、特に 好ましくは 140〜 190°Cである。温度が低すぎると加硫時間が長時間必要となつ たり、加硫密度が低くなつたりする場合がある。温度が高すぎる場合は、成形不良 になる場合がある。  The temperature during calosulphurization is preferably 100 to 200 ° C, more preferably 130 to 195 ° C, and particularly preferably 140 to 190 ° C. If the temperature is too low, the vulcanization time may be long and the vulcanization density may be low. If the temperature is too high, molding failure may occur.
また、加硫時間は、加硫方法、加硫温度、形状などにより異なるが、 1分間〜 4 時間が加硫密度と生産効率の面から好ましい。  The vulcanization time varies depending on the vulcanization method, vulcanization temperature, shape, etc., but is preferably 1 minute to 4 hours from the viewpoint of vulcanization density and production efficiency.
加硫するための加熱方法としては、プレス加熱、蒸気加熱、オーブン加熱、熱 風加熱などのゴムの加硫に用いられる方法から適宜選択すればよい。  A heating method for vulcanization may be appropriately selected from methods used for vulcanization of rubber, such as press heating, steam heating, oven heating, and hot air heating.
加硫物の形状、大きさなどによっては、表面は加硫していても、内部は十分に 加硫しないことがある。そのような場合、上記条件下に加硫した後、高温常態に保 持する二次加硫を行ってもよい。  Depending on the shape and size of the vulcanizate, the surface may be vulcanized but the inside may not be sufficiently vulcanized. In such a case, after vulcanization under the above conditions, secondary vulcanization may be carried out while maintaining a high temperature normal state.
以下に実施例、比較例を挙げて本発明を具体的に説明する。なお、部および 配合に関わる％は、特に記載しない限り、重量基準である。  Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. The percentages related to parts and blending are based on weight unless otherwise specified.
ゴム加硫物の物性は、下記の方法で測定した。  The physical properties of the rubber vulcanizate were measured by the following methods.
( 1 )常態特性  (1) Normal characteristics
調製した加硫性ゴム組成物を 170°Cで 20分間、プレス圧 1 OM Paで加硫を行 い、厚さ 2mmのシートを得た。このシートを用いて打ち抜いて、 JIS K6251の弓 I 張試験用試験片を作製した。この試験片を用いて、 JIS K6251に従い、加硫物 の引張強さ（MPa)および伸び（％)を測定し、 JIS K6253に従し、、マイクロサイズ 国際ゴム硬さ計を用いて、加硫物の硬さ（IRHD マイクロ）を測定した。  The prepared vulcanizable rubber composition was vulcanized at 170 ° C. for 20 minutes under a press pressure of 1 OM Pa to obtain a sheet having a thickness of 2 mm. The sheet was punched out to prepare a test piece for a JIS K6251 bow I tension test. Using this test piece, the tensile strength (MPa) and elongation (%) of the vulcanized product were measured in accordance with JIS K6251, and the vulcanized product was vulcanized using a micro-size international rubber hardness tester in accordance with JIS K6253. The hardness of the object (IRHD micro) was measured.
