JP2014025017A - Epichlorohydrin rubber composition used being subjected to vulcanization, excellent in vulcanizing characteristics and storage stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition used being subjected to vulcanization having good storage stability, regarding an epichlorohydrin rubber composition containing a triazine-type vulcanizer as a vulcanizer.SOLUTION: It is found that a problem can be solved by using an epichlorohydrin rubber (a), (b) a triazine-type vulcanizer (b), an acid-acceptor (c) and an acid anhydride (d) by various studies regarding an epichlorohydrin rubber composition containing a triazine-type vulcanizer as a vulcanizer.

Description

  The present invention relates to a vulcanized rubber composition containing an epichlorohydrin rubber excellent in vulcanization characteristics and storage stability, a vulcanized rubber material obtained by vulcanizing the vulcanized rubber composition, and the vulcanized rubber. The present invention relates to an automotive hose using the material.

  Generally, halogen-containing elastomers such as epichlorohydrin rubbers are widely used as materials having excellent physical properties by being vulcanized. Especially, epichlorohydrin rubbers make use of their heat resistance, oil resistance, ozone resistance, etc. In automobile applications, they are used as fuel hoses, air hoses, and tube materials.

  Examples of vulcanizing agents for epichlorohydrin rubber include quinoxaline vulcanizing agents, triazine vulcanizing agents, thiourea vulcanizing agents, thiadiazole vulcanizing agents, thiuram polysulfide vulcanizing agents, bisphenol vulcanizing agents, and polyamine vulcanizing agents. Sulfurizing agents, morpholine polysulfide vulcanizing agents, organic oxides, sulfur and the like are used.

  Among the above vulcanizing agents, the rubber composition for vulcanization containing epichlorohydrin rubber using a triazine vulcanizing agent can control the vulcanization speed and storage stability even when a number of retarders are used. It was difficult. Therefore, even in a vulcanizing rubber composition containing an epichlorohydrin rubber using a triazine vulcanizing agent, there is a demand for a compound having excellent storage stability by efficiently providing a delay effect (Patent Documents). 1).

JP 2000-63685 A

  In a composition of epichlorohydrin rubber using a triazine vulcanizing agent as a vulcanizing agent, a rubber composition for vulcanization having good storage stability is provided.

  As a result of various studies on the composition of an epichlorohydrin rubber using a triazine vulcanizing agent as a vulcanizing agent, the present inventors have found that (a) an epichlorohydrin rubber, (b) a triazine vulcanizing agent, and (c) a receiving agent. It has been found that the above problems can be solved by using a rubber composition for vulcanization containing an acid agent and (d) an acid anhydride.

  In the rubber composition for vulcanization of the present invention, (d) the acid anhydride is preferably maleic anhydride. Moreover, it is preferable to contain 0.5-10 weight part of (d) acid anhydride with respect to 100 weight part of (a) epichlorohydrin rubber.

  In the rubber composition for vulcanization | cure of this invention, it is preferable to contain 0.5-5 weight part of (b) triazine vulcanizing agents with respect to 100 weight part of (a) epichlorohydrin rubber.

  In the rubber composition for vulcanization | cure of this invention, it is preferable that (c) acid acceptor is hydrotalcite. Moreover, it is preferable to contain 1-10 weight part of (c) acid acceptor with respect to 100 weight part of (a) epichlorohydrin rubber.

  In the rubber composition for vulcanization | cure of this invention, it is preferable to contain (e) vulcanization retarder further, and it is more preferable that (e) vulcanization retarder is N-cyclohexyl thiophthalimide.

  The rubber composition for vulcanization of the present invention preferably further comprises (f) a vulcanization accelerator, and (f) the vulcanization accelerator is 1,8-diazabicyclo (5,4,0) undecene-7. More preferably, it is a salt.

  The vulcanized rubber material obtained by vulcanizing the rubber composition for vulcanization of the present invention is used for automobile hoses and the like.

  The rubber composition for vulcanization of the present invention is an epichlorohydrin rubber composition using a triazine vulcanizing agent as a vulcanizing agent, has good storage stability, and is excellent in processability. Moreover, the vulcanized rubber material obtained by vulcanizing the vulcanized rubber composition obtained by the present invention is useful for automobile hoses and the like by forming a laminate by adhering to a fluoropolymer.

  The present invention is described in detail below. The rubber composition for vulcanization of the present invention contains at least (a) an epichlorohydrin rubber, (b) a triazine vulcanizer, (c) an acid acceptor, and (d) an acid anhydride. It is preferable to contain a) vulcanization retarder and (f) a vulcanization accelerator.

