JP5644485B2 - Rubber laminate - Google Patents

Description

  The present invention relates to a rubber laminate having excellent adhesive strength, which is obtained by crosslinking and bonding hydrogenated nitrile rubber and acrylic rubber.

  Conventionally, hydrogenated nitrile rubber (hereinafter referred to as “highly saturated nitrile rubber”) is known as a rubber having heat resistance, oil resistance, and ozone resistance. Highly saturated nitrile rubber cross-linked products are used as materials for various automotive rubber products such as timing belts, hoses, gaskets, packings, and oil seals.

  When a highly saturated nitrile rubber is used for hoses, etc., an organic peroxide is used as a crosslinking agent for the highly saturated nitrile rubber, and it is crosslinked with an acrylic rubber and used as a rubber laminate (Patent Document 1). ).

  However, as in the case of these conventional technologies, when a high-saturation nitrile rubber is used as a cross-linking agent, an organic peroxide or sulfur is used, and a rubber laminate is obtained by vulcanizing and bonding (crosslinking adhesion) with acrylic rubber. There was a problem that the adhesive strength after vulcanization (after crosslinking) of saturated nitrile rubber and acrylic rubber was not sufficient.

JP 2003-286351 A

  An object of the present invention is to provide a rubber laminate having a high adhesive strength by crosslinking and bonding a highly saturated nitrile rubber and an acrylic rubber.

  As a result of diligent research to solve the above problems, the present inventors have achieved the above object by performing cross-linking adhesion of a specific highly saturated nitrile rubber and a specific acrylic rubber using a specific cross-linking agent. As a result, the present invention has been completed.

Thus, according to the present invention,
(1) a crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) comprising a carboxyl group-containing highly saturated nitrile rubber (A1) and a polyamine crosslinking agent (A2);
A crosslinkable carboxyl group-containing acrylic rubber composition (B3) containing a carboxyl group-containing acrylic rubber (B1) and a polyamine crosslinking agent (B2), or an epoxy group-containing acrylic rubber (C1) and an ammonium salt of carboxylic acid. A rubber laminate obtained by crosslinking and bonding a crosslinkable epoxy group-containing acrylic rubber composition (C3) containing a crosslinking agent (C2),
(2) The above (1), wherein the carboxyl group-containing highly saturated nitrile rubber (A1) contains 0.1 to 20% by weight of an α, β-ethylenically unsaturated dicarboxylic acid monoester monomer unit. The rubber laminate according to
(3) The rubber laminate according to (1) or (2 ) above, wherein the polyamine crosslinking agent (A2) is an aromatic polyvalent amine crosslinking agent ,
(4) The above characterized in that the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) and / or the crosslinkable carboxyl group-containing acrylic rubber composition (B3) further contains a basic crosslinking accelerator ( 1) to the rubber laminate according to any one of (3) ,
(5) The rubber laminate according to any one of (1) to (4) above, which is a hose,
(6) When the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) and the crosslinkable carboxyl group-containing acrylic rubber composition (B3) or the crosslinkable epoxy group-containing acrylic rubber composition (C3) are crosslinked and bonded. The method for producing a rubber laminate according to any one of the above (1) to (5) , characterized in that a cross-linking including steam cross-linking is performed.
Is provided.

  According to the present invention, a highly laminated nitrile rubber and an acrylic rubber are crosslinked and bonded to provide a rubber laminate having high adhesive strength.

The rubber laminate of the present invention comprises a crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) comprising a carboxyl group-containing highly saturated nitrile rubber (A1) and a polyamine crosslinking agent (A2),
A crosslinkable carboxyl group-containing acrylic rubber composition (B3) comprising a carboxyl group-containing acrylic rubber (B1) and a crosslinking agent (B2), or an epoxy group-containing acrylic rubber (C1) and a crosslinking agent (C2). And a crosslinkable epoxy group-containing acrylic rubber composition (C3).

[Crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3)]
The crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) used in the present invention comprises a carboxyl group-containing highly saturated nitrile rubber (A1) and a polyamine crosslinking agent (A2).

Carboxyl group-containing highly saturated nitrile rubber (A1)
The carboxyl group-containing highly saturated nitrile rubber (A1) is an α, β-ethylenically unsaturated nitrile monomer, a carboxyl group-containing monomer, and a monomer copolymerizable with each of the monomers added as necessary. It is a rubber having an iodine value of 120 or less, obtained through a step of copolymerizing a monomer.

  The α, β-ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an α, β-ethylenically unsaturated compound having a nitrile group. For example, acrylonitrile; α-chloroacrylonitrile, α-bromoacrylonitrile, etc. [Alpha] -halogenoacrylonitrile; [alpha] -alkylacrylonitrile such as methacrylonitrile; and the like. Among these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable. The α, β-ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.

  The content of the α, β-ethylenically unsaturated nitrile monomer unit is preferably 10 to 60% by weight, more preferably based on all monomer units constituting the carboxyl group-containing highly saturated nitrile rubber (A1). Is 15 to 55% by weight, more preferably 20 to 50% by weight. If the content of the α, β-ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the resulting cross-linked product may be lowered, and conversely if too much, cold resistance may be lowered. .

  The carboxyl group-containing monomer is a monomer that can be copolymerized with an α, β-ethylenically unsaturated nitrile monomer and has at least one unsubstituted (free) carboxyl group that is not esterified. There is no particular limitation as long as it is a monomer. Examples of such carboxyl group-containing monomers include α, β-ethylenically unsaturated monocarboxylic acid monomers, α, β-ethylenically unsaturated polyvalent carboxylic acid monomers, and α, β- And ethylenically unsaturated dicarboxylic acid monoester monomers. The carboxyl group-containing monomer also includes monomers in which the carboxyl group of these monomers forms a carboxylate. Furthermore, an anhydride of α, β-ethylenically unsaturated polyvalent carboxylic acid can also be used as a carboxyl group-containing monomer because it forms a carboxyl group by cleaving the acid anhydride group after copolymerization.

  Examples of the α, β-ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, and cinnamic acid.

  Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid monomer include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, and citraconic acid. Moreover, maleic anhydride etc. are mentioned as an anhydride of (alpha), (beta) -ethylenically unsaturated polyhydric carboxylic acid.

  As the α, β-ethylenically unsaturated dicarboxylic acid monoester monomer, maleic acid monoalkyl esters such as monomethyl maleate, monoethyl maleate, monopropyl maleate, mono n-butyl maleate; monocyclopentyl maleate, Maleic acid monocycloalkyl esters such as monocyclohexyl maleate and monocycloheptyl maleate; Monoalkyl cycloalkyl esters of maleic acid such as monomethylcyclopentyl maleate and monoethylcyclohexyl maleate; Monomethyl fumarate, monoethyl fumarate and monofumarate Monoalkyl esters of fumaric acid such as propyl and mono-n-butyl fumarate; mono-fumaric acid such as monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate Cycloalkyl esters; monoalkyl cycloalkyl esters of fumaric acid such as monomethylcyclopentyl fumarate and monoethylcyclohexyl fumarate; citraconic acid monoalkyl esters such as monomethyl citraconic acid and mono-n-butyl citraconic acid; Monocycloalkyl esters; citraconic acid monoalkyl cycloalkyl esters such as citraconic acid monomethylcyclopentyl, citraconic acid monoethylcyclohexyl; itaconic acid monoalkyl esters such as itaconic acid monomethyl and itaconic acid mono n-butyl; itaconic acid monocyclopentyl, itaconic acid Itaconic acid monocycloalkyl esters such as monocyclohexyl; Itaconic acid such as monomethylcyclopentyl itaconic acid Acid monoalkyl cycloalkyl esters, and the like.

  Among these, α, β-ethylenically unsaturated dicarboxylic acid monoester is preferable from the viewpoint that the effect of the present invention becomes more remarkable, and mono n-butyl fumarate, mono n-butyl itaconate, mono acid maleate n-Butyl is more preferred, and mono-n-butyl maleate is particularly preferred.

  The content of the carboxyl group-containing monomer unit is preferably 0.1 to 20% by weight, more preferably 0.2%, based on all monomer units constituting the carboxyl group-containing highly saturated nitrile rubber (A1). -15% by weight, more preferably 0.5-10% by weight. If the content of the carboxyl group-containing monomer unit is too small, the adhesive strength of the resulting rubber laminate may be reduced. Conversely, if the content is too large, the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) ) Scorch stability may deteriorate.