(2)耐油性  (2) Oil resistance
JIS K6258に従い、 150°Cの試験用潤滑油 IRM902油に試験片を 168時 間浸せきし、浸せき前後の体積を測定し、浸せき前に対する体積変化率を％で表 した。また、上記常態物性の硬さ測定と同様に浸せき後の硬さを測定し、浸せき前 に対する変化を測定した。耐油性の測定においては、体積変化率（％)および硬さ 変化の絶対値が小さいほど、耐油性に優れる。 (3)耐劣化油性 In accordance with JIS K6258, test specimens were immersed in 150 ° C test lubricating oil IRM902 oil for 168 hours, the volume before and after immersion was measured, and the volume change rate before immersion was expressed in%. Further, the hardness after immersion was measured in the same manner as in the measurement of the hardness of the above-mentioned normal physical properties, and the change from before immersion was measured. In the measurement of oil resistance, the smaller the absolute value of the volume change rate (%) and the change in hardness, the better the oil resistance. (3) Degradation oil resistance
浸せきしている間、試験用潤滑油 IRM902油 1200mlに対し、 1分当たり 50 mlの空気を定速度で吹き込む他は、上記耐油性の測定と同様に処理し、各物性 を測定した。なお、通常は、伸び（％)の測定時、クラックが発生した時点で破断す るが、耐劣化油性の測定においては、表面にクラックが発生しても破断しなかった ので、併せて、クラック発生時の伸び（％)の大きさを測定した。耐劣化油性の測定 においては、体積変化率（％)および硬さ変化の絶対値が小さ クラック発生時の 伸び（％ )が大きいほど、耐劣化油性に優れる。  During the immersion, the same treatment as in the above-mentioned oil resistance measurement was performed, except that air at 50 ml per minute was blown into the test lubricating oil IRM902 oil at a constant rate to 1200 ml, and each physical property was measured. Normally, when elongation (%) is measured, the sample breaks when a crack occurs. However, in the measurement of deterioration oil resistance, the sample did not break even if a crack occurred on the surface. The magnitude of elongation (%) at the time of occurrence was measured. In the measurement of the deterioration oil resistance, the smaller the absolute value of the volume change rate (%) and the change in hardness, the larger the elongation (%) at the time of crack generation, the better the deterioration oil resistance.
実施例 1  Example 1
二トリル基含有共重合ゴム A(Zetpol 1000L、 日本ゼオン社製、ァクリロニト リル—ブタジエン共重合ゴム水素添加物、ヨウ素価 7以下、アクリロニトリル単位含 有量 44重量％、ムーニー粘度 ML1+4, (100°C)70) 100部に、メタクリル酸亜鉛 15部、亜鉛華 1号 10部、 SRF力一ボンブラック（旭力一ボン社製、旭 #50)20部、 トリス（2—ェチルへキシル）トリメリテート 8部、置換ジフエニルァミン（老化防止剤、 ュニロイヤル社製、ナウガード 445) 1. 5部、 2—メルカプトべンゾチアゾ一ル亜鉛 塩（老化防止剤） 1. 5部および 1, 3—ビス（t一ブチルパーォキシイソプロピル）ベン ゼン（有機過酸化物） 400/0品（ハーキュレス社製、バルカップ 40KE) 6部（有機過 酸化物量 2. 4部）を配合し、 50°Cでロール混練して、加硫性ゴム組成物を調製し た。この加硫性ゴム組成物を 170°Cで 20分間、 10MPaの圧力でプレスすることに よリカ 0硫し、厚さ 2mmのシートとし、 3号形ダンベルを用いて打ち抜いて、試験片を 作製した。この試験片を用いて、常態物性、耐油性および耐劣化油性を測定した。 結果を表 1に示す。 Nitrile group-containing copolymer rubber A (Zetpol 1000L, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 7 or less, acrylonitrile unit content 44% by weight, Mooney viscosity ML 1 + 4 , ( 70) 100 parts, 100 parts, 15 parts of zinc methacrylate, 10 parts of zinc flower No. 1, 20 parts of SRF Riki Bon Black (Asahi Riki Bon Co., Ltd., Asahi # 50), 20 parts of Tris (2-ethylhexyl) ) Trimeritate 8 parts, Substituted diphenylamine (antiaging agent, manufactured by Uniroyal Co., Nowguard 445) 1.5 parts, 2-mercaptobenzothiazozinyl zinc salt (antiaging agent) 1. 5 parts and 1,3-bis (t 1-butylperoxyisopropyl) benzene (organic peroxide) 400/0 product (Hercules Co., Ltd., Valcup 40KE) 6 parts (organic peroxide amount 2.4 parts) are compounded and roll-kneaded at 50 ° C. Thus, a vulcanizable rubber composition was prepared. This vulcanizable rubber composition was cured by pressing it at 170 ° C for 20 minutes at a pressure of 10 MPa to form a 2 mm thick sheet and punched out using a No. 3 dumbbell to prepare a test piece. did. Using this test piece, normal physical properties, oil resistance, and deterioration oil resistance were measured. Table 1 shows the results.
