Title of the Invention: Acrylonitrile-butadiene rubber composition and a laminate containing the composition layer
Technical field
[0001]
　The present invention relates to an acrylonitrile-butadiene rubber (NBR) composition having improved adhesive strength with an ethylene-vinyl acetate copolymer saponified layer, and a laminate of the composition layer and an ethylene-vinyl acetate copolymer saponified layer. Regarding the body.
Background technology
[0002]
　For automobiles, industrial machinery, construction machinery, motorbikes, agricultural machinery, etc., radiator hoses for cooling engines, drain hoses for radiator overflow, heater hoses for room heating, air conditioner drain hoses, wiper water supply hoses, roof drain hoses, professionals Various hoses such as lacto hoses are installed. NBR having good oil resistance, heat resistance, and gas permeability is used for these hoses.
[0003]
　However, depending on the application, the gas permeability resistance of the NBR single layer is insufficient. Therefore, for example, the NBR layer and the ethylene / vinyl alcohol copolymer layer having more excellent gas barrier properties are laminated (Patent Document 1). Has been proposed.
[0004]
　However, it was found that the adhesive strength was insufficient even if the NBR layer and the ethylene / vinyl alcohol copolymer layer were simply laminated.
Prior art literature
Patent documents
[0005]
Patent Document 1: Japanese Unexamined Patent Publication No. 2009-006575
Outline of the invention
Problems to be solved by the invention
[0006]
　An object of the present invention is to develop an NBR composition having excellent adhesive strength with an ethylene-vinyl acetate copolymer saponified layer and a laminate having excellent adhesive strength between an NBR layer and an ethylene-vinyl acetate copolymer saponified layer. To do.
Means to solve problems
[0007]
　The present invention relates to the following [1] to [6].
[0008]
　[1] An acrylonitrile-butadiene rubber composition, which comprises 0 to 50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer with respect to 100 parts by mass of the acrylonitrile-butadiene rubber and the acrylonitrile-butadiene rubber.
[0009]
　[2] The acrylonitrile-butadiene rubber layer containing the composition according to item [1] and the ethylene-vinyl acetate copolymer saponified layer are laminated via the ethylene-vinyl acetate copolymer layer. A characteristic laminate.
[0010]
　[3] The laminate according to Item [2], wherein the ethylene-vinyl acetate copolymer layer contains a silane-modified ethylene-vinyl acetate copolymer.
[0011]
　[4] The acrylonitrile according to item [1], which comprises 2 to 50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer with respect to 100 parts by mass of the acrylonitrile-butadiene rubber and the acrylonitrile-butadiene rubber. -Butadiene rubber composition.
[0012]
　[5] The acrylonitrile-butadiene rubber composition according to Item [1] or Item [4], which further contains 1.7 to 20 parts by mass of dicumyl peroxide.
[0013]
　[6] A laminate characterized in that a layer made of the acrylonitrile-butadiene rubber composition according to item [4] or item [5] and an ethylene-vinyl acetate copolymer saponified layer are laminated.
Effect of the invention
[0014]
　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 ethylene-vinyl acetate copolymer saponified layer, and thus has excellent oil resistance, heat resistance, and resistance. It can be suitably used for various applications that require gas permeability.
[0015]
　Further, the laminate having the ethylene / vinyl acetate copolymer layer between the acrylonitrile / butadiene rubber layer and the ethylene / vinyl acetate copolymer saponified layer has excellent adhesive strength between the layers, and has oil resistance, heat resistance, and gas resistance. It can be suitably used for various applications that require transparency.
Mode for carrying out the invention
[0016]
　<< Acrylonitrile-butadiene rubber >>
　An acrylonitrile-butadiene rubber (NBR) layer (hereinafter, may be abbreviated as "NBR layer") and an acrylonitrile-butadiene rubber composition (hereinafter, "NBR") constituting the laminate of the present invention. The acrylonitrile-butadiene rubber (NBR) constituting (sometimes abbreviated as "composition") is a diene-based synthetic rubber obtained by emulsifying and polymerizing acrylonitrile and butadiene. NBR is generally extremely high (43% or more), high (36 to 42%), medium high (31 to 35%), medium (25 to 30%), low (24% or less) depending on the amount of acrylonitrile bound. It is classified into 5 stages, and middle and high schools are general-purpose types.
