JP2010144014A - Rubber composition for motor vehicle, and vulcanizate thereof - Google Patents

Abstract

[PROBLEMS] To blend a specific cyclic compound copper complex (anti-aging agent) regardless of the type of vulcanizing agent or acid-accepting agent used in epihalohydrin rubbers, thereby reducing the ozone resistance and heat resistance. Provided is an epihalohydrin-based rubber having an improved resistance.
An automotive rubber composition comprising (a) an epihalohydrin rubber, (b) an acid acceptor, (c) a vulcanizing agent, and (d) a copper complex of a cyclic compound.
[Selection figure] None

Description

  The present invention relates to an automotive rubber composition based on an epihalohydrin rubber having improved heat resistance and a vulcanized product (vulcanized rubber material) obtained by vulcanizing the composition.

  Epihalohydrin rubber materials are widely used as fuel hoses, air hoses, and tube materials in automobile applications, taking advantage of their heat resistance, oil resistance, ozone resistance and the like. However, heat resistance to rubber materials has been improved due to recent exhaust gas regulations and energy saving measures, engine room temperature rises due to higher performance and compactness, etc., and maintenance-free automotive parts. The demand to do is getting stricter year by year.

  In addition, organic nickel compounds, particularly nickel dibutyldithiocarbamate, have been widely used as effective antiaging agents that can improve heat resistance and ozone resistance in epihalohydrin rubbers. However, in recent years, the toxicity of organic nickel compounds has begun to be a concern, and there is a demand for an antiaging agent excellent in heat resistance and ozone resistance that does not use organic nickel compounds in epihalohydrin rubbers.

  Conventionally, as a method for improving the heat resistance of an epihalohydrin rubber, a method using an organic tin compound (see Patent Document 1), a method using a metal soap as an accelerator (see Patent Document 2), and the like have been proposed. There is a need for further improvements.

  Moreover, although the method (refer patent document 2) using a hindered amine compound etc. is proposed as an anti-aging agent which does not use an organic nickel compound, the further improvement is calculated | required.

JP 2003-155409 A JP 2005-002182 A

  On the other hand, general vulcanizing agents for vulcanizing epihalohydrin rubbers include thioureas, mercaptotriazines, quinoxalines, etc., and these are required storage stability, mechanical properties, compression of rubber materials. It is suitably selected according to properties such as permanent distortion, ozone resistance, cold resistance, oil resistance, rubber material processing method, and vulcanizing agent economy. Moreover, as an acid acceptor, magnesium oxide, a lead compound, zinc oxide, synthetic hydrotalcite, slaked lime, quicklime, etc. are suitably selected according to the vulcanizing agent used.

  When the heat resistance of the epihalohydrin rubber is improved by the method using the specific vulcanizing agent or the method using the specific acid acceptor, the processing method of the rubber material is limited, or the rubber material There is a concern that other required characteristics that are different from each other may not be sufficiently satisfied depending on the parts used.

  Therefore, in view of the above circumstances, the present inventors do not depend on the type of vulcanizing agent or acid acceptor used for the epihalohydrin rubber, but by blending a copper complex of a specific cyclic compound (anti-aging agent), An object of the present invention is to provide an epihalohydrin rubber having improved heat resistance without deteriorating ozone resistance.

  As a result of various studies to solve the above problems, the present inventors generally add to a rubber composition for vulcanization containing an epihalohydrin rubber, a vulcanizing agent, and an acid acceptor. By adding a copper complex of a cyclic compound, which is a kind of copper compound that is known to promote the deterioration of rubber and is considered unsuitable in recent automobile applications requiring severe conditions, The present inventors have found that ozone resistance can be further improved and have completed the present invention.

  That is, the automotive rubber composition of the present invention comprises (a) an epihalohydrin rubber, (b) an acid acceptor, (c) a vulcanizing agent, and (d) a copper complex of a cyclic compound. .

  In the automotive rubber composition of the present invention, the copper complex of the cyclic compound (d) is preferably a copper phthalocyanine derivative.

  In the automotive rubber composition of the present invention, the copper phthalocyanine derivative is preferably phthalocyanine blue and / or phthalocyanine green.

