阅读说明：本技术 丙烯腈-丁二烯橡胶组合物及包含该组合物层的层叠体 (Acrylonitrile-butadiene rubber composition and laminate comprising layer of the composition ) 是由 菊地义治 市野光太郎 于 2019-03-08 设计创作，主要内容包括：本发明的课题在于开发与乙烯-乙酸乙烯酯共聚物皂化物层的粘接强度优异的NBR组合物、以及NBR层与乙烯-乙酸乙烯酯共聚物皂化物层的粘接强度优异的层叠体；本发明涉及一种丙烯腈-丁二烯橡胶组合物,其特征在于,包含丙烯腈-丁二烯橡胶以及相对于该丙烯腈-丁二烯橡胶100质量份为0～50质量份的硅烷改性乙烯-乙酸乙烯酯共聚物；本发明还涉及一种层叠体,其特征在于,包含所述丙烯腈-丁二烯橡胶组合物的丙烯腈-丁二烯橡胶层与乙烯-乙酸乙烯酯共聚物皂化物层隔着乙烯-乙酸乙烯酯共聚物层而层叠。(The invention aims to develop an NBR composition with excellent bonding strength with an ethylene-vinyl acetate copolymer saponified layer and a laminated body with excellent bonding strength between the NBR layer and the ethylene-vinyl acetate copolymer saponified layer; the present invention relates to an acrylonitrile-butadiene rubber composition, which is characterized by comprising an acrylonitrile-butadiene rubber and 0 to 50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer per 100 parts by mass of the acrylonitrile-butadiene rubber; the present invention also relates to a laminate in which an acrylonitrile-butadiene rubber layer containing the acrylonitrile-butadiene rubber composition and an ethylene-vinyl acetate copolymer saponified layer are laminated with an ethylene-vinyl acetate copolymer layer interposed therebetween.)

1. An acrylonitrile-butadiene rubber composition is characterized by comprising an acrylonitrile-butadiene rubber and 0-50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer per 100 parts by mass of the acrylonitrile-butadiene rubber.

2. A laminate comprising an acrylonitrile-butadiene rubber layer and an ethylene-vinyl acetate copolymer saponified layer, which are laminated via an ethylene-vinyl acetate copolymer layer, the composition according to claim 1.

3. The laminate of claim 2, wherein the ethylene-vinyl acetate copolymer layer comprises a silane-modified ethylene-vinyl acetate copolymer.

4. The acrylonitrile-butadiene rubber composition according to claim 1, comprising 2 to 50 parts by mass of the silane-modified ethylene-vinyl acetate copolymer per 100 parts by mass of the acrylonitrile-butadiene rubber.

5. The acrylonitrile-butadiene rubber composition according to claim 1 or 4, further comprising 1.7 to 20 parts by mass of dicumyl peroxide.

6. A laminate comprising a layer comprising the acrylonitrile-butadiene rubber composition according to claim 4 or 5 and a saponified ethylene-vinyl acetate copolymer layer laminated thereon.

Technical Field

The present invention relates to an acrylonitrile-butadiene rubber (NBR) composition having improved adhesive strength with a saponified layer of an ethylene-vinyl acetate copolymer, and a laminate of the composition layer and a saponified layer of an ethylene-vinyl acetate copolymer.

Background

Various hoses such as a radiator hose for cooling an engine, a drain hose for a radiator overflow box, a heater hose for a room heater, an air conditioner drain hose, a wiper water supply hose, a ceiling drain hose, and a protection hose are mounted on automobiles, industrial machines, construction machines, motorcycles, agricultural machines, and the like. These hoses use NBR having excellent oil resistance, heat resistance, and gas permeation resistance.

However, since the NBR single layer may have insufficient gas permeation resistance depending on the application, for example, a laminate of an NBR layer and an ethylene-vinyl alcohol copolymer layer having more excellent gas barrier properties has been proposed (patent document 1).

However, although attempts have been made to simply laminate the NBR layer and the ethylene-vinyl alcohol copolymer layer, it has been found that the adhesive strength is still insufficient.

Disclosure of Invention

Problems to be solved by the invention

The invention aims to develop an NBR composition with excellent bonding strength with an ethylene-vinyl acetate copolymer saponified layer and a laminated body with excellent bonding strength between an NBR layer and an ethylene-vinyl acetate copolymer saponified layer.