[0017]
　<< Silane-modified ethylene-vinyl acetate copolymer >> The silane-modified ethylene-vinyl acetate copolymer
　blended in the NBR according to the present invention is modified by graft-modifying an unsaturated silane compound with an ethylene-vinyl acetate copolymer. It is a copolymer. The amount of the unsaturated silane compound grafted is usually 0.01 to 5% by weight, preferably 0.02 to 3% by weight.
[0018]
　The melt flow rate (MFR) of the silane-modified ethylene-vinyl acetate copolymer according to the present invention is usually 1.6 to 6.4 g as measured in accordance with JIS K7210 [190 ° C., 2.16 kg load]. It is in the range of / 10 minutes, preferably 1.6 to 4.6 g / 10 minutes.
[0019]
　The silane-modified ethylene-vinyl acetate copolymer usually has a vinyl acetate content present in the copolymer in the range of 5 to 50% by weight, preferably 5 to 40% by weight.
[0020]
　The melt flow rate (MFR) of the ethylene-vinyl acetate copolymer according to the present invention is usually 1.6 to 6.4 g / 10 as measured in accordance with JIS K7210 [190 ° C., 2.16 kg load]. Minutes, preferably in the range of 1.6-4.6 g / 10 minutes.
[0021]
　As a method for graft-modifying an unsaturated silane compound on an ethylene-vinyl acetate copolymer, various known modification methods, for example, graft modification can be performed in the presence or absence of a radical initiator. At that time, if graft modification is performed in the presence of a radical initiator, the unsaturated silane compound can be efficiently graft-modified.
[0022]
　As such a radical initiator, an organic peroxide, an azo compound or the like is used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di (peroxide benzoate) hexin-. 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butyl peroxide) hexin-3,2,5 -Dimethyl-2,5-di (t-butyl peroxide) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octate, t-butylperpi Valate, cumylperpivalate, t-butylperdiethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate and the like.
[0023]
　Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (t) Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.
[0024]
　
　Examples of the unsaturated silane compound grafted on the ethylene / vinyl acetate copolymer include various known compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyl (β-methoxyethoxy) silane. Examples thereof include vinyl silanes such as vinyl triacetoxysilane, acrylic silanes such as acryloxipropyltrimethoxysilane and metharoxypropyltrimethoxysilane.
[0025]
　<< NBR Composition >> In the NBR composition of the
　present invention, 0 to 50 parts by mass, preferably 2 to 50 parts by mass, more preferably the above-mentioned silane-modified ethylene-vinyl acetate copolymer with respect to the above NBR: 100 parts by mass. Is a composition containing 5 to 20 parts by mass.
[0026]
　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 dicumylperoxide in addition to the above-mentioned silane-modified ethylene-vinyl acetate copolymer. The adhesive strength with the layer made of vinyl copolymer saponified product is further improved.
[0027]
　In the NBR according to the present invention, in addition to the above-mentioned silane-modified ethylene-vinyl acetate copolymer and dicumyl peroxide, other components can be blended according to a desired purpose within a range that does not impair the effects of the present invention. Other components include, for example, fillers, cross-linking aids, vulcanization accelerators, vulcanization aids, softeners, anti-aging agents, processing aids, activators, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, etc. It may contain at least one selected from colorants, lubricants, thickeners, foaming agents and foaming aids. Also. Each additive may be used alone or in combination of two or more.
[0028]
　
　The filler blended in the NBR according to the present invention is a known rubber reinforcing agent blended in the NBR, and is an inorganic substance usually called carbon black or an inorganic reinforcing agent.
[0029]
　Specifically, the fillers according to the present invention include Asahi # 55G, Asahi # 60G (all manufactured by Asahi Carbon Co., Ltd.), Silica (SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT). Etc.), carbon black (manufactured by Tokai Carbon Co., Ltd.), these carbon blacks surface-treated with a silane coupling agent, etc., and silica, activated calcium carbonate, fine powder talc, fine powder silicic acid, light calcium carbonate, etc. Examples include heavy calcium carbonate, talc, and clay.
[0030]
　These fillers may be used alone or as a mixture of two or more kinds.
[0031]
　As the filler according to the present invention, preferably, silica such as hydrophilic silica and hydrophobic silica, carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay and the like are used.