  In the automotive rubber composition of the present invention, the blending amount of the copper complex of the cyclic compound (d) is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (a) epihalohydrin rubber.

  In the rubber composition for automobiles of the present invention, the (b) acid acceptor is preferably a metal compound and / or an inorganic microporous crystal.

  In the automotive rubber composition of the present invention, the inorganic microporous crystal is preferably at least one selected from the group consisting of synthetic hydrotalcite, Li—Al inclusion compounds, and zeolites.

  In the automotive rubber composition of the present invention, the (c) vulcanizing agent is at least one selected from the group consisting of a thiourea vulcanizing agent, a quinoxaline vulcanizing agent, and a triazine vulcanizing agent. It is preferable.

  In the rubber composition for automobiles of the present invention, the quinoxaline vulcanizing agent is preferably 6-methylquinoxaline-2,3-dithiocarbonate.

  The vulcanized product of the present invention is preferably formed by vulcanizing the rubber composition for automobiles.

  Hereinafter, the configuration of the present invention will be described in detail.

<Rubber composition>
The rubber composition of the present invention refers to a rubber composition before vulcanization, and includes at least (a) an epihalohydrin rubber, (b) an acid acceptor, (c) a vulcanizer, and (d) a copper complex of a cyclic compound. contains.

<Epihalohydrin rubber>
In the composition of the present invention, the (a) epihalohydrin rubber refers to an epihalohydrin homopolymer or a copolymer with other epoxides copolymerizable with epihalohydrin such as ethylene oxide, propylene oxide, allyl glycidyl ether and the like. For example, epichlorohydrin homopolymer, epibromohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epibromohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epibromohydrin -Propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epibromohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymer Examples thereof include quaternary copolymers, epibromohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymers, and the like. The epihalohydrin rubber is preferably an epichlorohydrin rubber which is an epichlorohydrin homopolymer or a copolymer of epoxide copolymerizable with epichlorohydrin. The epichlorohydrin rubber is preferably an epichlorohydrin homopolymer, an epichlorohydrin-ethylene oxide copolymer, or an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. The molecular weight of these homopolymers or copolymers is not particularly limited, but is usually about ML _{1 + 4} (100 ° C.) = 30 to 150 in terms of Mooney viscosity.

  In the case of the copolymer, the copolymerization ratio is, for example, epichlorohydrin 5 mol% to 95 mol%, preferably 10 mol% to 75 mol%, more preferably 10 mol% to 65 mol%, ethylene oxide 5 mol% to 95 mol%, preferably 25 mol. % To 90 mol%, more preferably 35 mol% to 90 mol%, allyl glycidyl ether 0 mol% to 10 mol%, preferably 1 mol% to 8 mol%, more preferably 1 mol% to 7 mol%.

<Acid acceptor>
As the acid acceptor (b) used in the present invention, a known acid acceptor can be used depending on the vulcanizing agent, but a metal compound and / or an inorganic microporous crystal is preferable. Examples of metal compounds include Group II (Group 2 and Group 12) metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and Group III of the Periodic Table. (Group 3 and Group 13) metal oxides, hydroxides, carboxylates, silicates, sulfates, nitrates, phosphates, periodic table Group IV (Groups 4 and 14) metal oxides, Examples thereof include metal compounds such as basic carbonates, basic carboxylates, basic phosphites, basic sulfites, and tribasic sulfates.

  Specific examples of the metal compound include magnesia, magnesium hydroxide, aluminum hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate. , Calcium phosphite, zinc oxide, tin oxide, lisage, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, base For example, basic lead sulfite and tribasic lead sulfate.

  The inorganic microporous crystal refers to a crystalline porous body, and can be clearly distinguished from amorphous porous bodies such as silica gel and alumina. Examples of such inorganic microporous crystals include zeolites, aluminophosphate type molecular sieves, layered silicates, synthetic hydrotalcites, Li-Al inclusion compounds, alkali metal titanates, and the like. A particularly preferred acid acceptor is synthetic hydrotalcite.