In the carboxyl group-containing highly saturated nitrile rubber (A1) used in the present invention, the α, β-ethylenically unsaturated nitrile monomer and the carboxyl group-containing monomer together with the resulting crosslinked product exhibit rubber elasticity. More preferably, it is a copolymer of conjugated diene monomers.
The proportion of each monomer in the case of copolymerization is preferably 10 to 60% by weight of α, β-ethylenically unsaturated nitrile monomer when the total amount of monomers used for copolymerization is 100 parts by weight. Parts, more preferably 15 to 55 parts by weight, particularly preferably 20 to 50 parts by weight, the carboxyl group-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, Particularly preferred is 0.5 to 10 parts by weight, and the conjugated diene monomer is preferably 20 to 89.9 parts by weight, more preferably 30 to 84.8 parts by weight, and particularly preferably 40 to 79.5 parts by weight. It is.

  The conjugated diene monomer is not particularly limited as long as it is copolymerizable with an α, β-ethylenically unsaturated nitrile monomer and a carboxyl group-containing monomer, and 1,3-butadiene, C4-C6 conjugated diene monomers such as isoprene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3- Butadiene is particularly preferred. The conjugated diene monomer may be used alone or in combination of two or more.

  The content of the conjugated diene monomer unit is preferably from 20 to 89.9% by weight, more preferably from 30 to 84.%, based on all monomer units constituting the carboxyl group-containing highly saturated nitrile rubber (A1). It is 8% by weight, more preferably 40 to 79.5% by weight. If the content of the conjugated diene monomer unit is too small, the rubber elasticity of the resulting crosslinked product may be lowered. Conversely, if the content is too large, heat resistance and chemical stability may be impaired. In addition, content of the said conjugated diene monomer unit is content also including the hydrogenated part, when the below-mentioned copolymer is hydrogenated.

  The carboxyl group-containing highly saturated nitrile rubber (A1) used in the present invention is copolymerized with an α, β-ethylenically unsaturated nitrile monomer, a carboxyl group-containing monomer, and a conjugated diene monomer. It may be a copolymer of other possible monomers. Examples of such other monomers include ethylene, α-olefin monomer, aromatic vinyl monomer, α, β-ethylenically unsaturated carboxylic acid ester monomer (the above-mentioned “carboxyl group-containing single monomer”). Excluding those corresponding to “body”), fluorine-containing vinyl monomers, copolymerizable anti-aging agents and the like.

  The α-olefin monomer preferably has 3 to 12 carbon atoms, and examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

  Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyl pyridine and the like.

  Examples of the α, β-ethylenically unsaturated carboxylic acid ester monomer include alkyl groups having 1 to 18 carbon atoms such as methyl acrylate, ethyl acrylate, n-dodecyl acrylate, methyl methacrylate, and ethyl methacrylate. (Meth) acrylic acid ester (abbreviation of “methacrylic acid ester and acrylic acid ester”, the same applies hereinafter); having a C2-C12 alkoxyalkyl group such as methoxymethyl acrylate and methoxyethyl methacrylate (meth) Acrylic acid ester; (meth) acrylic acid ester having a C2-C12 cyanoalkyl group such as α-cyanoethyl acrylate, α-cyanoethyl methacrylate, α-cyanobutyl methacrylate; 2-hydroxyethyl acrylate, acrylic acid 3-hydroxypropyl, methacrylic acid 2 -(Meth) acrylic acid ester having a hydroxyalkyl group having 1 to 12 carbon atoms such as hydroxyethyl; having a fluoroalkyl group having 1 to 12 carbon atoms such as trifluoroethyl acrylate and tetrafluoropropyl methacrylate (meth) Acrylic acid ester; α, β-ethylenically unsaturated dicarboxylic acid dialkyl ester such as dimethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl itaconate; α-containing dialkylamino groups such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate β-ethylenically unsaturated carboxylic acid ester; and the like.

  Examples of the fluorine-containing vinyl monomer include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.

  Examples of copolymerizable anti-aging agents include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4- Anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.

  These other copolymerizable monomers may be used alone or in combination of two or more. The content of other monomer units is preferably 50% by weight or less, more preferably 30% by weight or less, based on all monomer units constituting the carboxyl group-containing highly saturated nitrile rubber (A1). Preferably it is 10 weight% or less.

  The iodine value of the carboxyl group-containing highly saturated nitrile rubber (A1) is 120 or less, preferably 80 or less, more preferably 25 or less, and particularly preferably 15 or less. If the iodine value of the carboxyl group-containing nitrile rubber (A1) is too high, the heat resistance and ozone resistance of the resulting rubber laminate may be lowered.

The polymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the carboxyl group-containing highly saturated nitrile rubber (A1) is preferably 15 to 200, more preferably 20 to 150, and particularly preferably 30 to 120. If the polymer Mooney viscosity of the carboxyl group-containing highly saturated nitrile rubber (A1) is too low, the mechanical strength of the resulting rubber laminate may be reduced, and conversely if too high, the crosslinkable carboxyl group-containing highly saturated nitrile is low. The processability of the rubber composition may be reduced.

The carboxyl group content in the carboxyl group-containing highly saturated nitrile rubber (A1), that is, the number of moles of carboxyl groups per 100 g of the carboxyl group-containing highly saturated nitrile rubber (A1) is preferably 5 × 10 ^{−4 to} 5. × 10 ⁻¹ ephr, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻¹ ephr, and even more preferably 5 × 10 ^{−3 to} 6 × 10 ⁻² ephr. When the carboxyl group content of the carboxyl group-containing highly saturated nitrile rubber (A1) is in the above range, the effect of the present invention becomes even more remarkable.

  The production method of the carboxyl group-containing highly saturated nitrile rubber (A1) used in the present invention is not particularly limited. For example, α, β-ethylenically unsaturated nitrile monomer, carboxyl group-containing monomer, conjugated diene monomer And a method of copolymerizing the monomer and other monomers that can be copolymerized therewith if necessary. As the polymerization method, any of the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used, but the emulsion polymerization method is preferable because the polymerization reaction can be easily controlled. In addition, when the iodine value of the copolymer obtained by copolymerization is higher than 120, it is good to perform hydrogenation (hydrogenation reaction) of a copolymer. In this case, the hydrogenation method is not particularly limited, and a known method may be employed.

Polyamine crosslinking agent (A2)
The polyamine crosslinking agent (A2) used in the present invention is not particularly limited as long as it is a compound having two or more amino groups or a compound having two or more amino groups at the time of crosslinking. A compound in which a plurality of hydrogen atoms of an aromatic hydrocarbon or aromatic hydrocarbon are substituted with an amino group or a hydrazide structure (a structure represented by —CONHNH ₂ , CO represents a carbonyl group), and the form of the compound at the time of crosslinking Is preferred.
Examples of the polyamine crosslinking agent (A2) include an aromatic polyvalent amine crosslinking agent, an aliphatic polyvalent amine crosslinking agent, and a compound having two or more hydrazide structures. However, foaming during steam crosslinking is difficult to occur. Therefore, an aromatic polyvalent amine crosslinking agent is preferable. The aromatic polyvalent amine cross-linking agent is a polyvalent amine cross-linking agent having one or more aromatic rings in the molecule, and a plurality of hydrogen atoms of the aromatic hydrocarbon have an amino group or a hydrazide structure (—CONHNH _And a compound substituted with a structure represented by ₂ , CO represents a carbonyl group.

  Examples of the aromatic polyvalent amine crosslinking agent include 4,4′-methylenedianiline, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4 ′-(m-phenylenediene. Isopropylidene) dianiline, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzanilide, 4,4 Aromatic polyamines such as' -bis (4-aminophenoxy) biphenyl, 1,3,5-benzenetriamine, and 4,4'-methylenebis (o-chloroaniline) are exemplified. Among these, since the effect of the present invention becomes more remarkable, the number of amino groups in one molecule is preferably 2 to 5, more preferably 2 to 3, and more preferably 2. Some are particularly preferred. Further, those having 1 to 8 aromatic rings in one molecule are preferable, those having 2 to 7 are more preferable, and those having 3 to 6 are particularly preferable. Those having a phenoxy group in one molecule are preferable, those having 1 to 4 phenoxy groups in one molecule are more preferable, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable. preferable. In addition, an aromatic polyvalent amine crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more type.

Specific examples of the aliphatic polyvalent amine crosslinking agent include hexamethylenediamine, hexamethylenediamine carbamate, tetramethylenepentamine, hexamethylenediamine cinnamaldehyde adduct, hexamethylenediamine dibenzoate salt and the like.
Specific examples of the compound having two or more hydrazide structures include isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and the like. .