[0032]
　When the NBR according to the present invention contains a filler, it may be blended in a range of usually 100 to 300 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the NBR.
[0033]
　 When
　dicumyl peroxide is used as the crosslinking agent, a crosslinking aid may be used in combination. Examples of the cross-linking aid include sulfur; a quinone-dioxym-based cross-linking aid such as p-quinone dioxime; an acrylic cross-linking aid such as ethylene glycol dimethacrylate and trimethylpropantrimethacrylate; diallyl phthalate and triallyl isocyanurate. Allyl-based cross-linking aids such as; Maleimide-based cross-linking aids; Divinylbenzene; Zinc oxide (for example, ZnO # 1 and zinc oxide 2 types (JIS standard (K-1410)), manufactured by Huxitec Co., Ltd.), magnesium oxide, etc. Examples thereof include zinc oxide [for example, zinc oxide such as “META-Z102” (trade name; manufactured by Inoue Lime Industry Co., Ltd.)] and metal oxides such as active zinc white.
[0034]
　When a cross-linking aid is used, the amount of the cross-linking aid in the NBR is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, and more preferably 1 to 6 mol with respect to 1 mol of dicumyl peroxide. It is a mole.
[0035]
　Examples of the vulcanization accelerator according to the present invention include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N, N'.-Diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (for example, Sunseller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2- (4-morpholinodithio) penzothiazole (for example, Noxeller MDB) -P (trade name; manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothia Thiazole-based vulcanization accelerators such as zirdisulfide (for example, Sunseller DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorsotrilguanidine; acetaldehyde. Analdehyde amine-based vulcanization accelerators such as aniline condensates and butylaldehyde / aniline condensates; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazolin; tetramethylthiuram monosulfide (for example, Sunseller TS (trade name; Sanshin Kagaku)) (Industrial Co., Ltd.)), Tetramethylthiuram disulfide (for example, Sunseller TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), Tetraethylthiuram disulfide (for example, Sunseller TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), Tetra Thiuram-based vulcanization such as butyl thiuram disulfide (for example, Suncella TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and dipentamethylene thiuram tetrasulfide (for example, Suncella TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)). Accelerators; dithioates such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (eg, Sansera PZ, Sansera BZ and Sansera EZ (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and tellurium diethyldithiocarbamate. Vulcanization accelerators; ethylenethiourea (for example, Sunseller BUR (trade name: manufactured by Sanshin Chemical Industry Co., Ltd.), Sunseller 22-C (trade name: manufactured by Sanshin Chemical Industry Co., Ltd.)), N, N'-diethylthiourea and N, N'-Thiourea-based vulcanization accelerators such as dibutylthiourea; xanthate-based vulcanization accelerators such as zinc dibutylxatogenate.
[0036]
　When a vulcanization accelerator is used, the blending amount of these vulcanization accelerators in the NBR is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.2 to 15 parts by mass with respect to 100 parts by mass of NBR. Is 0.5 to 10 parts by mass. When the blending amount of the vulcanization accelerator is within the above range, NBR exhibits excellent cross-linking characteristics without blooming on the surface of the obtained laminate. When a sulfur-based compound is used as the cross-linking agent, a vulcanization aid can be used in combination.
[0037]
　Examples of the vulcanization aid according to the present invention include zinc oxide (for example, ZnO # 1 and zinc oxide 2 types, manufactured by HakusuiTech Co., Ltd.), magnesium oxide, and zinc oxide (for example, "META-Z102" (trade name). Zinc oxide) such as Inoue Lime Industry Co., Ltd.).
[0038]
　When a vulcanization aid is used, the blending amount of the vulcanization aid in the NBR composition is usually 1 to 20 parts by mass with respect to 100 parts by mass of NBR.
[0039]
　
　Examples of the softening agent according to the present invention include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; coultal-based softening agents such as coal tar; castor oil. , Amani oil, rapeseed oil, soybean oil, coconut oil and other fatty oil-based softeners; beeswax, carnauba wax and other waxes; naphthenic acid, pine oil, rosin or derivatives thereof; Synthetic polymer substances such as; ester-based softeners such as dioctylphthalate and dioctyl adipate; in addition, microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, sub (factis), etc. Of these, petroleum-based softeners are preferable, and process oils are particularly preferable.