  The zeolites are natural zeolite, A-type, X-type, Y-type synthetic zeolite, sodalite, natural or synthetic mordenite, various zeolites such as ZSM-5, and metal substitutes thereof. It may be used in combination of two or more. Further, the metal of the metal substitution product is often sodium. As the zeolite, those having a large acid-accepting ability are preferable, and A-type zeolite is preferable.

The synthetic hydrotalcite has the following general formula (1)
_{Mg X Zn Y Al Z (OH} ) 2 (X + Y) + 3Z-2 CO 3 · wH 2 O (1)
[Wherein x and y are real numbers of 0 to 10, where x + y is 1 to 10, z is a real number of 1 to 5, and w is a real number of 0 to 10, respectively].

As examples of the synthetic hydrotalcite represented by the general formula (1), Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ , Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3.5H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O, Mg ₃ Al _{2 (OH) 10 CO 3 ·} 1.7H 2 O, Mg 3 ZnAl 2 (OH) 12 CO 3 · 3.5H 2 O, can be cited _{Mg 3 ZnAl 2 (OH) 12} CO 3 and the like.

The Li—Al inclusion compound is represented by the following general formula (2).
[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (2)
(Wherein X is an inorganic or organic anion, n is the valence of anion X, and m is an integer of 3 or less)

  The blending amount of the (b) acid acceptor is 0.2 to 50 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the (a) epihalohydrin rubber. Part by weight is particularly preferred. When the amount of the acid acceptor is less than 0.2 parts by weight with respect to 100 parts by weight of the epihalohydrin rubber, crosslinking is insufficient, while when it exceeds 50 parts by weight with respect to 100 parts by weight of the epihalohydrin rubber, the vulcanized product Becomes too rigid, and physical properties normally expected as an epihalohydrin rubber vulcanizate cannot be obtained.

<Vulcanizing agent>
The vulcanizing agent (c) used in the present invention is not particularly limited as long as it can crosslink epihalohydrin rubber, but known vulcanizing agents utilizing the reactivity of chlorine atoms, that is, polyamines, thioureas, Thiadiazoles, mercaptotriazines, quinoxalines, etc., and known vulcanizing agents that utilize side chain double bond reactivity, such as organic peroxides, sulfur, morpholine polysulfides, thiuram polysulfides, etc. used.

  Examples of the vulcanizing agent (c) include polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N′-dicinenamilidene-1, 6-hexanediamine, ethylenediamine carbamate, hexamethylenediamine carbamate, and the like. Examples of thioureas include 2-mercaptoimidazoline, 1,3-diethylthiourea, 1,3-dibutylthiourea, trimethylthiourea, and the like, and thiadiazoles 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate and the like, and triazines include 2,4,6-triazol Lucapto-1,3,5-triazine, 1-hexylamino-3,5-dimercaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,5-dimercaptotriazine, 1- Examples include dibutylamino-3,5-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 1-phenylamino-3,5-dimercaptotriazine and the like. Mercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate and the like, and examples of the organic peroxide include tert -Butyl hydroperoxide, p-menthane hydroperoxy Id, dicumyl peroxide, tert-butyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, benzoylper Oxide, tert-butyl peroxybenzoate and the like, morpholine polysulfides include morpholine disulfide, and thiuram polysulfides include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuramtetrasulfide. Examples thereof include sulfide and dipentamethylene thiuram hexasulfide. Among these, (c) vulcanizing agents are preferably thioureas (thiourea vulcanizing agents), quinoxalines (quinoxaline vulcanizing agents), and triazines (triazine vulcanizing agents), particularly preferably 2- Examples include mercaptoimidazoline, 6-methylquinoxaline-2,3-dithiocarbonate, trimercapto-S-triazine. One vulcanizing agent may be used alone, or two or more vulcanizing agents may be used in combination.

  The compounding amount of the (c) vulcanizing agent is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the (a) epihalohydrin rubber. When the blending amount is less than 0.1 parts by weight with respect to 100 parts by weight of the epihalohydrin rubber, crosslinking is insufficient. On the other hand, when it exceeds 10 parts by weight with respect to 100 parts by weight of the epihalohydrin rubber, the vulcanizate becomes rigid. Therefore, the physical properties normally expected as an epihalohydrin rubber vulcanizate cannot be obtained.