The (a) epichlorohydrin rubber used in the rubber composition for vulcanization of the present invention is an epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. Examples thereof include quaternary copolymers and epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymers. Preferred are epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, and more preferred epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether. A terpolymer. The molecular weight of these homopolymers or copolymers is not particularly limited, but is usually a polymer having a Mooney viscosity display of ML _{1 + 4} (100 ° C.) = About 30 to 150.

  In the case of an epichlorohydrin-ethylene oxide copolymer, the copolymerization ratio of epichlorohydrin is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 75 mol%, and more preferably 10 mol% to 65 mol%. Particularly preferred. Ethylene oxide is preferably 5 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, and particularly preferably 35 mol% to 90 mol%.

  In the case of an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, the copolymerization ratio is, for example, preferably 4 mol% to 94 mol%, more preferably 9 mol% to 74 mol%, more preferably 9 mol% to It is especially preferable that it is 64 mol%. Ethylene oxide is preferably 5 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, and particularly preferably 35 mol% to 90 mol%. The allyl glycidyl ether is preferably 1 mol% to 10 mol%, more preferably 1 mol% to 8 mol%, and particularly preferably 1 mol% to 7 mol%.

Examples of the (b) triazine vulcanizing agent used in the present invention include 2,4,6-trimercapto-1,3,5-triazine, 2-methoxy-4,6-dimercaptotriazine, 2-hexylamino- 4,6-dimercaptotriazine, 2-diethylamino-4,6-dimercaptotriazine, 2-cyclohexylamino-4,6-dimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, 2-anilino- Examples thereof include 4,6-dimercaptotriazine and 2-phenylamino-4,6-dimercaptotriazine. Among these, 2,4,6-trimercapto-1,3,5-triazine represented by the general formula (I) is preferable.

  The content of the (b) triazine vulcanizing agent used in the vulcanizing rubber composition of the present invention is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber. It is more preferably ˜3 parts by weight, and particularly preferably 1-2 parts by weight.

  In the rubber composition for vulcanization of the present invention, (c) a metal compound and / or an inorganic microporous crystal is used as an acid acceptor.

  Examples of metal compounds that serve as acid acceptors include Group II metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and periodic table IVA. Group metal oxides, basic carbonates, basic carboxylates, basic phosphites, basic sulfites, tribasic sulfates and the like.

  Specific examples of metal compounds that serve as acid acceptors include magnesia (magnesium oxide), magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, sodium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, Calcium phthalate, calcium phosphite, zinc white, tin oxide, lisage, red lead, lead white, dibasic lead phthalate, basic lead silicate, tin stearate, basic lead phosphite, basic phosphorous acid Examples thereof include tin, basic lead sulfite, and tribasic lead sulfate. Particularly preferred acid acceptors include magnesia (magnesium oxide), sodium carbonate, quicklime, slaked lime, and calcium carbonate.

  The inorganic microporous crystal means a crystalline porous body, and can be clearly distinguished from an amorphous porous body such as silica gel, alumina and the like. Examples of such inorganic microporous crystals include zeolites, alumina phosphate type molecular sieves, layered silicates, hydrotalosites, alkali metal titanates and the like. Particularly preferred acid acceptors include hydrotalosites.

  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 or a 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.

（式中のｘとｙはそれぞれｘ＋ｙ＝１〜１０の関係を有する０〜１０の実数、ｚは１〜５、ｗは０〜１０の実数をそれぞれ示す。） Hydrotalcites are represented by the following general formula (II).

(Wherein x and y are 0 to 10 real numbers having a relationship of x + y = 1 to 10, respectively, z is 1 to 5, and w is a real number of 0 to 10.)

Examples of hydrotalcites represented by the general formula (II) include 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 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, Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ , Mg _4.3 Al ₂ (OH) _12.6 CO ₃ .3.5H ₂ O, etc. Can do.

  The content of the (c) acid acceptor used in the rubber composition for vulcanization of the present invention is preferably 1 to 10 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber, and 1 to 5 weights. More preferably, it is 2 to 4 parts by weight. Within these ranges, the physical properties normally expected as an epichlorohydrin rubber vulcanizate can be obtained without sufficient crosslinking and the vulcanizate becoming too rigid.

  Examples of the acid anhydride (d) used in the rubber composition for vulcanization of the present invention include acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride, and maleic anhydride. Preferably there is.

  The content of (d) acid anhydride used in the rubber composition for vulcanization of the present invention is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber, More preferably, it is -8 weight part, It is especially preferable that it is 0.5-5 weight part. Within these ranges, the rubber composition for vulcanization has good storage stability.