[0040]
　When the NBR according to the present invention contains a softener, the blending amount of the softener is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of NBR.
[0041]
　
　By blending an anti-aging agent (stabilizer) with the NBR according to the present invention, the life of the seal packing to be formed can be extended. Examples of such an anti-aging agent include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.
[0042]
　Examples of the anti-aging agent according to the present invention include aromatic secondary amine-based anti-aging agents such as phenylbutylamine, N, N-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3). , 5-di-t-butyl-4-hydroxy) hydrocinnamate] Phenolic anti-aging agents such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl ] Thioether-based anti-aging agents such as sulfide; Dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropio There are sulfur-based antioxidants such as nate and distearylthiodipropionate.
[0043]
　When the NBR according to the present invention contains an anti-aging agent, the blending amount of the anti-aging agent is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass with respect to 100 parts by mass of NBR. It is a mass part. When the blending amount of the anti-aging agent is within the above range, there is no bloom on the surface of the obtained laminate, and the occurrence of vulcanization inhibition can be further suppressed.
[0044]
　 As the processing auxiliary agent according to the
　present invention, a processing auxiliary agent generally blended with 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 or esters. Of these, stearic acid is preferred.
[0045]
　When the NBR according to the present invention contains a processing aid, it can be appropriately blended in an amount of usually 1 to 3 parts by mass with respect to 100 parts by mass of NBR. When the blending amount of the processing aid is within the above range, it is preferable because it is excellent in processability such as kneading processability, extrusion processability, and injection moldability.
[0046]
　The processing aid may be used alone or in combination of two or more.
[0047]
　
　Examples of the activator according to the present invention include amines such as di-n-butylamine, dicyclohexylamine and monoeranolamine; diethylene glycol, polyethylene glycol, lecithin, trialilutomerylate, aliphatic carboxylic acid or aromatic. Activators such as zinc compounds of group carboxylic acids; zinc peroxide modifiers; kutadecyltrimethylammonium bromide, synthetic hydrotalcites, special quaternary ammonium compounds.
[0048]
　When the NBR according to the present invention contains an activator, the blending amount of the activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of NBR. ..
[0049]
　
　The laminate formed by using the NBR according to the present invention may be a non- foaming material or a foaming material . When the laminate is a foam, it is preferable that the NBR composition contains a foaming agent.
[0050]
　As the foaming agent according to the present invention, any commercially available foaming agent is preferably used. Examples of such foaming agents include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N'-dinitrosoterephthalamide, N, N'-dinitroso. Nitroso compounds such as pentamethylenetetramine; azo compounds such as azodicarboxylicamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'- Oxybis (benzenesulfonylhydrazide) Sulfonylhydrazide compounds such as diphenylsulphon-3,3'-disulfonylhydrazide; azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide, and paratoluenemalhonyl azide can be mentioned. Of these, azo compounds, sulfonyl hydrazide compounds, and azide compounds are preferably used.
[0051]
　When the NBR according to the present invention contains a foaming agent, the blending amount of the foaming agent is appropriately selected depending on the performance required for the laminate produced from the NBR, but is usually compared to 100 parts by mass of the NBR. It is used in a proportion of 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass.
[0052]
　Further, if necessary, a foaming aid may be used in combination with the foaming agent. The addition of the foaming aid is effective in controlling the decomposition temperature of the foaming agent and homogenizing the bubbles. Specific examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and its derivatives.
[0053]
　When the NBR according to the present invention contains a foaming aid, the blending amount of the foaming aid is usually 1 to 100 parts by mass, preferably 2 to 80 parts by mass with respect to 100 parts by mass of the foaming agent. Used in.
[0054]
　
　The ethylene-vinyl acetate copolymer saponification constituting the laminate of the present invention is a copolymer of ethylene and vinyl alcohol, which is also called an ethylene-vinyl alcohol copolymer. It is a coalescence.
[0055]
　The ethylene-vinyl acetate copolymer saponified product according to the present invention is not particularly limited, but usually has an ethylene content in the range of 20 to 50 mol%, preferably 24 to 35 mol%. The ethylene-vinyl acetate copolymer saponified product according to the present invention has an MFR (load: 2160 g, measurement temperature: 190 ° C.) as long as it has melt extrusion moldability, but is usually 1.6. It is in the range of ~ 6.4 g / 10 minutes.