  The blending amount of the polyamine crosslinking agent (A2) in the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) is preferably 0.1 with respect to 100 parts by weight of the carboxyl group-containing highly saturated nitrile rubber (A1). -20 parts by weight, more preferably 0.2-15 parts by weight, still more preferably 0.5-10 parts by weight. When the compounding amount of the polyamine crosslinking agent is within the above range, the effect of the present invention becomes even more remarkable.

  The crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) preferably further contains a basic crosslinking accelerator. By further containing a basic crosslinking accelerator, the effect of the present invention becomes more remarkable.

  Specific examples of the basic crosslinking accelerator include guanidine-based basic crosslinking accelerators such as tetramethylguanidine, tetraethylguanidine, diphenylguanidine, 1,3-di-ortho-tolylguanidine, orthotolylbiguanide; 1,8-diazabicyclo [5,4,0] undecene-7,1,5-diazabicyclo [4,3,0] nonene-5, 1-methylimidazole, 1-ethylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1,2 -Dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methoxyethylimidazole, 1-phenyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-methyl-2-phenylimidazole, 1-methyl- 2-Benzylimidazole, 1,4-dimethylimidazole 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1-methyl-2-methoxyimidazole, 1-methyl-2-ethoxyimidazole, 1-methyl- 4-methoxyimidazole, 1-methyl-2-methoxyimidazole, 1-ethoxymethyl-2-methylimidazole, 1-methyl-4-nitroimidazole, 1,2-dimethyl-5-nitroimidazole, 1,2-dimethyl- 5-aminoimidazole, 1-methyl-4- (2-aminoethyl) imidazole, 1-methylbenzimidazole, 1-methyl-2-benzylbenzimidazole, 1-methyl-5-nitrobenzimidazole, 1-methylimidazoline, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazole 1,4-dimethyl-2-ethylimidazoline, 1-methyl-phenylimidazoline, 1-methyl-2-benzylimidazoline, 1-methyl-2-ethoxyimidazoline, 1-methyl-2-heptylimidazoline, 1-methyl A basic crosslinking accelerator having a cyclic amidine structure such as 2-undecylimidazoline, 1-methyl-2-heptadecylimidazoline, 1-methyl-2-ethoxymethylimidazoline, 1-ethoxymethyl-2-methylimidazoline; n -Aldehyde amine basic crosslinking accelerators such as butyraldehyde aniline and acetaldehyde ammonia; Of these, guanidine-based basic crosslinking accelerators and basic crosslinking accelerators having a cyclic amidine structure are preferred, and 1,3-di-ortho-tolylguanidine, 1,8-diazabicyclo [5,4,0] undecene. -7 and 1,5-diazabicyclo [4,3,0] nonene-5 are more preferred, and 1,3-di-ortho-tolylguanidine is particularly preferred.

  The amount of the basic crosslinking accelerator in the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) is preferably 0.1 to 100 parts by weight of the carboxyl group-containing highly saturated nitrile rubber (A1). 20 parts by weight, more preferably 0.2 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight. If the amount of the basic crosslinking accelerator is too small, the crosslinking rate of the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition may be too slow and the crosslinking density may decrease. On the other hand, if the blending amount is too large, the crosslinking rate of the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition may be too high to cause scorching, or the storage stability may be impaired.

In addition to the above, the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) may contain other compounding agents commonly used in the rubber field, such as reinforcing fillers such as carbon black and silica, calcium carbonate and clay. Non-reinforcing fillers such as, crosslinking accelerators other than basic crosslinking accelerators, crosslinking aids, crosslinking retarders, antioxidants, antioxidants, light stabilizers, primary amines and other scorch inhibitors, silane couplings An agent, a plasticizer, a processing aid, a lubricant, an adhesive, a lubricant, a flame retardant, an antifungal agent, an acid acceptor, an antistatic agent, a pigment, and the like can be blended. The compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose can be blended.
The amount of the reinforcing filler such as carbon black or silica is preferably 1 to 200 parts by weight, more preferably 10 parts per 100 parts by weight of the carboxyl group-containing highly saturated nitrile rubber (A1). ~ 100 parts by weight.

  The crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) may be blended with a polymer other than the carboxyl group-containing highly saturated nitrile rubber (A1) as long as the effects of the present invention are not impaired. Good. Other polymers include ethylene-acrylic acid copolymer rubber, fluorine rubber, styrene-butadiene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, natural rubber and Examples thereof include polyisoprene rubber. When blending other polymer, the blending amount in the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) is preferably 30 with respect to 100 parts by weight of the carboxyl group-containing highly saturated nitrile rubber (A1). The amount is not more than parts by weight, more preferably not more than 20 parts by weight, still more preferably not more than 10 parts by weight.

Preparation of crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) The method for preparing crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) is not particularly limited, but carboxyl group-containing highly saturated nitrile rubber (A1). The components other than the heat-labile polyamine crosslinking agent (A2) and the crosslinking aid are preferably 10 to 200 ° C., more preferably 20 to 170 ° C. at Banbury mixer, Brabender mixer, Kneading with a mixer such as a mixer or kneader, transferring to a roll or the like, adding a heat-labile polyamine cross-linking agent (A2), a cross-linking aid, etc., preferably secondary kneading at 10 to 80 ° C. Can be prepared.

The crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) thus obtained has a compound Mooney viscosity [ML _{1 + 4} , 100 ° C.] of preferably 10 to 200, more preferably 15 to 180, still more preferably. It is 20-150 and is excellent in workability.

[Crosslinkable carboxyl group-containing acrylic rubber composition (B3)]
The crosslinkable carboxyl group-containing acrylic rubber composition (B3) used in the present invention contains a carboxyl group-containing acrylic rubber (B1) and a crosslinking agent (B2).

Carboxyl group-containing acrylic rubber (B1)
The carboxyl group-containing acrylic rubber (B1) is a rubber having a (meth) acrylic acid ester monomer unit as a main constituent unit and a carboxyl group-containing monomer unit, preferably a carboxyl group-containing monomer, It is a rubber obtained through a step of copolymerizing a (meth) acrylic acid ester monomer and, if necessary, other monomers copolymerizable with these monomers.

  As the (meth) acrylic acid ester monomer which is the main raw material of the carboxyl group-containing acrylic rubber (B1), a (meth) acrylic acid alkyl ester monomer and a (meth) acrylic acid alkoxyalkyl ester monomer are preferable.

  The (meth) acrylic acid alkyl ester monomer is preferably an ester of an alkanol having 1 to 8 carbon atoms and (meth) acrylic acid, specifically, methyl (meth) acrylate or ethyl (meth) acrylate. , N-propyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate And cyclohexyl (meth) acrylate. Among these, ethyl acrylate and n-butyl acrylate are preferable.

  The (meth) acrylic acid alkoxyalkyl ester monomer is preferably an ester of an alkoxyalkanol having 2 to 8 carbon atoms and (meth) acrylic acid, specifically, methoxymethyl (meth) acrylate, (meth) Ethoxymethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, (meth) acrylic acid Examples include 3-methoxypropyl and 4-methoxybutyl (meth) acrylate. Among these, 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are more preferable.

  The content of the (meth) acrylic acid ester monomer unit is preferably 99.9 to 60% by weight, more preferably 99.99%, based on all monomer units constituting the carboxyl group-containing acrylic rubber (B1). It is 8 to 75% by weight, more preferably 99.5 to 90% by weight. When the content of the (meth) acrylic acid ester monomer unit is in the above range, the effect of the present invention becomes even more remarkable.

  The carboxyl group-containing monomer is not particularly limited as long as it is a carboxyl group-containing monomer copolymerizable with the (meth) acrylic acid ester monomer, but an α, β-ethylenic group having 3 to 12 carbon atoms. An unsaturated monocarboxylic acid, an α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms, and an α, β-ethylenically unsaturated dicarboxylic acid having 4 to 11 carbon atoms and an alkanol having 1 to 8 carbon atoms The monoester is preferably exemplified.

Examples of the α, β-ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, and cinnamic acid.
Examples of the α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, citraconic acid and chloromaleic acid.
As monoesters of α, β-unsaturated dicarboxylic acids having 4 to 11 carbon atoms and alkanols having 1 to 8 carbon atoms, monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, monomethyl maleate, maleic acid Butenedionic acid mono-chain alkyl esters such as monoethyl and mono-n-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate and monocyclohexenyl maleate, etc. Butenedioic acid monoesters having the following alicyclic structures; itaconic acid monoesters such as monomethyl itaconate, monoethyl itaconate and monobutyl itaconate; mono-2-hydroxyethyl fumarate;

  Of these, butenedionic acid mono-chain alkyl ester and butenedionic acid monoester having an alicyclic structure are preferable, and mono-n-butyl fumarate, mono-n-butyl maleate, monocyclohexyl fumarate and monocyclohexyl maleate are more preferable. These can be used individually by 1 type or in combination of 2 or more types.