実施例 2  Example 2
二トリル基含有共重合ゴム Aの代わりに二トリル基含有共重合ゴム B(Zetpol 1010、 日本ゼオン社製、アクリロニトリル一ブタジエン共重合ゴム水素添加物、ョ ゥ素価 10、アクリロニトリル単位含有量 44重量％、ムーニー粘度 ML 4, ( 10 0°C)85)を用いた他は、実施例 1と同様にゴム組成物を調製し、さらに加硫して、 加硫物の特性を測定した。結果を表 1に示す。 Instead of nitrile group-containing copolymer rubber A, nitrile group-containing copolymer rubber B (Zetpol 1010, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, oxygen value 10, acrylonitrile unit content 44 wt. %, Mooney viscosity ML 4, except for using (10 0 ° C) 85), likewise the rubber composition was prepared as in example 1, and further vulcanized was measured the properties of the vulcanizate. Table 1 shows the results.
比較例 1 メタクリル酸亜鉛を配合せず、力一ボンブラックの量を 20部から 40部に変えた 他は、実施例 1と同様にゴム組成物を調製し、さらに加硫して、加硫物の特性を測 定した。結果を表 1に示す。 Comparative Example 1 A rubber composition was prepared and vulcanized in the same manner as in Example 1, except that zinc methacrylate was not blended and the amount of bonbon black was changed from 20 parts to 40 parts. Was measured. Table 1 shows the results.
比較例 2  Comparative Example 2
二トリル基含有共重合ゴム Aの代わりに二トリル基含有共重合ゴム c(Zetpol 1020、 日本ゼオン社製、アクリロニトリル一ブタジエン共重合ゴム水素添加物、ョ ゥ素価 24、アクリロニトリル単位含有量 44重量0 /0、ム一二一粘度 ML,+4, ( 10 0°C)78)を用いた他は、実施例 1と同様にゴム組成物を調製し、さらに加硫して、 加硫物の特性を測定した。結果を表 1に示す。 Instead of nitrile group-containing copolymer rubber A, nitrile group-containing copolymer rubber c (Zetpol 1020, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 24, acrylonitrile unit content 44 weight 0/0, arm one hundred twenty-one viscosity ML, +4, (10 0 ° C) 78) except for using the rubber composition was prepared as in example 1, and further vulcanized, the vulcanizate Were measured. Table 1 shows the results.
比較例 3  Comparative Example 3
二トリル基含有共重合ゴム Aの代わりに二トリル基含有共重合ゴム d(Zetpol Instead of nitrile group-containing copolymer rubber A, nitrile group-containing copolymer rubber d (Zetpol
2000、 日本ゼオン社製、アクリロニトリル一ブタジエン共重合ゴム水素添加物、ョ ゥ素価 4、アクリロニトリル単位含有量 36重量％、ムーニー粘度 ML, +4, ( 100°C) 85)を用いた他は、実施例 1と同様にゴム組成物を調製し、さらに力 Q硫して、加硫 物の特性を測定した。結果を表 1に示す。 表 1 2000, manufactured by Nippon Zeon Co., Ltd., using hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 4, acrylonitrile unit content 36% by weight, Mooney viscosity ML, +4 , (100 ° C) 85) In the same manner as in Example 1, a rubber composition was prepared, and further subjected to force Q vulcanization, and the properties of the vulcanized product were measured. Table 1 shows the results. table 1
Figure imgf000010_0001
表 1にみられるとおり、 α, ーエチレン性不飽和カルボン酸金属塩を含有しな い比較例 1のコ'ム加硫物は、カーボンブラックの量を変えて、硬さを他の実施例、比 較例に近づけて測定したが、引張強度、伸びが小さく、耐劣化油性の測定におい て、硬さ変化が大き 小さな伸びでクラックが発生する。ヨウ素価が 20より大きな 二トリル基含有共重合ゴムを用いた比較例 2のゴム加硫物は、伸びが小さ 耐劣 化油性の測定において、小さな伸びでクラックが発生する。 a , yS—エチレン性不 飽和二トリル単量体単位含有量が 40重量％未満の二トリル基含有共重合ゴムを 用いた比較例 3のゴム加硫物は、耐油性の測定において、体積変化率の絶対値 が大きく、耐劣化油性の測定において、体積変化率の絶対値が大き 小さな伸 びでクラックが発生する。
Figure imgf000010_0001
As shown in Table 1, the rubber vulcanizates of Comparative Example 1 containing no α, -ethylenically unsaturated carboxylic acid metal salt were prepared by changing the amount of carbon black and changing the hardness in the other Examples, ratio It was measured close to the comparative example, but the tensile strength and elongation were small, and in the measurement of the oil resistance to deterioration, the change in hardness was large and cracks were generated at small elongation. The rubber vulcanizate of Comparative Example 2 using a nitrile group-containing copolymer rubber having an iodine value of more than 20 has a small elongation, and cracks occur at a small elongation in the measurement of deterioration resistance. a, yS—The rubber vulcanizate of Comparative Example 3 using a nitrile group-containing copolymer rubber having an ethylenically unsaturated nitrile monomer unit content of less than 40% by weight showed a volume change in oil resistance measurement. The absolute value of the rate of change is large and the absolute value of the rate of change in volume is large in the measurement of deterioration oil resistance.