Means for solving the problems

The present invention relates to the following [1] to [6 ].

[1] An acrylonitrile-butadiene rubber composition is characterized by comprising an acrylonitrile-butadiene rubber and 0-50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer per 100 parts by mass of the acrylonitrile-butadiene rubber.

[2] A laminate comprising an acrylonitrile-butadiene rubber layer and an ethylene-vinyl acetate copolymer saponified layer, the acrylonitrile-butadiene rubber layer and the ethylene-vinyl acetate copolymer saponified layer being laminated via an ethylene-vinyl acetate copolymer layer.

[3] The laminate according to item [2], wherein the ethylene-vinyl acetate copolymer layer comprises a silane-modified ethylene-vinyl acetate copolymer.

[4] The acrylonitrile-butadiene rubber composition according to item [1], which comprises an acrylonitrile-butadiene rubber and 2 to 50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer per 100 parts by mass of the acrylonitrile-butadiene rubber.

[5] The acrylonitrile-butadiene rubber composition according to item [1] or item [4], characterized by further comprising 1.7 to 20 parts by mass of dicumyl peroxide.

[6] A laminate comprising a layer comprising the acrylonitrile-butadiene rubber composition according to item [4] or item [5] and a saponified ethylene-vinyl acetate copolymer layer laminated thereon.

ADVANTAGEOUS EFFECTS OF INVENTION

The acrylonitrile-butadiene rubber composition containing the silane-modified ethylene-vinyl acetate copolymer of the present invention has excellent adhesive strength when laminated with the saponified ethylene-vinyl acetate copolymer layer, and therefore can be suitably used for various applications requiring oil resistance, heat resistance, and gas permeation resistance.

In addition, a laminate having an ethylene-vinyl acetate copolymer layer between an acrylonitrile-butadiene rubber layer and an ethylene-vinyl acetate copolymer saponified layer is excellent in interlayer adhesion strength, and can be suitably used for various applications requiring oil resistance, heat resistance, and gas permeation resistance.

Detailed Description

Acrylonitrile-butadiene rubber

The acrylonitrile-butadiene rubber (NBR) layer (hereinafter, may be simply referred to as "NBR layer") constituting the laminate of the present invention and the acrylonitrile-butadiene rubber (NBR) constituting the acrylonitrile-butadiene rubber composition (hereinafter, may be simply referred to as "NBR composition") are diene synthetic rubbers obtained by emulsion polymerization of acrylonitrile and butadiene. NBR is generally classified into 5 grades of extremely high (43% or more), high (36 to 42%), medium high (31 to 35%), medium (25 to 30%), and low (24% or less) according to the amount of bound acrylonitrile, and the medium high is a general-purpose type.

Silane-modified ethylene-vinyl acetate copolymer

The silane-modified ethylene-vinyl acetate copolymer blended in the NBR according to the present invention is a modified copolymer obtained by graft-modifying an unsaturated silane compound and an ethylene-vinyl acetate copolymer. The amount of the unsaturated silane compound grafted is usually 0.01 to 5% by weight, preferably 0.02 to 3% by weight.

The Melt Flow Rate (MFR) of the silane-modified ethylene-vinyl acetate copolymer according to the present invention is a value measured in accordance with JIS K7210 [ 190 ℃ C., 2.16kg load ], and is usually in the range of 1.6 to 6.4g/10 min, preferably 1.6 to 4.6g/10 min.

In the silane-modified ethylene-vinyl acetate copolymer, the vinyl acetate content present in the copolymer is usually in the range of 5 to 50% by weight, preferably 5 to 40% by weight.

The Melt Flow Rate (MFR) of the ethylene-vinyl acetate copolymer according to the present invention is a value measured in accordance with JIS K7210 [ 190 ℃ C., 2.16kg load ], which is usually 1.6 to 6.4g/10 min, preferably 1.6 to 4.6g/10 min.

The method of graft-modifying the ethylene-vinyl acetate copolymer with the unsaturated silane compound can employ various known modification methods, and for example, graft modification can be carried out in the presence or absence of a radical initiator. In this case, if the graft modification is performed in the presence of a radical initiator, the unsaturated silane compound can be graft-modified efficiently.