[0056]
　Specifically, the ethylene-vinyl acetate copolymer saponified product according to the present invention is manufactured and sold by Kuraray Co., Ltd. under the trade name of EVAL and by Nippon Synthetic Chemical Industry under the trade name of Soanol.
[0057]
　<< 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 high. Generally, 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.
[0058]
　The melt flow rate (MFR) of the ethylene-vinyl acetate copolymer according to the present invention is usually 1.6 to 6.4 g / 10 as measured in accordance with JIS K7210 [190 ° C., 2.16 kg load]. Minutes, preferably in the range of 1.6-4.6 g / 10 minutes.
[0059]
　The ethylene-vinyl acetate copolymer according to the present invention may be a modified copolymer obtained by graft-modifying an unsaturated silane compound. In that case, the graft amount of the unsaturated silane compound is usually in the range of 0.01 to 5% by weight, preferably 0.02 to 3% by weight.
[0060]
　The modified copolymer according to the present invention is obtained by graft-modifying an ethylene-vinyl acetate copolymer in the presence or absence of various known modification methods, for example, a radical initiator. At that time, if graft modification is performed in the presence of a radical initiator, the unsaturated silane compound can be efficiently graft-modified.
[0061]
　As such a radical initiator, an organic peroxide, an azo compound or the like is used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di (peroxide benzoate) hexin-. 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butyl peroxide) hexin-3,2,5 -Dimethyl-2,5-di (t-butyl peroxide) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octate, t-butylperpi Valate, cumylperpivalate, t-butylperdiethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate and the like.
[0062]
　Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (t) Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.
[0063]
　
　Examples of the unsaturated silane compound grafted on the ethylene / vinyl acetate copolymer include various known compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyl (β-methoxyethoxy) silane. Examples thereof include vinyl silanes such as vinyl triacetoxysilane, acrylic silanes such as acryloxipropyltrimethoxysilane and metharoxypropyltrimethoxysilane.
[0064]
　
　The laminated body of the present invention is a laminated body in which the above-mentioned NBR composition layer and the above-mentioned ethylene-vinyl acetate copolymer saponified layer are laminated.
[0065]
　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, but the NBR composition layer is usually 0.1 to 30 mm. The thickness is preferably 1 to 5 mm, and the ethylene-vinyl acetate copolymer saponified layer is usually 0.1 to 30 mm, preferably 1 to 5 mm. The thickness of the entire laminate is not particularly limited, but is usually 1 to 31 mm, preferably 5 to 20 mm.
[0066]
　Further, the laminate of the present invention is a laminate in which the NBR layer and the saponified ethylene / vinyl acetate copolymer layer are laminated via the ethylene / vinyl acetate copolymer layer.
[0067]
　The NBR layer constituting the laminate includes the NBR composition layer.
[0068]
　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, but the NBR layer is usually 0.1 to 30 mm, which is preferable. Is 1 to 5 mm, and the ethylene-vinyl acetate copolymer saponified layer is usually 0.1 to 30 mm, preferably 1 to 5 mm.
[0069]
　The thickness of the ethylene-vinyl acetate copolymer layer is not particularly limited, but is usually in the range of 30 to 300 μm, preferably 30 to 250 μm.
[0070]
　The thickness of the entire laminate is not particularly limited, but is usually 1 to 31 mm, preferably 5 to 20 mm.
[0071]
　The laminate of the present invention is co-extruded by various known molding methods, specifically, for example, NBR and an ethylene-vinyl acetate copolymer saponate with an ethylene-vinyl acetate copolymer as an intermediate layer. Method for forming a laminate, NBR, ethylene-vinyl acetate copolymer and ethylene-vinyl acetate copolymer saponified product are each extruded or press-molded, and then the NBR layer and ethylene-vinyl acetate copolymer saponified product layer are formed. And are laminated via an ethylene-vinyl acetate copolymer layer, an ethylene-vinyl acetate copolymer layer is extruded and laminated on an NBR layer or an ethylene-vinyl acetate copolymer saponified layer, and then both ethylene-vinyl acetate are used. A laminate can be obtained by a method of laminating a polymer saponified layer or an NBR layer, or by various molding processing methods such as injection molding, calendar molding, and hollow molding.