それに対し、本発明の加硫物（実施例 1および 2 )は、耐劣化油性の測定にお いて、体積および硬さが変化しにくく、クラックが発生しにくい。 産業上の利用可能性  On the other hand, the vulcanizates of the present invention (Examples 1 and 2) hardly change in volume and hardness and hardly cause cracks in the measurement of deterioration oil resistance. Industrial applicability
本発明のコ'ム加硫物は、二トリル基含有共重合ゴムが有する良好な物性、耐 油性などを実質的に保持しながら、優れた耐劣化油性を示す。  The rubber vulcanizates of the present invention exhibit excellent degradation oil resistance while substantially retaining the good physical properties and oil resistance of the nitrile group-containing copolymer rubber.
従って、 このコ'ム加硫物は、その特性を活かして、 自動車、船舶、および工業用 機械などの潤滑油と接触するゴム部品、例えば、 自動車の駆動系のホース、パッ キン、シールなどに使用することができる。  Therefore, this rubber vulcanizate can be used for rubber parts that come into contact with lubricating oils such as automobiles, ships, and industrial machines, such as hoses, packings, and seals for automobile drive trains. Can be used.

Claims

請求の範囲 The scope of the claims
1. ヨウ素価 20以下、 α, ーエチレン性不飽和二トリル単量体単位含有量 40~ 60重量％の二トリル基含有共重合ゴム（Α) 100重量部に対し、 な ， ーェ チレン性不飽和カルボン酸金属塩（Β)3〜 100重量部を含有してなるゴム組成 物。 1. With 100 parts by weight of a nitrile group-containing copolymer rubber (I) having an iodine value of 20 or less and an α, -ethylenically unsaturated nitrile monomer unit content of 40 to 60% by weight, a non-ethylenic unsaturated A rubber composition comprising 3 to 100 parts by weight of a metal salt of a saturated carboxylic acid (II).
2. 二トリル基含有共重合ゴム（Α)が、 a , ーエチレン性不飽和二トリル単量 体単位 40〜 60重量％と、共役ジェン単量体、非共役ジェン単量体および α—才 レフイン単量体の中から選ばれた少なくとも一種の単量体の単位 40〜 60重量％ とからなる共重合ゴムである請求の範囲 1に記載のゴム組成物。  2. The nitrile group-containing copolymer rubber (Α) is composed of a, -ethylenically unsaturated nitrile monomer unit of 40 to 60% by weight, conjugated diene monomer, non-conjugated diene monomer and α-olefin. 2. The rubber composition according to claim 1, which is a copolymer rubber comprising 40 to 60% by weight of units of at least one monomer selected from monomers.