As such a radical initiator, an organic peroxide, an azo compound, or the like is used. As such a radical initiator, specifically, there may be mentioned benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (peroxybenzoate) hexyne-3, 1, 4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperoxy acetate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylperoxy benzoate, t-butylperoxy phenyl acetate, t-butylperoxy isobutyrate, t-butylperoxy sec-octanoate, t-butylperoxy pivalate, cumyl peroxypivalate, t-butylperoxy diethyl acetate; azobisisobutyronitrile, dimethyl azoisobutyrate, and the like.

Among them, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and 1, 4-bis (t-butylperoxyisopropyl) benzene are preferably used.

Unsaturated silane compounds

Examples of the unsaturated silane compound grafted to the ethylene-vinyl acetate copolymer include various known compounds, for example, vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (. beta. -methoxyethoxy) silane and vinyltriacetoxysilane, acrylic silanes such as acryloxypropyltrimethoxysilane and methacryloxypropyltrimethoxysilane, and the like.

NBR composition

The NBR composition of the present invention is prepared by mixing the NBR: 100 parts by mass of the composition, which contains 0 to 50 parts by mass, preferably 2 to 50 parts by mass, and more preferably 5 to 20 parts by mass of the silane-modified ethylene-vinyl acetate copolymer.

When the NBR composition of the present invention contains 1.7 to 20 parts by mass, more preferably 3.4 to 10.2 parts by mass of dicumyl peroxide in addition to the silane-modified ethylene-vinyl acetate copolymer, the adhesive strength with the layer made of the saponified ethylene-vinyl acetate copolymer is further improved.

The NBR of the present invention can contain other components in addition to the silane-modified ethylene-vinyl acetate copolymer and dicumyl peroxide in the range not to impair the effects of the present invention, depending on the intended purpose. As the other component, for example, at least 1 selected from the group consisting of fillers, crosslinking aids, vulcanization accelerators, vulcanization aids, softeners, anti-aging agents, processing aids, active agents, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, colorants, lubricants, thickeners, foaming agents, and foaming aids may be contained. In addition, each additive can be used alone in 1, also can be combined with more than 2.

Packing

The filler blended in the NBR according to the present invention is a known rubber reinforcing agent blended with the NBR, and is usually carbon black or an inorganic substance called an inorganic reinforcing agent.

Specific examples of the filler according to the present invention include Carbon blacks of asahi #55G, asahi #60G (manufactured by asahi Carbon corporation), sea (SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc.) (manufactured by eastern sea Carbon corporation), products obtained by surface-treating these Carbon blacks with a silane coupling agent, etc., and silica, activated calcium carbonate, fine talc, fine silicic acid powder, light calcium carbonate, heavy calcium carbonate, talc, clay, etc.

These fillers may be used alone or in combination of two or more.

As the filler according to the present invention, silica such as hydrophilic silica and hydrophobic silica, carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like are preferably used.

When the NBR of the present invention contains a filler, the NBR may be blended in an amount of usually 100 to 300 parts by mass, preferably 100 to 250 parts by mass, based on 100 parts by mass of the NBR.

Crosslinking assistant, vulcanization accelerator and vulcanization assistant

In the case of using dicumyl peroxide as the crosslinking agent, a crosslinking assistant may be used in combination. Examples of the crosslinking assistant include, for example, sulfur; quinone dioxime-based crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; a maleimide-based crosslinking assistant; divinylbenzene; zinc oxide (for example, ZnO # 1. Zinc oxide 2 (JIS Standard (K-1410)), HakusuiTech (manufactured by HakusuiTech Co., Ltd.), magnesium oxide, zinc oxide such as zinc white [ for example, "META-Z102" (trade name; manufactured by UK lime industry Co., Ltd.), active zinc white, and other metal oxides.

When a crosslinking assistant is used, the amount of the crosslinking assistant in the NBR is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, and more preferably 1 to 6 mol, based on 1 mol of dicumyl peroxide.

