Rubber-resin laminate
Disclosed is a vulcanized rubber laminate, wherein a thermoplastic resin layer and an unvulcanized epichlorohydrin rubber composition layer containing a specific maleimide compound, vulcanizing agent, and acid acceptor are heated and bonded. Specifically disclosed is a laminate configured by heating and bonding an unvulcanized epichlorohydrin rubber composition layer (A) and a thermoplastic resin (B), wherein the unvulcanized epichlorohydrin rubber composition contains: an epichlorohydrin rubber (a), a compound containing one or more maleimide group within the molecule (b), a vulcanizing agent (c), and an acid acceptor (d).
1. A laminate comprising (A) an unvulcanized epichlorohydrin-based rubber composition layer and (B) a thermoplastic resin layer,
wherein (A) the unvulcanized epichlorohydrin-based rubber composition and (B) the thermoplastic resin layer are heated to bond them together and to vulcanize (A) the unvulcanized epichlorohydrin-based rubber composition, and
the unvulcanized epichlorohydrin-based rubber composition (A) contains the following (a) to (d):
(a) an epichlorohydrin-based rubber,
(b) a compound having one or more maleimide groups in the molecule,
(c) a vulcanizing agent, said vulcanizing agent (c) containing at least one kind of a vulcanizing agent selected from a quinoxaline-based vulcanizing agent a thiourea-based vulcanizing agent, a triazine-based vulcanizing agent and a bisphenol-based vulcanizing agent, and
(d) an acid acceptor.
2. The laminate according to claim 1 , wherein the mixing amount of the compound having one or more maleimide groups in the molecule (b) is from 0.1 to 10 parts by weight based on 100 parts by weight of the epichlorohydrin-based rubber (a).
3. The laminate according to claim 1 , wherein the compound having one or more maleimide groups in the molecule (b) is at least one kind selected from maleimide, 1,2-bis(maleimide)ethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 4,4′-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N′-1,3-phenylenedimaleimide, N,N′-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-cyclohexylmaleimide, N-ethylmaleimide, N-methylmaleimide, N-phenylmaleimide, N-succinimidyl 3-maleimidebenzoate, N-succinimidyl 3-maleimidepropionate, N-succinimidyl 4-maleimidebutyrate, N-succinimidyl 6-maleimidehexanoate and N-[4-(2-benzoimidazolyl)phenyl]maleimide.
4. The laminate according to claim 1 , wherein the compound having one or more maleimide groups in the molecule (b) is at least one kind selected from maleimide, 1,6-bismaleimidehexane, 4,4′-bismaleimidediphenylmethane, N,N′-1,3-phenylenedimaleimide, N,N′-1,4-phenylenedimaleimide, N-benzylmaleimide and N-phenylmaleimide.
5. The laminate according to claim 1 , wherein
the quinoxaline-based vulcanizing agent comprises at least one member selected form the group consisting of 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate and 5,8-dimethylquinoxaline-2,3-dithiocarbonate,
thiourea-based vulcanizing agent comprises at least one member selected form the group consisting of 2-mercaptoimidazoline(ethylenethiourea), 1,3-diethylthiourea, 1,3-dibutylthiourea and trimethylthiourea,
triazine-based vulcanizing agent comprises at least one member selected form the group consisting of 2,4,6-trimercapto-1,3,5-triazine, 1-hexylamino-3,5-dimercaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,5-dimercaptotriazine, 1-dibutylamino-3,5-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine and 1-phenylamino-3,5-dimercaptotriazine, and
bisphenol-based vulcanizing agent comprises at least one member selected form the group consisting of bisphenol AF and bisphenol S.
6. The laminate according to claim 1 , wherein the acid acceptor (d) is a metal compound and/or an inorganic microporous crystal.
7. The laminate according to claim 1 , wherein the acid acceptor (d) is a synthetic hydrotalcite.
8. The laminate according to claim 1 , wherein an oxygen permeation rate of the thermoplastic resin layer (B) is 500 cc·20 μm/m 2 ·day·atm or less.
9. The laminate according to claim 1 , wherein the thermoplastic resin layer (B) is at least one kind selected from a polyvinylidene chloride resin, a polyvinyl alcohol resin, an ethylene-vinyl alcohol copolymer resin, a nylon resin, a polyacrylonitrile resin, a polyester resin and a polybutylene naphthalate resin.
10. The laminate according to claim 1 , wherein the thermoplastic resin layer (B) is made of an ethylene-vinyl alcohol copolymer resin or a polybutylene naphthalate resin.
11. A laminate hose using formed from the laminate according to claim 1 .