3. 二トリル基含有共重合ゴム（Α)が、 α， ーエチレン性不飽和二トリル単量 体単位 42〜 55重量％と、共役ジェン単量体、非共役ジェン単量体および or—才 レフイン単量体の中から選ばれた少なくとも一種の単量体の単位 45〜 58重量％ とからなる共重合ゴムである請求の範囲 1に記載のゴム組成物。  3. The nitrile group-containing copolymer rubber (Α) contains 42 to 55% by weight of α, -ethylenically unsaturated nitrile monomer units, conjugated diene monomer, non-conjugated diene monomer and or The rubber composition according to claim 1, which is a copolymer rubber comprising 45 to 58% by weight of units of at least one monomer selected from monomers.
4. 二トリル基含有共重合ゴム（A)が、ヨウ素価 15以下を有するものである請 求の範囲 1 〜 3のいずれかに記載のゴム組成物。  4. The rubber composition according to any one of claims 1 to 3, wherein the nitrile group-containing copolymer rubber (A) has an iodine value of 15 or less.
5. 二トリル基含有共重合ゴム（A)が、ム一二一粘度（ML1 +4, 100°C) 10~ 300を有するものである請求の範囲 1 ~ 4のいずれかに記載のゴム組成物。 5. The rubber according to any one of claims 1 to 4, wherein the nitrile group-containing copolymer rubber (A) has a viscosity of 10 to 300 (ML 1 +4 , 100 ° C). Composition.
6. a , yS —エチレン性不飽和カルボン酸金属塩（C)が、 or , ーエチレン性 不飽和モノカルボン酸、 α, 一エチレン性不飽和ジカルボン酸および α, β —工千 レン性不飽和ジカルボン酸モノエステルの中から選ばれる少なくとも 1種の α, β一 エチレン性不飽和カルボン酸の金属塩である請求の範囲 1〜5のいずれかに記載 のゴム組成物。  6. a, yS —Ethylenic unsaturated carboxylic acid metal salt (C) is or, -ethylenically unsaturated monocarboxylic acid, α, monoethylenically unsaturated dicarboxylic acid and α, β —kosenren unsaturated unsaturated dicarboxylic acid The rubber composition according to any one of claims 1 to 5, wherein the rubber composition is at least one metal salt of an α, β-ethylenically unsaturated carboxylic acid selected from acid monoesters.
7. a , 一エチレン性不飽和カルボン酸金属塩（C)が、 α , 一エチレン性 不飽和モノカルボン酸および α, β一エチレン性不飽和ジカルボン酸の中から選ば れる少なくとも 1種の β—エチレン性不飽和カルボン酸の金属塩である請求の 範囲 1〜 5のいずれかに記載のゴム組成物。  7. a, wherein the metal salt of monoethylenically unsaturated carboxylic acid (C) is at least one β- selected from α, monoethylenically unsaturated monocarboxylic acid and α, β monoethylenically unsaturated dicarboxylic acid. The rubber composition according to any one of claims 1 to 5, which is a metal salt of an ethylenically unsaturated carboxylic acid.
9. a, ーエチレン性不飽和カルボン酸金属塩（C)が、 な ， ーエチレン性 不飽和モノカルボン酸および or , β一エチレン性不飽和ジカルボン酸の中から選ば れる少なくとも 1種のな ， β—エチレン性不飽和カルボン酸と亜鉛、マグネシウム、 カルシウムおよびアルミニウムの中から選ばれる金属との塩である請求の範囲 7に 記載のゴム組成物。 9. a, the -ethylenically unsaturated carboxylic acid metal salt (C) is selected from the group consisting of na, -ethylenically unsaturated monocarboxylic acid and or, β-ethylenically unsaturated dicarboxylic acid The rubber composition according to claim 7, which is a salt of at least one kind of β-ethylenically unsaturated carboxylic acid and a metal selected from zinc, magnesium, calcium and aluminum.
10. a, 一エチレン性不飽和カルボン酸金属塩（C)が、ゴム組成物の製造 時に、二トリル基含有共重合ゴム（A)に ， β一エチレン性不飽和カルボン酸と金 属または金属化合物とを配合して、両者を反応させて生成させたものである請求 の範囲 1ないし 9のいずれかに記載のゴム組成物。  10. a, The metal salt of monoethylenically unsaturated carboxylic acid (C) is added to the nitrile group-containing copolymer rubber (A) during the production of the rubber composition by adding β-ethylenically unsaturated carboxylic acid to a metal or metal. The rubber composition according to any one of claims 1 to 9, wherein the rubber composition is produced by compounding a compound and reacting the two.