Examples of the vulcanization accelerator according to the present invention include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N, thiazole-based vulcanization accelerators such as N' -diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (e.g., Sanceler M (trade name; manufactured by Sanneo chemical industries, Ltd.)), 2- (4-morpholinodithio) benzothiazole (e.g., Nocceller MDB-P (trade name; manufactured by Nippon chemical industries, Ltd.)), 2- (2, 4-dinitrophenyl) mercaptobenzothiazole, 2- (2, 6-diethyl-4-morpholinothio) benzothiazole, and dibenzothiazyl disulfide (e.g., Sanceler DM (trade name; manufactured by Sanceler chemical industries, Ltd.); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine and di-o-tolylguanidine; aldehyde-amine vulcanization accelerators such as acetaldehyde-aniline condensates and butylaldehyde-aniline condensates; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; thiuram-based vulcanization accelerators such as tetramethylthiuram monosulfide (for example, Sanceler TS (trade name; manufactured by Sanxin chemical industries)), tetramethylthiuram disulfide (for example, Sanceler TT (trade name; manufactured by Sanxin chemical industries)), tetraethylthiuram disulfide (for example, Sanceler TET (trade name; manufactured by Sanxin chemical industries)), tetrabutylthiuram disulfide (for example, Sanceler TBT (trade name; manufactured by Sanneo chemical industries)), and dipentamethylenethiuram tetrasulfide (for example, Sanceler TRA (trade name; manufactured by Sanceler chemical industries)); dithioates-based vulcanization accelerators such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (for example, Sanceler PZ, Sanceler BZ and Sanceler EZ (trade name; manufactured by Sanxin chemical industries Co., Ltd.)), and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators such as, for example, Sanceler BUR (trade name; manufactured by Sanceler chemical industries, Ltd.) and Sanceler 22-C (trade name; manufactured by Sanneo chemical industries, Ltd.), N '-diethylthiourea and N, N' -dibutylthiourea; and a xanthate vulcanization accelerator such as zinc dibutylxanthate.

When a vulcanization accelerator is used, the amount of the vulcanization accelerator in the NBR is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the NBR. When the compounding amount of the vulcanization accelerator is within the above range, the resulting laminate will not be frosted on the surface, and the NBR will exhibit excellent crosslinking characteristics. When a sulfur-based compound is used as the crosslinking agent, a vulcanization aid can be used in combination.

Examples of the vulcanization aid according to the present invention include zinc oxide (e.g., ZnO # 1. Zinc oxide 2, manufactured by HakusuiTech Co., Ltd.), magnesium oxide, zinc white (e.g., "META-Z102" (trade name; manufactured by the Wellkushik industries Co., Ltd.), and the like).

When a vulcanization aid is used, the amount of the vulcanization aid in the NBR composition is usually 1 to 20 parts by mass per 100 parts by mass of the NBR.

Softener

Examples of the softener according to the present invention include petroleum softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; coal tar system softeners such as coal tar; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic high molecular substances such as terpene resin, petroleum resin, coumarone indene resin and the like; ester softeners such as dioctyl phthalate and dioctyl adipate; and microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and vulcanized factice (factice), among which petroleum-based softeners are preferred, and process oil is particularly preferred.

When the NBR of the present invention contains a softener, the amount of the softener to be blended is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, based on 100 parts by mass of the NBR.

Anti-aging agent (stabilizer)

By blending an antioxidant (stabilizer) in the NBR according to the present invention, the life of the gasket formed of the NBR can be extended. As such an antioxidant, conventionally known antioxidants, for example, amine antioxidants, phenol antioxidants, sulfur antioxidants, and the like are available.

Examples of the antioxidant according to the present invention include aromatic secondary amine antioxidants such as phenylbutylamine and N, N-di-2-naphthyl-p-phenylenediamine; phenol antioxidants such as dibutylhydroxytoluene and tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxy) hydrocinnamate ] methane; thioether-based antioxidants such as bis [ 2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl ] sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; and sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, and distearyl thiodipropionate.

When the NBR of the present invention contains an antioxidant, the amount of the antioxidant to be blended is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, based on 100 parts by mass of the NBR. If the amount of the antioxidant is within the above range, the surface of the laminate to be obtained is not frosted, and the occurrence of vulcanization inhibition can be further suppressed.

Processing aid

As the processing aid according to the present invention, in general, a processing aid blended in rubber can be widely used. Specific examples thereof include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, esters, and the like. Among them, stearic acid is preferable.