  The rubber composition for vulcanization of the present invention may further contain (e) a vulcanization retarder. As the vulcanization retarder, a known vulcanization retarder generally used can be used without limitation. Specific examples of known vulcanization retarders include N-cyclohexylthiophthalimide, organic zinc compounds such as zinc stearate, acidic silica, and the like. Among these, N-cyclohexylthiophthalimide is preferable.

  In the rubber composition for vulcanization of the present invention, the content of (e) vulcanization retarder is preferably 0 to 10 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber, More preferably, it is 5 parts by weight.

  The rubber composition for vulcanization of the present invention may further contain (f) a vulcanization accelerator. (F) Vulcanization accelerators include morpholine sulfides, amines, weak acid salts of amines, basic silica, quaternary ammonium salts, quaternary phosphonium salts, alkali metal salts of fatty acids, thiuramsphides, mercaptobenzothiazole , Sulfenamides, 1,8-diazabicyclo (5,4,0) undecene-7 (abbreviated as DBU) salt, 1,5-diazabicyclo (4,3,0) nonene-5 (abbreviated as DBN) salt And is preferably a DBU salt.

  Specific examples of morpholine sulfides include morpholine disulfide.

  Specific examples of amines include n-hexylamine, octylamine, dibutylamine, tributylamine, and hexamethylenediamine.

  Specific examples of the weak acid salts of amines include n-butylamine / acetate, hexamethylenediamine / carbamate, and dicyclohexylamine salt of 2-mercaptobenzothiazole.

  Specific examples of quaternary ammonium salts include tetrabutylammonium chloride and tetrabutylammonium bromide.

  Specific examples of quaternary phosphonium salts include tetrabutylphosphonium chloride and tetrabutylphosphonium bromide.

  Specific examples of the fatty acid alkali metal salts include sodium salts and potassium salts such as stearic acid, oleic acid, sebacic acid, and castor oil.

  Specific examples of thiuram sulfides include tetramethyl thiuram disulfide, tetramethyl thiuram monosulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and dipentamethylene thiuram tetrasulfide.

  Specific examples of mercaptobenzothiazoles include 2-mercaptobenzothiazole and zinc salt of 2-mercaptobenzothiazole.

  Specific examples of the sulfenamides include N-ethyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazylsulfenamide, N, N-di-cyclohexyl-2-benzo Thiazylsulfenamide is mentioned.

  Specific examples of DBU salts include DBU-carbonate, DBU-stearate, DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, DBU-3-hydroxy-2-naphthoate. DBU-phenol resin salt, DBU-2-mercaptobenzothiazole salt, DBU-2-mercaptobenzimidazole salt and the like.

  Specific examples of 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.

  In the rubber composition for vulcanization of the present invention, the content of the (f) vulcanization accelerator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (a) epichlorohydrin rubber. More preferably, it is 5 to 3 parts by weight.

  A known anti-aging agent can be used in the rubber composition for vulcanization of the present invention. Known anti-aging agents include amine anti-aging agents, phenol anti-aging agents, benzimidazole anti-aging agents, dithiocarbamate anti-aging agents, thiourea anti-aging agents, organic thio acid anti-aging agents, Phosphoric acid-based antioxidants are exemplified, and amine-based antioxidants, phenol-based antioxidants, benzimidazole-based antioxidants, and dithiocarbamate-based antioxidants are preferable.

  Specific examples of the amine-based antiaging agent 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, diphenylamine and acetone and low temperature reaction product, diphenylamine, aniline, acetone low temperature reaction product, diphenylamine and diisobutylene reaction product, octyl Diphenylamine, dioctylated diphenylamine, p, p'-dioctyl diphenylamine, mixed product of octylated diphenylamine, substituted diphenylamine, alkylated diphenylamine, mixed product of alkylated diphenylamine, aralkylation 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-ph There are nylenediamine, a mixture of diallyl-p-phenylenediamine, phenyl, hexyl-p-phenylenediamine, phenyl, octyl-p-phenylenediamine, etc. Other amines are condensation products of aromatic amines and aliphatic ketones, butyl Examples include aldehyde-aniline condensate, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.