[0072]
　Further, the laminate of the present invention includes, for example, a method of coextruding an NBR composition and an ethylene-vinyl acetate copolymer saponified product to obtain a laminate, and NBR and an ethylene-vinyl acetate copolymer saponified product. After each extrusion molding or press molding, the NBR composition layer and the ethylene / vinyl acetate copolymer saponified layer are laminated, or by various molding processing methods such as injection molding, calendar molding, and hollow molding. It can be a laminate.
[0073]
　The laminate of the present invention has various applications that require oil resistance, heat resistance, and gas permeability, for example, a tube or hose for automobile fuel piping, a tube or hose for automobile cooling system piping, an automobile radiator hose, a brake hose, and the like. Air conditioner hoses, electric wire coating materials, tubes such as optical fiber coating materials, hoses, agricultural films, linings, building interior materials (wallpapers, etc.), laminated steel plates and other films, sheets, automobile radiator tanks, chemical bottles, chemical tanks. , Suitable for tanks such as chemical containers and gasoline tanks. The laminated structure of the present invention is particularly useful as a tube or hose for automobile fuel piping because of its low fuel permeability.
Example
[0074]
　Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0075]
　The polymers and the like used in Examples and Comparative Examples are shown below.
(1) NBR: Trade name Nipol 1042, amount of bound acrylonitrile (AN): 33.5%, ML (1 + 4) 100 ° C.: 77.5, non-staining, specific gravity: 0.98 [manufactured by Nippon Zeon Corporation]
(2) Ethylene-vinyl acetate copolymer
(2-1) Ethylene-vinyl acetate copolymer As
　ethylene-vinyl acetate copolymer (EVA-1), trade name EVAFREC brand EVA150 MFR: 30 g / 10 minutes, VA contained Amount: 33% by weight and density: 960 kg / m 3　Mitsui-Dupont Polychemical Co., Ltd. was used.
(2-2) Silane-Modified Ethylene-Vinyl Acetate Copolymer The
　silane-modified ethylene-vinyl acetate copolymer (modified EVA) used in Examples was produced in Production Example 1 below.
[0076]
　[Production Example 1]
　Ethylene-vinyl acetate copolymer [Product name Evaflex brand EV260 (MFR: 6 g / 10 minutes, density: 950 kg / m 3 , vinyl acetate content: 28% by mass, manufactured by Mitsui / Dupont Polychemical) 100 parts by mass, vinyl trimethoxysilane: 1.7 parts by mass, dicumyl peroxide: 0.15 parts by mass, and dodecyl mercaptan: 0.03 parts by mass are mixed and supplied to a 65 mmφ multi-screw extruder. After melt-kneading and extrusion at an extrusion temperature of 200 ° C. or higher, the mixture was cooled and pelletized to obtain a silane-modified ethylene-vinyl acetate copolymer (modified EVA).
[0077]
　(3) Saponified
　ethylene / vinyl acetate copolymer As a film made of saponified ethylene / vinyl acetate copolymer, a film having an EVOH product surface F101B [manufactured by Kuraray Co., Ltd.] having a melting point of 180 ° C. and a thickness of 100 μm is used. Used (EVOH film).
[0078]
　The EVOH film was dried under reduced pressure at 100 ° C. for 3 hours before being laminated with NBR, and stored in a package container.
[0079]
　[Example 1]
　(Preparation of NBR composition) As a
　first step, the above NBR is kneaded for 30 seconds using a BB-2 type Banbury mixer (manufactured by Kobe Steel), and then NBR: 100 mass is added. 140 parts by mass of zinc oxide (manufactured by Inoue Lime Industry Co., Ltd.), 40 parts by mass of FEF carbon black (Asahi # 60UG, manufactured by Asahi Carbon Co., Ltd.) and 1 part by mass of stearic acid. Kneaded at ° C for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.
[0080]
　Next, as the second step, the compound obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). 16 rpm, rear roll rotation speed 18 rpm), and 0.7 parts by mass of N-tert-butyl-2-benzothiazolyl sulfeneamide (Noxeller NS-P, Ouchi Shinko Co., Ltd.) ) And 1.5 parts by mass of sulfur were added and kneaded for 10 minutes to obtain an uncrosslinked NBR composition (NBR compound).