When the NBR of the present invention contains a processing aid, the NBR can be appropriately blended in an amount of usually 1 to 3 parts by mass per 100 parts by mass of the NBR. If the amount of the processing aid is within the above range, the processability such as kneading processability, extrusion processability and injection moldability is excellent, and therefore, the amount is suitable.

The processing aid may be 1 kind alone or 2 or more kinds.

Active agent

Examples of the active agent according to the present invention include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; active agents such as diethylene glycol, polyethylene glycol, lecithin, triallyl 1,2, 4-benzenetricarboxylate (triallyl trimetallate), and zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; a zinc peroxide modulator; octadecyl trimethyl ammonium bromide, synthetic hydrotalcite and special quaternary ammonium compounds.

When the NBR of the present invention contains an activator, the amount of the activator blended is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the NBR.

Foaming agent and foaming aid

The laminate formed using the NBR according to the present invention may be a non-foam or a foam. When the laminate is a foam, the NBR composition preferably contains a foaming agent.

As the blowing agent of the present invention, any commercially available blowing agent can be suitably used. Examples of such a foaming agent include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; nitroso compounds such as N, N '-dinitrosoterephthalamide and N, N' -dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p '-oxybis (benzenesulfonyl hydrazide) diphenyl sulfone-3, 3' -disulfonyl hydrazide and the like; azide compounds such as calcium azide, 4' -diphenyldisulfonylazide and p-toluenesulfonylazide. Among them, azo compounds, sulfonyl hydrazide compounds, azide compounds are preferably used.

When the NBR of the present invention contains a foaming agent, the amount of the foaming agent to be blended may be appropriately selected depending on the performance required for the laminate produced from the NBR, and is usually used in an amount of 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the NBR.

Further, a foaming aid may be used in combination with the foaming agent as needed. The addition of the foaming aid has an effect on the adjustment of the decomposition temperature of the foaming agent, the homogenization of bubbles, and the like. Specific examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea and its derivatives, and the like.

When the NBR of the present invention contains a foaming aid, the amount of the foaming aid to be blended is usually 1 to 100 parts by mass, preferably 2 to 80 parts by mass, based on 100 parts by mass of the foaming agent.

< ethylene-vinyl acetate copolymer saponification product >

The saponified ethylene-vinyl acetate copolymer constituting the laminate of the present invention is a copolymer of ethylene and vinyl alcohol, also referred to as an ethylene-vinyl alcohol copolymer.

The ethylene-vinyl acetate copolymer saponified material according to the present invention is not particularly limited, and the ethylene content is usually 20 to 50 mol%, preferably 24 to 35 mol%. The saponified ethylene-vinyl acetate copolymer according to the present invention is not particularly limited as long as it has melt extrusion moldability, and usually has an MFR (load: 2160g, measurement temperature: 190 ℃) within the range of 1.6 to 6.4g/10 min.

Specifically, the ethylene-vinyl acetate copolymer saponified product of the present invention is manufactured and sold by glai, inc under the trade name Eval, and by saikoku, having the trade name solarnol.

Ethylene-vinyl acetate copolymer

The ethylene-vinyl acetate copolymer constituting the laminate of the present invention is a copolymer of ethylene and vinyl acetate, and the vinyl acetate content present in the copolymer is usually 5 to 50% by weight, preferably 5 to 40% by weight.

The Melt Flow Rate (MFR) of the ethylene-vinyl acetate copolymer according to the present invention is a value measured in accordance with JIS K7210 [ 190 ℃ C., 2.16kg load ], which is usually 1.6 to 6.4g/10 min, preferably 1.6 to 4.6g/10 min.

The ethylene-vinyl acetate copolymer according to the present invention may be a modified copolymer obtained by graft modification of an unsaturated silane compound. The graft amount of the unsaturated silane compound in this case is usually 0.01 to 5% by weight, preferably 0.02 to 3% by weight.

The modified copolymer according to the present invention is obtained by graft-modifying an ethylene-vinyl acetate copolymer by various known modification methods, for example, in the presence or absence of a radical initiator. In this case, if the graft modification is performed in the presence of a radical initiator, the unsaturated silane compound can be graft-modified efficiently.