  In addition, known accelerators (that is, vulcanization accelerators), retarders and the like which are usually used together with these vulcanizing agents can be used as they are in the rubber composition for vulcanization of the present invention. Examples of these vulcanization accelerators include sulfur, thiuram sulfides, morpholine sulfides, amines, weak acid salts of amines, basic silica, quaternary ammonium salts, quaternary phosphonium salts, polyfunctional vinyl compounds, mercapto Examples include benzothiazoles, sulfenamides, and dimethylthiocarbamates. Examples of the retarder include N-cyclohexanethiophthalimide, an organic zinc compound, and acidic silica. As a particularly preferred accelerator, 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU) salt, 1,5-diazabicyclo (4,3,0) nonene-5 (hereinafter abbreviated as DBN) salt And white carbon.

  Examples of the DBU salt include DBU-carbonate, DBU-stearate, DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, DBU-3-hydroxy-2-naphthoate, DBU- Phenol resin salts, DBU-2-mercaptobenzothiazole salts, DBU-2-mercaptobenzimidazole salts, etc., and DBN salts include DBN-carbonate, DBN-stearate, DBN-2-ethylhexylate, DBN -Benzoate, DBN-salicylate, DBN-3-hydroxy-2-naphthoate, DBN-phenol resin salt, DBN-2-mercaptobenzothiazole salt, DBN-2-mercaptobenzimidazole salt and the like. The blending amount of the accelerator or retarder is preferably 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the epihalohydrin rubber.

<Copper complex of cyclic compound>
The copper complex of the cyclic compound (d) used in the present invention is a compound having a structure in which copper is coordinated inside the ring of the cyclic organic compound, and imparts characteristics as an anti-aging agent. For example, a copper phthalocyanine derivative, a copper porphyrin derivative, a copper crown ether derivative, etc. are mentioned, Preferably a copper phthalocyanine derivative is mentioned. Examples of the copper phthalocyanine derivative include phthalocyanine copper and chlorinated phthalocyanine. Specifically, phthalocyanine blue, phthalocyanine green, and the like can be used. Two or more kinds of cyclic complexes of the copper complex may be used in combination.

  The amount of the copper complex of the (d) cyclic compound is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the (a) epihalohydrin rubber. If the blending amount is less than this range, the effect of improving heat resistance is small, and blending a large amount is not economical.

<Other additives>
Furthermore, known anti-aging agents usually used in the rubber composition for vulcanization of the present invention can be used as they are as long as the desired properties of the present invention are not impaired. Known anti-aging agents here are amine, phenol, benzimidazole, dithiocarbamate, thiourea, special wax, organic thioacid, phosphorous acid, salicylic acid derivative, benzophenone, A benzotriazole type | system | group etc. can be mentioned, Especially preferably, they are a phenol type, a benzimidazole type | system | group, an organic thioacid type | system | group, and a phosphorous acid type | system | group.

  Examples of the amine-based antioxidants include phenyl-α-naphthylamine, phenyl-β-naphthylamine, p- (p-toluenesulfonylamide) -diphenylamine, 4,4 ′-(α, α′-dimethylbenzyl) diphenylamine, 4 , 4'-dioctyl diphenylamine, high temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine, aniline, acetone, reaction product of diphenylamine and diisobutylene, octylated diphenylamine, Dioctylated diphenylamine, p, p'-dioctyl diphenylamine, octylated diphenylamine mixture, substituted diphenylamine, alkylated diphenylamine, alkylated diphenylamine mixture, aralkylated diphenylamine Mixtures of alkyl and aralkyl-substituted phenols with diphenylamine, diphenylamine derivatives, N, N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N, N′-di-2-naphthyl -P-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N′-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N′-bis (1-ethyl-3-methylpentyl) -p -Phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine , Diallyl-p-phenylenediamine, phenyl, hexyl-p-phenylenediamine, phenyl, octyl-p-phenylenediamine, etc., and other amine-based condensation products of aromatic amines and aliphatic ketones, butyl Examples include aldehyde-aniline condensate, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and the like.