  The content of the carboxyl group-containing monomer unit is preferably 0.1 to 40% by weight, more preferably 0.2 to 25%, based on all monomer units constituting the carboxyl group-containing acrylic rubber (B1). % By weight, more preferably 0.5 to 10% by weight. If the content of the carboxyl group-containing monomer unit is too small, the adhesive strength of the resulting rubber laminate may be reduced. Conversely, if the content is too large, the crosslinkable carboxyl group-containing acrylic rubber composition (B3) Scorch stability may deteriorate.

  The carboxyl group-containing acrylic rubber (B1) can be copolymerized with these in addition to the (meth) acrylic acid ester monomer and the carboxyl group-containing monomer as long as the effects of the present invention are not impaired. These monomers may be copolymerized. Examples of such other monomers include aromatic vinyl monomers and α, β-ethylenically unsaturated nitrile monomers. The content of other monomer units in the carboxyl group-containing acrylic rubber (B1) is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, divinylbenzene, and the like.
Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.

The polymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the carboxyl group-containing acrylic rubber (B1) is preferably 15 to 200, more preferably 20 to 150, and particularly preferably 30 to 120. If the polymer Mooney viscosity of the carboxyl group-containing acrylic rubber (B1) is too low, the mechanical strength of the resulting rubber laminate may be reduced. Conversely, if it is too high, the crosslinkable carboxyl group-containing acrylic rubber composition Workability may be reduced.

  The method for producing the carboxyl group-containing acrylic rubber (B1) is not particularly limited. For example, it can be copolymerized with (meth) acrylic acid ester monomer, carboxyl group-containing monomer, and those used as necessary. A method of copolymerizing other monomers is preferable. As the polymerization method, any of the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used. However, since the polymerization reaction is easily controlled, the emulsion weight under normal pressure can be controlled. Legal is preferred.

Cross-linking agent (B2)
Examples of the crosslinking agent (B2) used in the present invention include polyamine crosslinking agents, polyvalent epoxy crosslinking agents, polyvalent isocyanate crosslinking agents, aziridine crosslinking agents, basic metal oxides, and organometallic halides. From the viewpoint of improving the adhesive strength of the rubber laminate, a polyamine crosslinking agent is preferred.

  As the polyamine crosslinking agent, those similar to the above-mentioned polyamine crosslinking agent (A2) are used, but an aromatic polyvalent amine crosslinking agent is preferred because the effects of the present invention become more remarkable.

  Examples of the aromatic polyvalent amine crosslinking agent include 4,4′-methylenedianiline, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4 ′-(m-phenylenediene. Isopropylidene) dianiline, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzanilide, 4,4 Aromatic polyamines such as' -bis (4-aminophenoxy) biphenyl, 1,3,5-benzenetriamine, and 4,4'-methylenebis (o-chloroaniline) are exemplified. Among these, since the effect of the present invention becomes more remarkable, the number of amino groups in one molecule is preferably 2 to 5, more preferably 2 to 3, and more preferably 2. Some are particularly preferred. Further, those having 1 to 8 aromatic rings in one molecule are preferable, those having 2 to 7 are more preferable, and those having 3 to 6 are particularly preferable. Those having a phenoxy group in one molecule are preferable, those having 1 to 4 phenoxy groups in one molecule are more preferable, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable. preferable. In addition, an aromatic polyvalent amine crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more type.

  Polyhydric epoxy crosslinking agents include compounds having two or more epoxy groups in the molecule, such as phenol novolac type epoxy compounds, bisphenol A type epoxy compounds, alicyclic epoxy compounds, glycidyl ester type epoxy compounds, and isocyanurate type epoxy compounds. Is mentioned.

  Examples of the polyvalent isocyanate crosslinking agent include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and 4,4′-diphenylmethane diisocyanate. (MDI).

  Examples of aziridine crosslinking agents include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphinoxide, hexa [1- (2-methyl) Aziridinyl] triphosphatriazine and the like.

  Examples of the basic metal oxide include zinc oxide, lead oxide, calcium oxide, and magnesium oxide.

  Examples of the organic metal halide include dicyclopentadienyl metal dihalide, and examples of the metal include titanium, zirconium, hafnium and the like.

  The blending amount of the crosslinking agent (B2) in the crosslinkable carboxyl group-containing acrylic rubber composition (B3) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acrylic rubber (B1). More preferably, it is 0.2-15 weight part, More preferably, it is 0.5-10 weight part. When the blending amount of the crosslinking agent (B2) is in the above range, the effect of the present invention becomes even more remarkable.

  Moreover, it is preferable that the crosslinkable carboxyl group-containing acrylic rubber composition (B3) further contains a basic crosslinking accelerator. By further containing a basic crosslinking accelerator, the effect of the present invention becomes more remarkable. In addition, as a specific example of a basic crosslinking accelerator, the same thing as the case of the above-mentioned crosslinkable carboxyl group containing highly saturated nitrile rubber composition (A3) is mentioned.

  The amount of the basic crosslinking accelerator in the crosslinkable carboxyl group-containing acrylic rubber composition (B3) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acrylic rubber (B1). Yes, more preferably 0.2 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight. If the blending amount of the basic crosslinking accelerator is too small, the crosslinking rate of the crosslinkable carboxyl group-containing acrylic rubber composition may be too slow and the crosslinking density may decrease. On the other hand, if the blending amount is too large, the crosslinking rate of the crosslinkable carboxyl group-containing acrylic rubber composition may be too high to cause scorching, or the storage stability may be impaired.

In addition to the above, the crosslinkable carboxyl group-containing acrylic rubber composition (B3) may contain other compounding agents commonly used in the rubber field, such as reinforcing fillers such as carbon black and silica, calcium carbonate and clay, etc. Non-reinforcing fillers, crosslinking accelerators other than basic crosslinking accelerators, crosslinking aids, crosslinking retarders, anti-aging agents, antioxidants, light stabilizers, scorch inhibitors such as primary amines, silane coupling agents, Plasticizers, processing aids, lubricants, adhesives, lubricants, flame retardants, antifungal agents, acid acceptors, antistatic agents, pigments, and the like can be blended. The compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose can be blended.
In addition, the compounding amount in the case of compounding a reinforcing filler such as carbon black or silica is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts per 100 parts by weight of the carboxyl group-containing acrylic rubber (B1). Parts by weight.

  You may mix | blend other polymers other than the carboxyl group-containing acrylic rubber (B1) mentioned above with the crosslinkable carboxyl group-containing acrylic rubber composition (B3) as long as the effect of the present invention is not inhibited. Other polymers include ethylene-acrylic acid copolymer rubber, fluorine rubber, styrene-butadiene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, natural rubber and Examples thereof include polyisoprene rubber. When the other polymer is blended, the blending amount in the crosslinkable carboxyl group-containing acrylic rubber composition (B3) is preferably 30 parts by weight or less with respect to 100 parts by weight of the carboxyl group-containing acrylic rubber (B1). More preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.

Preparation of the crosslinkable carboxyl group-containing acrylic rubber composition (B3) The method for preparing the crosslinkable carboxyl group-containing acrylic rubber composition (B3) is not particularly limited, but the carboxyl group-containing acrylic rubber (B1) is unstable to heat. The components other than the crosslinking agent (B2) and the crosslinking aid are preferably mixed at 10 to 200 ° C., more preferably 20 to 170 ° C., such as Banbury mixer, Brabender mixer, intermixer, kneader Kneading, and transferring to a roll or the like, adding a heat-labile crosslinking agent (B2), a crosslinking aid, and the like, and preferably performing secondary kneading under conditions of 10 to 80 ° C.

The crosslinkable carboxyl group-containing acrylic rubber composition (B3) thus obtained has a compound Mooney viscosity [ML _{1 + 4} , 100 ° C.] of preferably 10 to 200, more preferably 15 to 180, and still more preferably 20 to 150, which is excellent in workability.

[Crosslinkable epoxy group-containing acrylic rubber composition (C3)]
The crosslinkable epoxy group-containing acrylic rubber composition (C3) used in the present invention comprises an epoxy group-containing acrylic rubber (C1) and a crosslinking agent (C2).

Epoxy group-containing acrylic rubber (C1)
The epoxy group-containing acrylic rubber (C1) is a rubber having a (meth) acrylate monomer unit as a main constituent unit and an epoxy group-containing monomer unit, preferably an epoxy group-containing monomer, It is a rubber obtained through a step of copolymerizing a (meth) acrylic acid ester monomer and, if necessary, other monomers copolymerizable with these monomers.