  Specific examples of phenolic anti-aging agents include 2,5-di- (t-amyl) -hydroquinone, 2,5-di-t-butylhydroquinone, hydroquinone monomethyl ether, etc. Oxy-3-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-butylphenol), 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-methyl) (Cyclohexyl) -5,5-dimethyl diphenylmethane, alkylated bisphenol, p-cresol and dicyclopentadiene Reaction product, 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) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, buty Acid 3,3-bis (3-tert-butyl-4-hydroxyphenyl) ethylene ester, 1,3,5-tri (2-hydroxyethyl) -s-triazine-2,4,6- (1H, 3H, 5H) Trione 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester, modified polyalkyl phosphite polyhydric phenol, 4,4'-thiobis (6-tert-butyl-3-methyl) Phenol), 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-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-) tert-Butylphenyl) propionate, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) 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-diethylene bis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylebis (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-hydroxynaphthalene-3-carboyl-2 ' -Methylanilide, 2-hydroxynaphthalene-3-carboyl-4'-methoxyanilide, 4,4'-bis (N, N'-dimethylamino) -triphenylmethane, 2-hydroxynaphthalene-3-carboylanilide, 1,1′-bis (4,4′-N, N′-dimethylaminophenyl) -cyclohexane.

  Specific 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, 2- A metal salt of mercaptomethylbenzimidazole, a metal salt of 4 and 5-mercaptomethylbenzimidazole, and a metal salt of 4 and 5-mercaptomethylbenzimidazole.

  Specific examples of the dithiocarbamate antioxidant include nickel diethyldithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel diisobutyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, N -Copper of ethyl-N-phenyldithiocarbamate, copper N-pentamethylenedithiocarbamate, copper dibenzyldithiocarbamate.

  Specific examples of the thiourea anti-aging agent include 1,3-bis (dimethylaminopropyl) -2-thiourea, tributylthiourea and the like.

  Specific examples of the organic thioic acid antioxidant include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipro Pionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), dilauryl thiodipropionate can be mentioned.

Specific examples of phosphite antioxidants 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) pentaerythris Tall tetraphosphite, 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 neopentanetetraylbis (2,4-di-tert-butylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-tert-butyl-4-phenylphosphite), cyclic neo Pentanetetraylbis (nonylphenyl phosphite), bis (nonylphenyl) pentae Sri tall diphosphite, dibutyl hydrogenphosphite phosphite, distearyl pentaerythritol diphosphite, include hydrogenated bisphenol A · pentaerythritol phosphite polymer.

  In the rubber composition for vulcanization according to the present invention, the blending amount of the antioxidant is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber, and 0.1 to 5 parts by weight. More preferred are parts by weight, and particularly preferred is 0.3 to 3 parts by weight. If the blending amount is less than this range, there is little effect on ozone resistance and heat resistance, and it is not economical to blend a large amount, and there is a problem that a large amount of bloom occurs on the surface of the vulcanized rubber material. It becomes easy to do.

  In the rubber composition for vulcanization of the present invention, only epichlorohydrin rubber may be used as a rubber component, but rubber, resin, etc., which are usually used in the technical field as long as the characteristics of the present invention are not lost. It is also possible to perform blending. Specifically, acrylic rubber (ACM, AEM, ANM), acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (H-NBR), butyl rubber (IIR), halo-isobutene-isoprene rubber (CIIR, BIIR), Rubber-like copolymer of ethylene and butene (EBM), rubber-like copolymer of ethylene and octene (EOM), rubber-like copolymer of ethylene, propylene and diene (EPDM), rubber of ethylene and propylene Copolymer (EPM), ethylene-vinyl acetate rubber-like copolymer (EVM), butadiene rubber (BR), styrene butadiene rubber (SBR), chloroprene rubber (CR), chlorinated polyethylene (CM, CPE) , Chlorosulfonated polyethylene (CSM), urethane elastomer, polycarbonate Boneto resins, vinyl acetate resins, polyacetal resins, polyester resins, polystyrene resins, polypropylene resins, polyamide resins, silicon resins, vinylidene chloride resins, acrylic resins, melamine resins, blends of such DAP resin.

  In the rubber composition for vulcanization of the present invention, a compounding agent other than the above, for example, a lubricant such as sorbitan monostearate, a filler, a reinforcing agent such as carbon black, A plasticizer such as (butoxyethoxyethyl), a processing aid, a flame retardant, a foaming aid, a conductive agent, an antistatic agent, a light stabilizer, and the like can be arbitrarily blended.

  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 heat molding, any method such as compression molding using a mold, injection molding, steam can, air bath, infrared ray, or heating using microwaves can be used.

  Next, in order to specifically explain the present invention, some examples of the present invention and comparative examples for comparing with the examples will be given.