11. α, 一エチレン性不飽和カルボン酸 1モルに対し金属または金属化合物 を金属量として 0. 5-3. 2モル配合して、両者を反応させたものである請求の範 囲 10に記載のゴム組成物。  11. Claim 10 in which 0.5 to 3.2 moles of a metal or a metal compound is blended as a metal amount with respect to 1 mole of the α, monoethylenically unsaturated carboxylic acid and the two are reacted. Rubber composition.
12. a, 一エチレン性不飽和カルボン酸金属塩（C)の含有量が、二トリル基 含有共重合ゴム（A) 100重量部に対し、 10〜80重量部である請求の範囲 1〜1 1のいずれかに記載のゴム組成物。  12. The content of the metal salt of monoethylenically unsaturated carboxylic acid (C) is 10 to 80 parts by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber (A). 2. The rubber composition according to any one of 1.
13. 請求の範囲 1〜12のいずれかに記載のゴム組成物に、さらに、二トリル基 含有共重合ゴム（A) 100重量部当たり、有機過酸化物加硫剤（C)0. 2〜10重 量部を含有せしめてなる加硫性ゴム組成物。  13. The rubber composition according to any one of claims 1 to 12, further comprising an organic peroxide vulcanizing agent (C) 0.2 to 100 parts by weight per a nitrile group-containing copolymer rubber (A). A vulcanizable rubber composition containing 10 parts by weight.
14. 有機過酸化物加硫剤（D)の含有量が、二トリル基含有共重合ゴム（A) 1 00重量部当たり、 0. 3〜 7重量部である請求の範囲 13に記載の加硫性ゴム組 成物。  14. The vulcanizing agent according to claim 13, wherein the content of the organic peroxide vulcanizing agent (D) is 0.3 to 7 parts by weight per 100 parts by weight of the nitrile group-containing copolymer rubber (A). Vulcanizable rubber composition.
15. 有機過酸化物加硫剤（D)が、ジアルキルパーオキサイド、ジァシルバーォ キサイドおよびパーォキシエステルの中から選ばれる少なくとも一種である請求の 範囲 13または 14に記載の加硫性ゴム組成物。  15. The vulcanizable rubber composition according to claim 13 or 14, wherein the organic peroxide vulcanizing agent (D) is at least one selected from dialkyl peroxides, dialuminoxides, and peroxyesters.
6. 請求の範囲 13~ 15のいずれかに記載の加硫性ゴム組成物を加硫してな るゴム加硫物。  6. A rubber vulcanizate obtained by vulcanizing the vulcanizable rubber composition according to any one of claims 13 to 15.
PCT/JP2003/000933 2002-01-30 2003-01-30 Rubber composition, vulcanizable rubber composition, and vulcanizate WO2003064518A1 (en)

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EP1876191B1 (en) * 2005-04-28 2011-12-28 Mitsubishi Chemical Corporation Acid-modified polypropylene resin, method for producing same, and resin composition using same
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01306445A (en) * 1988-06-03 1989-12-11 Nippon Zeon Co Ltd Rubber composition for heat-resistant high-pressure hose
JPH01311142A (en) * 1988-06-08 1989-12-15 Nippon Zeon Co Ltd Rubber composition for rubber roll
JPH03188138A (en) * 1989-09-18 1991-08-16 Nippon Zeon Co Ltd Rubber composition for tire slip preventing apparatus and tire slip preventing apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01306445A (en) * 1988-06-03 1989-12-11 Nippon Zeon Co Ltd Rubber composition for heat-resistant high-pressure hose
JPH01311142A (en) * 1988-06-08 1989-12-15 Nippon Zeon Co Ltd Rubber composition for rubber roll
JPH03188138A (en) * 1989-09-18 1991-08-16 Nippon Zeon Co Ltd Rubber composition for tire slip preventing apparatus and tire slip preventing apparatus

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