  As the (meth) acrylic acid ester monomer which is the main raw material of the epoxy group-containing acrylic rubber (C1), an acrylic acid alkyl ester monomer and an acrylic acid alkoxyalkyl ester monomer are preferable.

  As the (meth) acrylic acid alkyl ester monomer, those similar to the case of the carboxyl group-containing acrylic rubber (B1) are preferably used, but ethyl acrylate and n-butyl acrylate are more preferable.

  As the (meth) acrylic acid alkoxyalkyl ester monomer, those similar to the above-mentioned carboxyl group-containing acrylic rubber (B1) are preferably used, but 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are preferable. Is more preferable.

  The content of the (meth) acrylic acid ester monomer unit is preferably 99.9 to 60% by weight, more preferably 99.99%, based on all monomer units constituting the epoxy group-containing acrylic rubber (C1). It is 8 to 75% by weight, more preferably 99.5 to 90% by weight. When the content of the (meth) acrylic acid ester monomer unit is in the above range, the effect of the present invention becomes even more remarkable.

  The epoxy group-containing monomer is not limited as long as it is an epoxy group-containing monomer copolymerizable with the (meth) acrylic acid ester monomer, and examples thereof include an epoxy group-containing unsaturated hydrocarbon compound and glycidyl ester. Examples thereof include a group-containing unsaturated hydrocarbon compound and a glycidyl ether group-containing unsaturated hydrocarbon compound.

  Examples of the epoxy group-containing unsaturated hydrocarbon compound include 3,4-epoxy-1-butene, 1,2-epoxy-3-pentene, 1,2-epoxy-5,9-cyclododecadiene, and the like.

  Examples of the unsaturated hydrocarbon compound containing a glycidyl ester group include glycidyl (meth) acrylate, glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl ester of 3-cyclohexenecarboxylic acid, 4-methyl-3 -Glycidyl ester of cyclohexene carboxylic acid, glycidyl-4-methyl-3-pentenoate, etc. are mentioned.

  Examples of the glycidyl ether group-containing unsaturated hydrocarbon compound include vinyl glycidyl ether, allyl glycidyl ether, o-allylphenyl glycidyl ether, and the like.

  Among these, glycidyl ether group-containing unsaturated hydrocarbon compounds are preferable, and allyl glycidyl ether is particularly preferable. In addition, the said epoxy group containing monomer can be used individually by 1 type or in combination of 2 or more types.

  The content of the epoxy group-containing monomer unit is preferably 0.1 to 40% by weight, more preferably 0.2 to 25%, based on all monomer units constituting the epoxy group-containing acrylic rubber (C1). % By weight, more preferably 0.5 to 10% by weight. If the content of the epoxy group-containing monomer unit is too small, the adhesive strength of the resulting rubber laminate may be reduced. Conversely, if the content is too large, the crosslinkable epoxy group-containing acrylic rubber composition (C3) Scorch stability may deteriorate.

  The epoxy group-containing acrylic rubber (C1) can be copolymerized with (meth) acrylic acid ester monomer and epoxy group-containing monomer as long as the effects of the present invention are not impaired. These monomers may be copolymerized. Examples of such other monomers include aromatic vinyl monomers and α, β-ethylenically unsaturated nitrile monomers. The content of other monomer units in the epoxy group-containing acrylic rubber (C1) is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, divinylbenzene, and the like.
Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.

The polymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the epoxy group-containing acrylic rubber (C1) is preferably 15 to 200, more preferably 20 to 150, and particularly preferably 30 to 120. If the polymer Mooney viscosity of the epoxy group-containing acrylic rubber (C1) is too low, the mechanical strength of the resulting rubber laminate may be reduced. Conversely, if it is too high, the crosslinkable epoxy group-containing acrylic rubber composition Workability may be reduced.

  The production method of the epoxy group-containing acrylic rubber (C1) is not particularly limited. For example, (meth) acrylic acid ester monomer, epoxy group-containing monomer, and these can be copolymerized with these if necessary. A method of copolymerizing other monomers is preferable. As the polymerization method, any of the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used. However, since the polymerization reaction is easily controlled, the emulsion weight under normal pressure can be controlled. Legal is preferred.

Cross-linking agent (C2)
Examples of the crosslinking agent (C2) used in the present invention include ammonium salts of carboxylic acids such as ammonium benzoate, ammonium phthalate, ammonium glutarate, ammonium adipate, ammonium pimelate, and ammonium suberate; tetraethylammonium bromide, tetrabutylammonium Halogen-containing quaternary ammonium salts such as chloride, cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide; aliphatic polyvalent amine compounds such as hexamethylenediamine and hexamethylenediamine carbamate, and carbonates thereof; 4,4′- Aromatic polyvalent amine compounds such as methylene dianiline; dithiocarbamic acid metal salts such as zinc dimethyldithiocarbamate; polyvalent carboxylic acids such as tetradecanedioic acid; Imidazole compounds such as 2-methylimidazole; isocyanuric acid compounds such as ammonium isocyanurate; Among these, from the viewpoint of improving the scorch stability of the crosslinkable epoxy group-containing acrylic rubber composition, an ammonium salt of a carboxylic acid is preferable, and ammonium benzoate is more preferable. In addition, as a carboxylic acid ammonium salt, a C3-C15 thing is preferable and a C5-C10 thing is more preferable.
Moreover, the said crosslinking agent (C2) can be used individually by 1 type or in combination of 2 or more types.

  In the crosslinkable epoxy group-containing acrylic rubber composition (C3), the amount of the crosslinking agent (C2) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing acrylic rubber (C1). More preferably, it is 0.2-15 weight part, More preferably, it is 0.5-10 weight part. When the blending amount of the crosslinking agent (C2) is in the above range, the effect of the present invention becomes even more remarkable.

  The crosslinkable epoxy group-containing acrylic rubber composition (C3) may further contain a basic crosslinking accelerator. Specific examples of the basic crosslinking accelerator include the same ones as in the case of the above-mentioned crosslinkable nitrile rubber composition (A3).

In addition to the above, the crosslinkable epoxy group-containing acrylic rubber composition (C3) includes a compounding agent usually used in the rubber field, such as reinforcing fillers such as carbon black and silica, calcium carbonate and clay, etc. Non-reinforcing fillers, crosslinking accelerators other than basic crosslinking accelerators, crosslinking aids, crosslinking retarders, anti-aging agents, antioxidants, light stabilizers, scorch inhibitors such as primary amines, silane coupling agents, Plasticizers, processing aids, lubricants, adhesives, lubricants, flame retardants, antifungal agents, acid acceptors, antistatic agents, pigments, and the like can be blended. The compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose can be blended.
In addition, the compounding quantity in the case of compounding reinforcing fillers such as carbon black and silica is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts per 100 parts by weight of the epoxy group-containing acrylic rubber (C1). Parts by weight.

  In the crosslinkable epoxy group-containing acrylic rubber composition (C3), other polymers than the epoxy group-containing acrylic rubber (C1) described above may be blended as long as the effects of the present invention are not inhibited. Other polymers include ethylene-acrylic acid copolymer rubber, fluorine rubber, styrene-butadiene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, natural rubber and Examples thereof include polyisoprene rubber. When blending other polymers, the blending amount in the crosslinkable epoxy group-containing acrylic rubber composition (C3) is preferably 30 parts by weight or less with respect to 100 parts by weight of the epoxy group-containing acrylic rubber (C1). More preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.

Preparation of Crosslinkable Epoxy Group-Containing Acrylic Rubber Composition (C3) The preparation method of the crosslinkable epoxy group-containing acrylic rubber composition (C3) is not particularly limited, but the epoxy group-containing acrylic rubber (C1) is unstable to heat. The components except for the crosslinking agent (C2) and the crosslinking aid are preferably 10 to 200 ° C., more preferably 20 to 170 ° C., and a mixer such as a Banbury mixer, a Brabender mixer, an intermixer, or a kneader Kneading, and transferring to a roll or the like, adding a heat-labile crosslinking agent (C2), a crosslinking aid, and the like, and preferably performing secondary kneading under conditions of 10 to 80 ° C.

The crosslinkable epoxy group-containing acrylic rubber composition (C3) thus obtained has a compound Mooney viscosity [ML _{1 + 4} , 100 ° C.] of preferably 10 to 200, more preferably 15 to 180, still more preferably 20 to 150, which is excellent in workability.