As such a radical initiator, an organic peroxide, an azo compound, or the like is used. As such a radical initiator, specifically, there may be mentioned benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (peroxybenzoate) hexyne-3, 1, 4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperoxy acetate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylperoxy benzoate, t-butylperoxy phenyl acetate, t-butylperoxy isobutyrate, t-butylperoxy-sec-octanoate, t-butylperoxy pivalate, cumyl peroxypivalate, t-butylperoxy diethyl acetate; azobisisobutyronitrile, dimethyl azoisobutyrate, and the like.

Among them, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and 1, 4-bis (t-butylperoxyisopropyl) benzene are preferably used.

Unsaturated silane compounds

Examples of the unsaturated silane compound grafted to the ethylene-vinyl acetate copolymer include various known compounds, for example, vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (. beta. -methoxyethoxy) silane and vinyltriacetoxysilane, acrylic silanes such as acryloxypropyltrimethoxysilane and methacryloxypropyltrimethoxysilane, and the like.

< laminate >

The laminate of the present invention is a laminate in which the NBR composition layer and the ethylene-vinyl acetate copolymer saponified material layer are laminated.

The thickness of the NBR composition layer and the ethylene-vinyl acetate copolymer saponified layer constituting the laminate of the present invention is not particularly limited, and the NBR composition layer is usually 0.1 to 30mm, preferably 1 to 5mm, and the ethylene-vinyl acetate copolymer saponified layer is usually 0.1 to 30mm, preferably 1 to 5 mm. The thickness of the entire laminate is not particularly limited, but is usually 1 to 31mm, preferably 5 to 20 mm.

The laminate of the present invention is a laminate in which the NBR layer and the ethylene-vinyl acetate copolymer saponified layer are laminated with the ethylene-vinyl acetate copolymer layer interposed therebetween.

The NBR layer constituting the laminate includes the NBR composition layer.

The thickness of the NBR layer and the ethylene-vinyl acetate copolymer saponified layer constituting the laminate of the present invention is not particularly limited, and the NBR layer is usually 0.1 to 30mm, preferably 1 to 5mm, and the ethylene-vinyl acetate copolymer saponified layer is usually 0.1 to 30mm, preferably 1 to 5 mm.

The thickness of the ethylene-vinyl acetate copolymer layer is not particularly limited, but is usually 30 to 300. mu.m, and preferably in the range of 30 to 250. mu.m.

The thickness of the entire laminate is not particularly limited, but is usually 1 to 31mm, preferably 5 to 20 mm.

The laminate of the present invention can be produced by various known molding methods, specifically, for example, a method of co-extruding NBR and a saponified ethylene-vinyl acetate copolymer with an ethylene-vinyl acetate copolymer as an intermediate layer to produce a laminate; a method in which the NBR layer and the saponified ethylene-vinyl acetate copolymer layer are laminated with the ethylene-vinyl acetate copolymer layer interposed therebetween after the NBR, the ethylene-vinyl acetate copolymer, and the saponified ethylene-vinyl acetate copolymer are respectively extrusion-molded or press-molded; a method of extruding an ethylene-vinyl acetate copolymer layer onto an NBR layer or an ethylene-vinyl acetate copolymer saponified layer and laminating, and then attaching the ethylene-vinyl acetate copolymer saponified layer or the NBR layer; or various molding methods such as injection molding, calender molding, hollow molding, etc.

The laminate of the present invention can be produced, for example, by a method of co-extruding the NBR composition and the saponified ethylene-vinyl acetate copolymer; a method of laminating the NBR composition layer and the ethylene-vinyl acetate copolymer saponified layer after extruding or press-molding the NBR and the ethylene-vinyl acetate copolymer saponified material, respectively; or various molding methods such as injection molding, calender molding, and blow molding.

The laminate of the present invention is suitably used in various applications requiring oil resistance, heat resistance and gas permeation resistance, for example, pipes or hoses for automobile fuel piping, pipes or hoses for automobile cooling system piping, automobile radiator hoses, brake hoses, air-conditioning hoses, pipes such as wire coating materials and optical fiber coating materials, hoses, agricultural films, linings (lining), building interior materials (wall paper and the like), films and sheets of laminated steel sheets and the like, cans such as automobile radiator cans, liquid medicine bottles, liquid medicine tanks, liquid medicine containers, gasoline tanks and the like. The laminated structure of the present invention is particularly useful as a pipe or a hose for an automobile fuel pipe because of its low fuel permeability.