  Examples of the phenolic anti-aging agent include 2,5-di- (t-amyl) -hydroquinone, 2,5-di-t-butylhydroquinone, hydroquinone monomethyl ether, and the like. Methyl-4-isopropylbenzene, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6 -Di-t-butyl-4-sec-butylphenol, butyl hydroxyanisole, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-t-butyl-α-dimethylamino-p -Cresol, alkylated phenol, aralkyl-substituted phenol, phenol derivative, 2,2'-methylenebis (4-methyl-6-tert-butyl) Ruphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6- Di-tert-butylphenol), 2,2-methylenebis (6-α-methyl-benzyl-p-cresol), 4,4′-butylidenebis (3-methyl-6-tert-butylcresol), 2,2′- Ethylidenebis (4,6-di-tert-butylphenol), 1,1′-bis (4-hydroxyphenyl) -cyclohexane, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl)- 5,5-dimethyl diphenylmethane, alkylated bisphenol, butylated reaction product of p-cresol and dicyclopentadiene, 1,3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5- Di-tert-pentylphenyl) -ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3 (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, butyric acid 3,3-bis (3-tert-butyl-4-hydroxyphenyl) ethylene ester 1 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester of 3,5-tri (2-hydroxyethyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, Modified polyalkyl phosphited polyphenols, 4,4′-thiobis (6-tert-butyl-3-methylphenol), 4,4′-thiobis- (6-tert-butyl-o-cresol), 4 , 4′-di and tri-thiobis- (6-tert-butyl-o-cresol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 1,1,3-tris- ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol) ), N-o Tadecyl-3- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxy Phenyl) propionate] methane, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl) -4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio)- 6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tris- (3,5-di-tert-butyl-4 Hydroxybenzyl) -isocyanurate, 2,2-thio-diethylenebis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylbis (3,5-tert-butyl- 4-hydroxy-hydrocinnamamide), 2,4-bis [(octylthio) methyl] -o-cresol, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate-diethyl ester, tetrakis [methylene ( 3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester, hindered phenol, hindered Bisphenol, 2-hydroxynaphthalene-3-carboyl-2'-methoxyanilide, 2-hydride Xinaphthalene-3-carboyl-2′-methylanilide, 2-hydroxynaphthalene-3-carboyl-4′-methoxyanilide, 4,4′-bis (N, N′-dimethylamino) -triphenylmethane, 2- Examples include hydroxynaphthalene-3-carbylanilide, 1,1′-bis (4,4′-N, N′-dimethylaminophenyl) -cyclohexane, and the like.

  Examples of the benzimidazole antioxidant include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, a mixture of 2-mercaptobenzimidazole and a phenol condensate, a metal salt of 2-mercaptobenzimidazole, and 2-mercaptomethylbenzimidazole. 4 and 5-mercaptomethylbenzimidazole, and metal salts of 4 and 5-mercaptomethylbenzimidazole.

  Examples of the dithiocarbamate-based anti-aging agent include nickel diethyl dithiocarbamate, nickel dimethyl dithiocarbamate, nickel dibutyl dithiocarbamate, nickel diisobutyl dithiocarbamate and the like.

  Examples of the thiourea antioxidant include 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.

  Examples of the organic thioic acid type antioxidant include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, penta Examples include erythritol-tetrakis- (β-lauryl-thiopropionate), dilauryl thiodipropionate, and the like.

Examples of the phosphorous acid-based antioxidant include tris (nonylphenyl) phosphite, tris (mixed mono- and di-nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite Diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, diphenyl nonylphenyl phosphite, triphenyl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-ethylhexyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritoltetra Phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butyl- Di-tridecyl phosphite), 2,2′-ethylidenebis (4,6-di-tert-butylphenol) fluorophosphite, 4,4′-isopropylidene-diphenol alkyl (C ₁₂ -C ₁₅ ) phosphite , Cyclic neopentanetetrayl bis (2,4-di-tert-butylphenyl phosphite), cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4-phenyl phosphite), cyclic neopentanetetra Irbis (nonylphenyl phosphite), bis (nonylphenyl) pentaerythritol diphosphite, dibutyl hydro Examples thereof include genphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, and the like.