Rubber Laminate The rubber laminate of the present invention comprises a crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3), a crosslinkable carboxyl group-containing acrylic rubber composition (B3), or a crosslinkable epoxy group-containing acrylic rubber composition ( C3) is cross-linked and bonded.

The method of cross-linking adhesion is not particularly limited, but a crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) and a crosslinkable carboxyl group-containing acrylic rubber composition (B3) or a crosslinkable epoxy group-containing acrylic rubber composition ( C3) is molded into a sheet shape (thickness is preferably 0.02 to 10 mm) while remaining uncrosslinked so as to have a desired thickness depending on the purpose and effect of the rubber laminate, After lamination and contact, crosslinking may be performed.
Moreover, when manufacturing a laminated tube, a crosslinkable carboxyl group containing highly saturated nitrile rubber composition (A3), a crosslinkable carboxyl group containing acrylic rubber composition (B3), or a crosslinkable epoxy group containing acrylic rubber composition (C3) ) In a laminated tube (preferably the thickness of each layer is 0.02 to 10 mm) by a two-layer extrusion method, followed by crosslinking.
Examples of the molding machine include an extruder, an injection molding machine, a compressor, and a roll.

The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C., and the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 12 hours, particularly preferably 3 minutes to 6 hours. .
Depending on the shape and size of the cross-linked product, even if the surface is cross-linked, it may not be sufficiently cross-linked to the inside. Therefore, secondary cross-linking may be performed by heating.
As a crosslinking method, a general method used for rubber crosslinking such as press crosslinking, steam crosslinking, oven crosslinking, and the like can be appropriately selected, but crosslinking including steam crosslinking is preferably performed.

The thickness of the rubber laminate of the present invention is preferably 0.04 to 20 mm, more preferably 0.1 to 10 mm.
Moreover, the thickness of the carboxyl group-containing highly saturated nitrile rubber crosslinked product layer constituting the rubber laminate is preferably 0.02 to 10 mm, more preferably 0.5 to 5 mm. And the thickness of the carboxyl group-containing acrylic rubber crosslinked product layer and the crosslinkable epoxy group-containing acrylic rubber crosslinked product layer constituting the rubber laminate is preferably 0.02 to 10 mm, more preferably 0.5 to 5 mm.

The rubber laminate of the present invention thus obtained is excellent in adhesive strength.
For this reason, the rubber laminate of the present invention makes use of such characteristics, such as packing, diaphragm, oil seal, shaft seal, bearing seal, well head seal, pneumatic equipment seal, air conditioner cooling device and air conditioner. Fluorocarbon or fluorohydrocarbon or carbon dioxide sealing seals used in compressors for refrigerators, supercritical carbon dioxide or subcritical carbon dioxide sealing seals used as cleaning media for precision cleaning, rolling devices (rolling bearings) , Automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.), seals such as valves and valve seats, BOP (Blow Out Preventor), platters, etc .; connection of intake manifold and cylinder head INTE Cylinder manifold gasket, cylinder head gasket attached to the joint between the cylinder block and cylinder head, rocker cover gasket attached to the joint between the rocker cover and cylinder head, oil pan and cylinder block or transmission case Various types of gaskets such as oil pan gaskets attached to the parts, gaskets for fuel cell separators attached between a pair of housings sandwiching a unit cell having a positive electrode, an electrolyte plate and a negative electrode, and top cover gaskets for hard disk drives; for printing Various rolls such as rolls, iron rolls, paper rolls, industrial rolls, and office machine rolls; flat belts (film core flat belts, cord flat belts, laminated flat belts, single flat belts, etc.), V belts ( Wrapped V Belt, low edge V belt, etc.), V-ribbed belt (single V-ribbed belt, double V-ribbed belt, wrapped V-ribbed belt, back rubber V-ribbed belt, upper cog V-ribbed belt, etc.), CVT belt, timing belt, toothed belt, conveyor belt, etc. Various belts; fuel hose, turbo air hose, oil hose, radiator hose, heater hose, water hose, vacuum brake hose, control hose, air conditioner hose, brake hose, power steering hose, air hose, marine hose, riser, flow line Various hoses such as CVJ boots, propeller shaft boots, constant velocity joint boots, rack and pinion boots, etc .; cushion materials, dynamic dampers, rubber couplings Attenuating rubber parts such as dust covers, automobile interior parts, tires, covered cables, shoe soles, electromagnetic wave shields, flexible printed circuit board adhesives, fuel cell separators, etc. Although it can be used for a wide range of applications such as the electronics field, it is particularly suitably used for hose applications.

  The present invention will be specifically described below with reference to examples and comparative examples. In the following, “parts” are based on weight unless otherwise specified. The test and evaluation were as follows.

The iodine value of the nitrile rubber was measured according to JIS K6235.

To 0.2 g of nitrile rubber having a carboxyl group content of 2 mm square, 100 ml of 2-butanone was added and stirred for 16 hours. Then, 20 ml of ethanol and 10 ml of water were added, and a 0.02N aqueous ethanol solution of potassium hydroxide was used while stirring. Then, by titration using thymolphthalein as an indicator at room temperature, it was determined as the number of moles of carboxyl groups relative to 100 g of nitrile rubber (unit: ephr).

Acrylonitrile unit content According to JIS K6384, the content was determined by calculation from the nitrogen content in the nitrile rubber measured by the Kjeldahl method (unit:% by weight).

Mooney viscosity The Mooney viscosity (polymer Mooney) of nitrile rubber was measured according to JIS K6300 (unit: (ML _{1 + 4} , 100 ° C.)).

Normal physical properties (tensile strength, elongation, hardness)
The crosslinkable nitrile rubber composition or the crosslinkable acrylic rubber composition is placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and is pressed at 160 ° C. for 45 minutes while being pressed at a press pressure of 10 MPa. Then, the obtained primary cross-linked product was further heated and cross-linked at 170 ° C. for 4 hours in a gear oven to obtain a sheet-like press cross-linked product. The obtained press-crosslinked product was punched out with a No. 3 dumbbell to prepare a test piece. Next, using this test piece, tensile strength and elongation were measured according to JIS K6251, and hardness was measured using a durometer hardness tester (type A) according to JIS K6253.

The compression set crosslinkable nitrile rubber composition or the crosslinkable acrylic rubber composition was subjected to primary crosslinking by pressing at a temperature of 160 ° C. for 45 minutes using a mold, and a cylindrical type having a diameter of 29 mm and a height of 12.7 mm. A primary cross-linked product was obtained, and then the obtained primary cross-linked product was further subjected to secondary cross-linking by heating in a gear-type oven at 170 ° C. for 4 hours to obtain a press cross-linked product. Then, using the obtained press-crosslinked product, in accordance with JIS K6262, the press-crosslinked product was compressed by 25% and placed in an environment of 150 ° C. for 168 hours, and then the compression set was measured.
The smaller this value, the better the compression set resistance.

The presence or absence of foaming of a steam cross-linked product A cross- linkable nitrile rubber composition or a cross-linkable acrylic rubber composition is molded using a mold at 100 ° C. for 5 minutes under a pressure of 5 MPa, and is molded into a sheet shape having a thickness of 2 mm. The resulting molded product was used for steam crosslinking at 150 ° C. for 4 hours in a vulcanizer to obtain a sheet-like steam crosslinked product. Next, the number of foams of the steam cross-linked product was counted by visually observing the surface.

Peel test The cross-linking adhesion was evaluated by a peel test according to JIS K6256. The rubber laminates (crosslinked products) shown in the examples and comparative examples were punched into strips having a width of 25.4 mm and a length of 100 mm, and both ends thereof were gripped by an air-driven gripping tool of a tensile tester, and 50 mm / min. It peeled at the speed of. The load at this time was read with a load cell of a tensile tester, and expressed as peel strength: T _F (N / mm). Moreover, the state of the adhesion interface was visually confirmed.
The notation of “rubber break” indicates that the rubber layer is broken during peeling (part of the material remains on the other rubber), and the notation of “interfacial peel” destroys each rubber layer. It shows that it peeled along the interface without.
The larger the peel strength value and the more “rubber breakage” than “interfacial peel”, the more the rubber laminate (cross-linked product) has a stronger adhesive strength by cross-linking adhesion.