Preparation of rubber composition for vulcanization After kneading the kneading compound A shown in Table 1 for 4 to 5 minutes with a kneader or Banbury heated to 120 ° C., the kneaded material was taken out and then mixed with a mixing roll heated to 60 ° C. And was used as A-kneaded material. A B kneading compound was added to this A kneaded material and kneaded with a mixing roll heated to 60 ° C. to obtain a rubber composition for vulcanization.

Mooney scorch test, storage stability test The rubber compositions for vulcanization of Examples 1 to 6 and Comparative Examples 1 and 2 were used in accordance with JIS K 6300-1 using Mooney Viscometer SMV-201 manufactured by Shimadzu Corporation. A scorch test was conducted. Further, after storing the rubber compositions for vulcanization of Examples 1 to 6 and Comparative Examples 1 and 2 at 35 ° C. and a relative humidity of 75% for 3 days, the same Mooney scorch test was performed to obtain a storage stability test. . The results of these tests are shown in Table 2.

The compounding agents used in Examples and Comparative Examples are shown below.
* 1 “Epichromer C” manufactured by Daiso Corporation (epichlorohydrin / ethylene oxide (50/50 mol ratio) copolymer, ML _{1 + 4} 100 ° C. 65)
* 2 “Seast SO” manufactured by Tokai Carbon Co., Ltd.
* 3 “Splendor R-300” manufactured by Kao Corporation
* 4 “ADEKA SIZER RS-107” manufactured by ADEKA Corporation
* 5 “NOCRACK NBC” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 6 “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd.
* 7 “Kyowa Mug # 150” manufactured by Kyowa Chemical Industry Co., Ltd.
* 8 “P-152” manufactured by Daiso Corporation
* 9 "Noxeller TS" manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 10 “ZISNET-F” manufactured by Sankyo Chemical Co., Ltd.
* 11 Made by Nippon Oil & Fats Co., Ltd. * 12 "Retarder CTP" made by Ouchi Shinsei Chemical

In the rubber compositions for vulcanization of Examples 1 to 6, the viscosity (Vm) after storage for 3 days under wet heat does not significantly increase with respect to the initial viscosity (Vm) (that is, ΔVm is small), and the storage stability The property was excellent.
On the other hand, in the rubber compositions for vulcanization of Comparative Examples 1 and 2, the viscosity (Vm) after wet heat storage for 3 days greatly increased with respect to the initial viscosity (Vm). Compared with the rubber composition for use, the storage stability was remarkably inferior. In addition, Vm of the comparative example 2 after a 3-day wet heat storage exceeded 200 (range over), (DELTA) Vm was not measurable, and t5 and (DELTA) t5 were not able to be measured.

Vulcanized rubber materials obtained by vulcanizing the rubber composition for vulcanization of the present invention are rubber products such as various fuel-based laminated hoses for automobiles, air-based laminated hoses, tubes, belts, diaphragms, seals, etc. It is useful as a rubber product for industrial equipment and devices.

Claims (12)

  A rubber composition for vulcanization comprising (a) epichlorohydrin rubber, (b) triazine vulcanizing agent, (c) acid acceptor, and (d) acid anhydride.   The rubber composition for vulcanization according to claim 1, wherein (d) the acid anhydride is maleic anhydride.   The rubber composition for vulcanization according to claim 1 or 2, comprising 0.5 to 10 parts by weight of (d) acid anhydride with respect to 100 parts by weight of (a) epichlorohydrin rubber.   (C) Acid acceptor is hydrotalcite, The rubber composition for vulcanization | cure in any one of Claims 1-3.   The rubber composition for vulcanization | cure in any one of Claims 1-4 which contains 0.5-5 weight part of (b) triazine-type vulcanizing agents with respect to 100 weight part of (a) epichlorohydrin-type rubber | gum.   The rubber composition for vulcanization according to any one of claims 1 to 5, comprising 1 to 10 parts by weight of (c) an acid acceptor with respect to 100 parts by weight of (a) epichlorohydrin rubber.   The rubber composition for vulcanization according to any one of claims 1 to 6, further comprising (e) a vulcanization retarder.   The rubber composition for vulcanization according to claim 7, wherein (e) the vulcanization retarder is N-cyclohexylthiophthalimide.   The rubber composition for vulcanization according to any one of claims 1 to 8, further comprising (f) a vulcanization accelerator.   The rubber composition for vulcanization according to claim 9, wherein (f) the vulcanization accelerator is 1,8-diazabicyclo (5,4,0) undecene-7 salt.   A vulcanized rubber material obtained by vulcanizing the vulcanized rubber composition according to claim 1. An automotive hose made of the vulcanized rubber material according to claim 11.