  Examples of the salicylic acid derivative anti-aging agent include phenyl salicylate and pt-butylphenyl salicylate.

  Examples of the benzophenone anti-aging agent include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy benzophenone, 2,2′-dihydroxy-4-methoxy benzophenone, 2,2′-dihydroxy-4,4- Dimethoxy benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxy benzophenone, 2,2 ', 4,4-tetrahydroxy benzophenone, 4-dodecyloxy-2 -Hydroxy-benzophenone, 2-hydroxy-4-acryloyloxyethoxybenzophenone, 4- (2-acryloyloxyethoxy) -2-hydroxybenzophenone polymer, 3,5-di-t-butyl-4-hydroxybenzoyl acid, n -F Sa decyl esters, such as bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like.

  As the benzotriazole-based anti-aging agent, 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole , 2- [2′-Hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazo 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol, 2- [2-hydroxy-3,5 -Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like.

  Other anti-aging agents include oxalic anilide derivatives, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-ethylhexyl-2-cyano-3,3 -Diphenyl acrylate, 1,3-bis- (4-benzoyl-3-hydroxyphenoxy) -2-propyl acrylate, 1,3-bis- (4-benzoyl-3-hydroxyphenoxy) -2-propyl methacrylate, 1 , 3-bis- (4-benzoyl-3-hydroxyphenoxy) -2-propyl methacrylate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, methyl o-benzoylbenzoate, ethyl-2-cyano-3, 3-diphenyl acrylate, 2-hydroxy-4-benzyloxy benzophenone, [2,2 ′ Thiobis- (4-t-octylphenolato)]-n-butylamine nickel II, [2,2′-thiobis- (4-t-octylphenolato)]-2-ethylhexylamine nickel II, semicarbazone light Examples include stabilizers.

  The blending ratio of the anti-aging agent is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the epihalohydrin rubber. It is. These two or more types are used in combination. In addition, unless the effect of this invention is impaired, it is not limited to the said well-known anti-aging agent, a ultraviolet absorber, and a light stabilizer.

  In the rubber composition for vulcanization of the present invention, unless the effects of the present invention are impaired, compounding agents other than the above, for example, lubricants, fillers, reinforcing agents, plasticizers, processing aids, flame retardants, foaming aids. Further, a conductive agent, an antistatic agent and the like can be arbitrarily blended. Furthermore, it is possible to perform blending of rubber, resin, etc., which is usually performed in the technical field, as long as the characteristics of the present invention are not lost.

  In order to produce the rubber composition for vulcanization according to the present invention, any mixing means conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneaders and the like can be used. The vulcanized rubber material of the present invention is usually obtained by heating the vulcanized rubber composition of the present invention to 100 to 200 ° C. The vulcanization time varies depending on the temperature, but is usually between 0.5 and 300 minutes. As a method of vulcanization molding, any method such as compression molding using a mold, injection molding, a steam can, an air bath, infrared rays, or heating by microwaves can be used.

  The vulcanized product of the present invention can be widely applied to fields where epihalohydrin rubbers are usually used. For example, it is useful as a rubber material such as various fuel-based laminated hoses, air-based laminated hoses, tubes, belts, diaphragms, seals and the like for automobile applications.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

[Example]
<Examples 1-4, Comparative Examples 1-10>
Each material shown in the following Table 1 and Table 2 was kneaded with a kneader and an open roll to prepare an unvulcanized rubber sheet. The Mooney scorch test defined in JIS K6300 was performed using the obtained unvulcanized rubber sheet. Further, the obtained unvulcanized rubber sheet was press vulcanized at 170 ° C. for 15 minutes to obtain a primary vulcanizate having a thickness of 2 mm. Further, this was heated in an air oven at 150 ° C. for 2 hours to obtain a secondary vulcanizate. Using the obtained secondary vulcanizate, tensile tests (initial physical properties), heat resistance and ozone resistance were evaluated. Each evaluation test was performed according to the method described in JIS K6251, JIS K6257, and JIS K6259, respectively.