[0081]
　(Preparation and evaluation of laminate)
　( Preparation of laminate for T-type peeling test)
　The NBR composition obtained by the preparation of the above NBR composition was dispensed into a sheet. Next, 50 g of the dispensed NBR composition sheet was sandwiched between the upper and lower sides of the copolymer composition sheet with a stretched polyethylene terephthalate film (trade name: Toray). The NBR composition sheet sandwiched between the upper and lower sides of the rumirror film was pressed at 120 ° C. for 2 minutes using a 50-ton press molding machine to prepare an NBR composition sheet having t (thickness) = 1 mm and 20 cm square.
[0082]
　After the press was performed, the NBR composition sheet (layer 1) was cut into the main press dimensions (15 cm × 15 cm × t = 1 mm). After cutting, the upper and lower Lumirror films were peeled off.
[0083]
　The EVOH film (layer 3) dried at 110 ° C. for 3 hours in a vacuum state was cut into the present press dimensions (15 cm × 15 cm × t = 1 mm).
[0084]
　A film (layer 2) having a thickness of 250 μm was prepared using the modified EVA.
[0085]
　Next, the respective sheets (layer 1), film (layer 3) and film (layer 2) were superposed with the layer (2) as an intermediate layer.
[0086]
　When superimposing, the layer (1) and the layer (2) are sandwiched between a part of the layers (width 3 cm, length 15 cm: gripping margin at the time of peeling test) and a lumirror film (t = 0.2 mm). ) And the layer (3) are overlapped, and then the laminated sheet and film having the rumirror film sandwiched in a part thereof are pressed at 180 ° C. for 10 minutes using a 100-ton press molding machine (book). Press) to crosslink the NBR sheet to obtain a laminate having a thickness of 2 mm.
[0087]
　The Lumirror film is removed from the obtained laminate, and the layer between the NBR composition sheet [layer (1)] and the modified EVA layer or the EVA-1 layer [layer (2)], the modified EVA layer or the EVA-1 layer [ The interface between the layer (2)] and the EVOH layer [layer (3)] is peeled off by hand, and the peelability (adhesiveness) is set to 1 without adhesion, and the state where it is firmly adhered and cannot be peeled off by hand. The value was set to 5, and evaluation was performed on a scale of 1 to 5, and the state of the EVOH layer was observed.
[0088]
　The evaluation results are shown in Table 1.
[0089]
　[Example 2] A
　laminate was obtained in the same manner as in Example 1 except that EVA-1 was used instead of the modified EVA used in Example 1. The evaluation results are shown in Table 1.
[0090]
　[Comparative Example 1] In
　Example 1, a sheet (layer 1) and a film (layer 3) were directly laminated to obtain a laminated body without using the modified EVA used for the intermediate layer. The evaluation results are shown in Table 1.
[0091]
　[Example 3]
　Except for using a dicumyl peroxide 40% masterbatch (DCP-40C, manufactured by NOF CORPORATION) in place of the noxeller NS-P and sulfur used in Example 1, the same as in Example 1. The same was performed to obtain a laminate. The evaluation results are shown in Table 1.
[0092]
　[Example 4] A
　laminate was obtained in the same manner as in Example 3 except that EVA-1 was used instead of the modified EVA used in Example 3. The evaluation results are shown in Table 1.
[0093]
　[Comparative Example 2] In
　Example 3, the sheet (layer 1) and the film (layer 3) were directly laminated to obtain a laminated body without using the modified EVA used for the intermediate layer. The evaluation results are shown in Table 1.
[0094]
[Table 1]

　[Example 5]
　(Preparation of NBR composition) As a
　first step, the above NBR was kneaded for 30 seconds using a BB-2 type Banbury mixer (manufactured by Kobe Steel), and then this was added . NBR: 10 parts by mass of silane modified EVA, 5 parts by mass of zinc oxide (manufactured by Inoue Lime Industry Co., Ltd.), and 40 parts by mass of FEF carbon black (Asahi # 60UG, Asahi Carbon Co., Ltd.) with respect to 100 parts by mass. ) And 1 part by mass of stearic acid were kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.
[0095]
　Next, as the second step, the compound obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). N-tert-butyl-2-benzothiazolyl sulphenamide (Noxeller NS-P, Ouchi Shinko Co., Ltd.) ) And 1.5 parts by mass of sulfur were added and kneaded for 10 minutes to obtain an uncrosslinked NBR composition (NBR compound).