Production Example 1 (Production of carboxyl group-containing highly saturated nitrile rubber (a1))
In a metal bottle, 180 parts of ion-exchanged water, 25 parts of an aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by weight, 37 parts of acrylonitrile, 6 parts of mono-n-butyl maleate, t-dodecyl mercaptan (molecular weight regulator) 0.75 In order of parts, the internal gas was replaced with nitrogen three times, and then 57 parts of 1,3-butadiene was charged. The metal bottle was kept at 5 ° C., 0.1 part of cumene hydroperoxide (polymerization initiator) was charged, and the polymerization reaction was carried out for 16 hours while rotating the metal bottle. Thereafter, 0.1 part of a 10 wt% aqueous hydride quinone solution (polymerization terminator) was added to stop the polymerization reaction. Subsequently, the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C., and acrylonitrile-butadiene was removed. -A latex of mono n-butyl maleate copolymer rubber (solid content concentration of about 30% by weight) was obtained.
Next, a palladium catalyst (a solution in which 1 wt% palladium acetate / acetone solution and equal weight of ion exchange water are mixed) is added to the autoclave so that the palladium content becomes 1000 ppm with respect to the rubber weight contained in the latex. Then, a hydrogenation reaction was carried out at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a latex of carboxyl group-containing highly saturated nitrile rubber (a1).
The resulting latex of the carboxyl group-containing highly saturated nitrile rubber (a1) was coagulated by adding twice the volume of methanol, and then vacuum-dried at 60 ° C. for 12 hours to obtain a carboxyl group-containing highly saturated nitrile rubber (a1). ) The obtained carboxyl group-containing highly saturated nitrile rubber (a1) had an iodine value of 10, a carboxyl group content of 3.2 × 10 ⁻² ephr, and a polymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 45.
In addition, the acrylonitrile unit content was calculated | required by the Kjeldahl method, the mono n-butyl maleate unit content was calculated | required from carboxyl group content, and the carboxyl group-containing highly saturated nitrile rubber | gum which calculated | required the remainder as a 1, 3- butadiene unit ( The composition of a1) was 36% by weight of acrylonitrile units, 58.5% by weight of butadiene units (including those hydrogenated), and 5.5% by weight of mono-n-butyl maleate units.

Production Example 2 (Production of carboxyl group-containing acrylic rubber (b1))
A polymerization reactor equipped with a thermometer and a stirrer was charged with 200 parts of water, 3 parts of sodium lauryl sulfate, 49 parts of ethyl acrylate, 49 parts of n-butyl acrylate, and 2 parts of mono-n-butyl maleate. After performing oxygen and nitrogen substitution twice to sufficiently remove oxygen, 0.005 part of cumene hydroperoxide and 0.002 part of sodium formaldehydesulfoxylate were added, and emulsion polymerization was started at a temperature of 30 ° C. under normal pressure. The reaction was continued until the polymerization conversion reached 95%. The obtained emulsion polymerization solution was coagulated with a calcium chloride solution, washed with water and dried to obtain a carboxyl group-containing acrylic rubber (b1). The composition of the carboxyl group-containing acrylic rubber (b1) was 49% by weight of ethyl acrylate units, 49% by weight of n-butyl acrylate units, and 2% by weight of mono n-butyl maleate units, and the polymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) was 35.

Production Example 3 (Production of epoxy group-containing acrylic rubber (c1))
A polymerization reactor equipped with a thermometer and a stirrer was charged with 200 parts of water, 3 parts of sodium lauryl sulfate, 48 parts of ethyl acrylate, 48 parts of n-butyl acrylate and 4 parts of allyl glycidyl ether. After two substitutions to remove oxygen sufficiently, 0.005 part of cumene hydroperoxide and 0.002 part of sodium formaldehydesulfoxylate were added, and emulsion polymerization was started at a temperature of 30 ° C. under normal pressure. The reaction was continued until the rate reached 95%. The obtained emulsion polymerization solution was coagulated with a calcium chloride solution, washed with water and dried to obtain an epoxy group-containing acrylic rubber (c1). The composition of the epoxy group-containing acrylic rubber (c1) is 48% by weight of ethyl acrylate unit, 48% by weight of n-butyl acrylate unit and 4% by weight of allyl glycidyl ether unit, and polymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) Was 35.

Production Example 4 (Production of active chlorine group-containing acrylic rubber (f1))
A polymerization reactor equipped with a thermometer and a stirrer was charged with 200 parts of water, 3 parts of sodium lauryl sulfate, 49 parts of ethyl acrylate, 49 parts of n-butyl acrylate and 2 parts of vinyl chloroacetate under reduced pressure degassing and nitrogen After two substitutions to remove oxygen sufficiently, 0.005 part of cumene hydroperoxide and 0.002 part of sodium formaldehydesulfoxylate were added, and emulsion polymerization was started at a temperature of 30 ° C. under normal pressure. The reaction was continued until the rate reached 95%. The obtained emulsion polymerization solution was coagulated with a calcium chloride solution, washed with water and dried to obtain an active chlorine group-containing acrylic rubber (f1). The composition of the active chlorine group-containing acrylic rubber (f1) was 49% by weight of ethyl acrylate unit, 49% by weight of n-butyl acrylate unit and 2% by weight of vinyl chloroacetate unit, and polymer Mooney viscosity (ML _{1 + 4} , 100 ° C. ) Was 35.

Crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3)
Using a Banbury mixer, 100 parts of the carboxyl group-containing highly saturated nitrile rubber (a1) obtained in Production Example 1, 30 parts of FEF carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.), silica (trade name: Nipsil ER, manufactured by Tosoh Silica Corporation), 10 parts, trimellitic acid ester (trade name: Adeka Sizer C-8, manufactured by ADEKA, plasticizer), 5 parts, 4,4′-di- (α, α-dimethylbenzyl) 1.5 parts of diphenylamine (trade name: Naugard 445, manufactured by Crompton, anti-aging agent) and 1 part of stearic acid (crosslinking accelerator) were added and mixed at 50 ° C. for 5 minutes. The resulting mixture was then transferred to a roll at 50 ° C. and 2,2-bis [4- (4-aminophenoxy) phenyl] propane (aromatic polyvalent amine crosslinker, crosslinker (a2)) 6.77. 2 parts of 1,3-di-o-tolylguanidine (trade name: Noxeller DT, manufactured by Ouchi Shinsei Chemical Co., Ltd., basic crosslinking accelerator) are mixed and kneaded to form a crosslinkable carboxyl group A contained highly saturated nitrile rubber composition (a3) was obtained. Using the cross-linked product of the cross-linkable carboxyl group-containing highly saturated nitrile rubber composition (a3), normal properties, compression set, and presence / absence of foaming of the steam cross-linked product were evaluated. The results are shown in Table 1.

Crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (d3)
Instead of 6.77 parts of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (aromatic polyvalent amine crosslinking agent), hexamethylenediamine carbamate (trade name: Diak # 1, DuPont Dow Elastomer Co., Ltd.) Manufactured, aliphatic polyvalent amine crosslinker, crosslinker (d2)), except that 2.6 parts were used, in the same manner as the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3), A highly saturated nitrile rubber composition (d3) was obtained. Using the cross-linked product of the cross-linkable carboxyl group-containing highly saturated nitrile rubber composition (d3), each of normal properties, compression set, and presence / absence of foaming of the steam cross-linked product was evaluated. The results are shown in Table 1.

Crosslinkable highly saturated nitrile rubber composition (e3)
Using a Banbury mixer, hydrogenated nitrile rubber (trade name: Zetpol 2000L, manufactured by Nippon Zeon Co., Ltd., acrylonitrile unit content 36% by weight, butadiene unit (including hydrogenated) 64% by weight, iodine value 4, Mooney Viscosity 65) 100 parts FEF carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.), silica (trade name: Nipsil ER, manufactured by Tosoh Silica Co., Ltd.), 10 parts, trimellitic acid ester (trade name: Adeka) Sizer C-8, manufactured by ADEKA, plasticizer) 5 parts, 4,4′-di- (α, α-dimethylbenzyl) diphenylamine (trade name: Nowguard 445, manufactured by Crompton, anti-aging agent) 1.5 parts Then, 1 part of stearic acid (crosslinking accelerator) was added and mixed at 50 ° C. for 5 minutes. Next, the resulting mixture was transferred to a roll at 50 ° C. and 8 parts of an organic peroxide crosslinking agent (1,3-bis (t-butylperoxyisopropyl) benzene, trade name: Vulcup 40KE, manufactured by Hercules) was blended. By kneading, a crosslinkable highly saturated nitrile rubber composition (e3) was obtained. Using the cross-linked product of the cross-linkable highly saturated nitrile rubber composition (e3), each evaluation of normal properties, compression set, and presence / absence of foaming of the steam cross-linked product was performed. The results are shown in Table 1.