Tables 3 and 4 show the test results of Examples and Comparative Examples obtained from each test method. In each table, M ₁₀₀ is the tensile stress at 100% elongation defined in the tensile test of JIS K6251, Tb is the tensile strength defined in the tensile test of JIS K6251, Eb is the elongation defined in the tensile test of JIS K6251, and Hs is the elongation defined in JIS K6253. The symbol in the hardness test and the symbol in the ozone test mean the state of cracks in JIS K6259. Moreover, the symbol in an ozone test means the following state of the crack of JISK6259. In addition, in this invention, that heat resistance is favorable means that the tensile strength Tb after a heat test is large.
N.C .: No crack C-3: A crack is deep and relatively large (less than 1 mm) and countless.

Details of the blending contents used in the examples of the present invention are shown below.
* 1 "Epichromer H" manufactured by Daiso Corporation, epichlorohydrin polymer
* 2 “NOCRACK White” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 3 “Noxeller TTCu” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 4 "DHT-4A" manufactured by Kyowa Chemical Industry Co., Ltd.
* 5 "NS Soap" manufactured by Kao Corporation
* 6 “Neuiser P” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
* 7 “Daisonette XL-21S” manufactured by Daiso Corporation
* 8 “Kyowa Mug # 150” manufactured by Kyowa Chemical Industry Co., Ltd.
* 9 “Nokutizer SS” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 10 "Axel 22-S" manufactured by Kawaguchi Chemical Industry Co., Ltd.
* 11 “Noxeller TS” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 12 “Gisnet F” manufactured by Sankyo Kasei Co., Ltd.

  Comparative Examples 1, 9, and 10 not containing an anti-aging agent, Comparative Example 2 not being a complex of a cyclic compound, Comparative Examples 3 and 4 containing a complex other than copper of a cyclic compound, Pigment Red 101 being a general pigment, and In Comparative Examples 5 and 6 containing Pigment Blue 29, and Comparative Example 7 containing N, N-di-2-naphthyl-p-phenylenediamine which is a general anti-aging agent, Examples 1-4 of the present application were used. In comparison example 8 containing a copper compound that is not a cyclic compound, the ozone resistance is found to be inferior compared to Examples 1 to 4 of the present invention. It was confirmed that the above characteristics were improved in the examples of the present application.

INDUSTRIAL APPLICABILITY According to the present invention, an automotive rubber composition having improved heat resistance and ozone resistance in an epihalohydrin rubber and a vulcanized product (vulcanized rubber material) thereof can be provided.

Claims (9)

  An automotive rubber composition comprising (a) an epihalohydrin rubber, (b) an acid acceptor, (c) a vulcanizing agent, and (d) a copper complex of a cyclic compound.   The automotive rubber composition according to claim 1, wherein the copper complex of the cyclic compound (d) is a copper phthalocyanine derivative.   The automotive rubber composition according to claim 2, wherein the copper phthalocyanine derivative is phthalocyanine blue and / or phthalocyanine green.   The amount of the copper complex of the (d) cyclic compound is 0.1 to 5 parts by weight with respect to 100 parts by weight of the (a) epihalohydrin rubber. The rubber composition for automobiles as described.   The automotive rubber composition according to any one of claims 1 to 4, wherein the acid acceptor (b) is a metal compound and / or an inorganic microporous crystal.   6. The automotive rubber composition according to claim 5, wherein the inorganic microporous crystal is at least one selected from the group consisting of synthetic hydrotalcite, Li-Al inclusion compounds, and zeolites. .   7. The vulcanizing agent (c) is at least one selected from the group consisting of a thiourea vulcanizing agent, a quinoxaline vulcanizing agent, and a triazine vulcanizing agent. The rubber composition for automobiles according to any one of the above.   The rubber composition for automobiles according to claim 7, wherein the quinoxaline vulcanizing agent is 6-methylquinoxaline-2,3-dithiocarbonate.   A vulcanized product obtained by vulcanizing the rubber composition for automobiles according to any one of claims 1 to 8.