[0096]
　(Preparation and evaluation of laminate)
　( Preparation of laminate for T-type peeling test)
　The NBR composition obtained by the preparation of the above NBR composition was dispensed into a sheet. Next, 50 g of the dispensed NBR composition sheet was sandwiched between the upper and lower sides of the copolymer composition sheet with a stretched polyethylene terephthalate film (trade name: Toray). The NBR composition sheet sandwiched between the upper and lower sides of the rumirror film was pressed at 120 ° C. for 2 minutes using a 50-ton press molding machine to prepare an NBR composition sheet having t (thickness) = 1 mm and 20 cm square.
[0097]
　Next, after the press was performed, the NBR composition sheet (layer 1) was cut into the main press dimensions (15 cm × 15 cm × t = 1 mm). After cutting, the upper and lower Lumirror films were peeled off.
[0098]
　Next, the EVOH film (layer 2) dried at 110 ° C. for 3 hours in a vacuum state was cut into the present press dimensions (15 cm × 15 cm × t = 1 mm). Next, each sheet (layer 1) and film (layer 2) were superposed. When stacking, the sheet and film are stacked with the lumirror film (t = 0.2 mm) sandwiched between a part of the NBR composition sheet (width 3 cm, length 15 cm: gripping margin during peeling test). Then, the laminated sheet and film having the rumirror film sandwiched in a part thereof are pressed (main press) at 180 ° C. for 10 minutes using a 100-ton press molding machine to crosslink the NBR sheet. A laminated body having a thickness of 2 mm was obtained.
[0099]
　The Lumirror film is removed from the obtained laminate, the interface between the NBR composition sheet and the EVOH film is peeled off by hand, and the peelability (adhesiveness) is set to 1 without adhesion, and firmly adhered by hand. The state in which the film could not be peeled off was set to 5, and the evaluation was performed on a scale of 1 to 5, and the state of the EVOH film was observed.
[0100]
　The evaluation results are shown in Table 2.
[0101]
　[Example 6]
　Example 5 and Example 5 except that a dicumyl peroxide 40% masterbatch (DCP-40C, manufactured by NOF CORPORATION) is used in place of the noxeller NS-P and sulfur used in Example 5. The same procedure was carried out to obtain an NBR composition and a laminate.
[0102]
　The evaluation results are shown in Table 2.
[0103]
　[Comparative Example 3]
　An NBR composition and a laminate thereof were obtained in the same manner as in Example 5 except that an NBR composition not containing silane-modified EVA was used instead of the NBR composition used in Example 5.
[0104]
　The evaluation results are shown in Table 2.
[0105]
　[Comparative Example 4]
　An NBR composition and a laminate thereof were obtained in the same manner as in Example 6 except that an NBR composition not containing silane-modified EVA was used instead of the NBR composition used in Example 6.
[0106]
　The evaluation results are shown in Table 2.
[0107]
[Table 2]

The scope of the claims
[Claim 1]
　An acrylonitrile-butadiene rubber composition, which comprises 0 to 50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer with respect to 100 parts by mass of the acrylonitrile-butadiene rubber and the acrylonitrile-butadiene rubber.
[Claim 2]
　Lamination characterized in that the acrylonitrile-butadiene rubber layer containing the composition according to claim 1 and the ethylene-vinyl acetate copolymer saponified layer are laminated via the ethylene-vinyl acetate copolymer layer. body.
[Claim 3]
　The laminate according to claim 2, wherein the ethylene-vinyl acetate copolymer layer contains a silane-modified ethylene-vinyl acetate copolymer.
[Claim 4]
　The acrylonitrile-butadiene rubber composition according to claim 1, wherein the acrylonitrile-butadiene rubber and 100 parts by mass of the acrylonitrile-butadiene rubber contain 2 to 50 parts by mass of a silane-modified ethylene-vinyl acetate copolymer. Stuff.
[Claim 5]
　The acrylonitrile-butadiene rubber composition according to claim 1 or 4, further comprising 1.7 to 20 parts by mass of dicumyl peroxide.
[Claim 6]
　A laminate characterized by laminating a layer made of the acrylonitrile-butadiene rubber composition according to claim 4 or 5 and an ethylene-vinyl acetate copolymer saponified layer.