Crosslinkable carboxyl group-containing acrylic rubber composition (b3)
Using a Banbury mixer, 100 parts of the carboxyl group-containing acrylic rubber (b1) obtained in Production Example 2, 60 parts of FEF carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.), silica (trade name: Nipsil ER) , Manufactured by Tosoh Silica Co., Ltd.), 10 parts, 4,4′-di- (α, α-dimethylbenzyl) diphenylamine (trade name: Naugard 445, manufactured by Crompton, anti-aging agent), stearic acid (crosslinking accelerator) 2 parts) was added and mixed at 50 ° C. for 5 minutes. The resulting mixture was then transferred to a 50 ° C. roll and 1 part of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (aromatic polyamine amine crosslinker, crosslinker (b2)), And 2 parts of 1,3-di-o-tolylguanidine (trade name: Noxeller DT, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., basic crosslinking accelerator) are mixed and kneaded to obtain a crosslinkable carboxyl group-containing acrylic. A rubber composition (b3) was obtained. Using the cross-linked product of the cross-linkable carboxyl group-containing acrylic rubber composition (b3), each evaluation of normal properties, compression set, and presence / absence of foaming of the steam cross-linked product was performed. The results are shown in Table 1.

Crosslinkable epoxy group-containing acrylic rubber composition (c3)
Using a Banbury mixer, 100 parts of the epoxy group-containing acrylic rubber (c1) obtained in Production Example 3, 60 parts of FEF carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.), silica (trade name: Nipsil ER) , Manufactured by Tosoh Silica Co., Ltd.), 10 parts, 4,4′-di- (α, α-dimethylbenzyl) diphenylamine (trade name: Naugard 445, manufactured by Crompton, anti-aging agent), stearic acid (crosslinking accelerator) 2 parts) was added and mixed at 50 ° C. for 5 minutes. Next, the obtained mixture is transferred to a roll at 50 ° C., and 1.5 parts of ammonium benzoate (trade name: Balnock AB, manufactured by Ouchi Shinsei Chemical Co., Ltd., cross-linking agent (c2)) is blended and kneaded. As a result, a crosslinkable epoxy group-containing acrylic rubber composition (c3) was obtained. Using the cross-linked product of the cross-linkable epoxy group-containing acrylic rubber composition (c3), each evaluation of normal properties, compression set, and presence / absence of foaming of the steam cross-linked product was performed. The results are shown in Table 1.

Crosslinkable active chlorine group-containing acrylic rubber composition (f3)
Using a Banbury mixer, 100 parts of the active chlorine group-containing acrylic rubber (f1) obtained in Production Example 4, 60 parts of FEF carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.), silica (trade name: Nipsil) ER, manufactured by Tosoh Silica Co., Ltd., 10 parts, 4,4′-di- (α, α-dimethylbenzyl) diphenylamine (trade name: Naugard 445, manufactured by Crompton, anti-aging agent), 2 parts, stearic acid (assisting crosslinking aid) 2 parts) was added and mixed at 50 ° C. for 5 minutes. Subsequently, the obtained mixture was transferred to a roll at 50 ° C., 0.5 part of 2,4,6-trimercapto-s-triazine (trade name: ZISNET-F, manufactured by Nippon Zeon Co., Ltd., cross-linking agent), Zinc di-n-butyldithiocarbamate (product name: Noxeller BZ, manufactured by Ouchi Shinsei Co., Ltd.), 1.5 parts, N- (cyclohexylthio) phthalimide (trade name: Santguard PVI, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) 0.2 A crosslinkable active chlorine group-containing acrylic rubber composition (f3) was obtained by blending and kneading 0.3 parts of diethylthiourea (trade name: Noxeller EUR, manufactured by Ouchi Shinsei). Using the cross-linked product of the cross-linkable active chlorine group-containing acrylic rubber composition (f3), each evaluation of normal properties, compression set, and presence / absence of foaming of the steam cross-linked product was performed. The results are shown in Table 1.

Example 1
The crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3) and the crosslinkable carboxyl group-containing acrylic rubber composition (b3) were each molded into a sheet shape having a thickness of 2 mm. They are laminated and press-crosslinked at 160 ° C. for 45 minutes to crosslink and bond the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3) and the crosslinkable carboxyl group-containing acrylic rubber composition (b3) to obtain a rubber. A laminate (crosslinked product) was obtained. Table 2 shows the results of a peel test using the obtained rubber laminate (crosslinked product).

Example 2
A rubber laminate (crosslinked product) was prepared in the same manner as in Example 1 except that the crosslinkable carboxyl group-containing acrylic rubber composition (b3) was used instead of the crosslinkable carboxyl group-containing acrylic rubber composition (b3). Obtained. Table 2 shows the results of a peel test using the obtained rubber laminate (crosslinked product).

Comparative Example 1
A rubber laminate (crosslinked product) was obtained in the same manner as in Example 1 except that the crosslinkable active chlorine group-containing acrylic rubber composition (f3) was used instead of the crosslinkable carboxyl group-containing acrylic rubber composition (b3). Got. Table 2 shows the results of a peel test using the obtained rubber laminate (crosslinked product).

Comparative Example 2
A rubber laminate (crosslinked product) was obtained in the same manner as in Example 1 except that the crosslinkable highly saturated nitrile rubber composition (e3) was used instead of the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3). Got. Table 2 shows the results of a peel test using the obtained rubber laminate (crosslinked product).

Comparative Example 3
A rubber laminate (crosslinked product) was obtained in the same manner as in Example 2 except that the crosslinkable highly saturated nitrile rubber composition (e3) was used instead of the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3). Got. Table 2 shows the results of a peel test using the obtained rubber laminate (crosslinked product).

Comparative Example 4
Instead of the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (a3), a crosslinkable carboxyl group-containing acrylic rubber composition (b3) is used instead of the crosslinkable carboxyl group-containing acrylic rubber composition (b3). A rubber laminate (crosslinked product) was obtained in the same manner as in Example 1 except that the active chlorine group-containing acrylic rubber composition (f3) was used. Table 2 shows the results of a peel test using the obtained rubber laminate (crosslinked product).

Table 2 shows the following.
Since the active chlorine group-containing acrylic rubber was used, when the requirements of the present invention were not satisfied, the adhesive strength of the rubber laminate was inferior (Comparative Example 1).
When a highly saturated nitrile rubber not containing a carboxyl group was used and an organic peroxide crosslinking agent was used as a crosslinking agent, when the requirements of the present invention were not satisfied, the adhesive strength of the rubber laminate was inferior ( Comparative Example 2 and Comparative Example 3).
If a highly saturated nitrile rubber not containing a carboxyl group is used, an organic peroxide cross-linking agent is used as a cross-linking agent, and an active chlorine group-containing acrylic rubber is used, the rubber lamination is not performed. The adhesion strength of the body was poor (Comparative Example 4).
On the other hand, when the requirements of the present invention were satisfied, the rubber laminate obtained by cross-linking adhesion was excellent in adhesive strength (Examples 1 and 2).
From Table 1, it was found that when an aromatic polyvalent amine crosslinking agent was used as the crosslinking agent, foaming during steam crosslinking was suppressed, which is suitable for crosslinking including steam crosslinking.

Claims (6)

A crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) comprising a carboxyl group-containing highly saturated nitrile rubber (A1) and a polyamine crosslinking agent (A2);
A crosslinkable carboxyl group-containing acrylic rubber composition (B3) containing a carboxyl group-containing acrylic rubber (B1) and a polyamine crosslinking agent (B2), or an epoxy group-containing acrylic rubber (C1) and an ammonium salt of carboxylic acid. A rubber laminate obtained by cross-linking and bonding a crosslinkable epoxy group-containing acrylic rubber composition (C3) containing a cross-linking agent (C2).   The rubber according to claim 1, wherein the carboxyl group-containing highly saturated nitrile rubber (A1) contains 0.1 to 20% by weight of an α, β-ethylenically unsaturated dicarboxylic acid monoester monomer unit. Laminated body. The rubber laminate according to claim 1 or 2, wherein the polyamine crosslinking agent (A2) is an aromatic polyvalent amine crosslinking agent. Claim 1-3 crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) and / or crosslinkable carboxyl group-containing acrylic rubber composition (B3), characterized in that it contains further basic crosslinking accelerator The rubber laminate according to any one of the above. It is a hose, The rubber laminated body of any one of Claims 1-4 characterized by the above-mentioned. When the crosslinkable carboxyl group-containing highly saturated nitrile rubber composition (A3) and the crosslinkable carboxyl group-containing acrylic rubber composition (B3) or the crosslinkable epoxy group-containing acrylic rubber composition (C3) are crosslinked and bonded, steam is used. The method for producing a rubber laminate according to any one of claims 1 to 5 , wherein crosslinking including crosslinking is performed.