Title of the invention: A laminate containing an ethylene / α-olefin / non-conjugated polyene copolymer composition, and an ethylene / α-olefin / non-conjugated polyene copolymer composition.
Technical field
[0001]
　The present invention relates to a laminate of an ethylene / α-olefin / non-conjugated polyene copolymer composition layer having improved adhesive strength and an ethylene / vinyl acetate copolymer saponified layer, and an ethylene / vinyl acetate copolymer. The present invention relates to an ethylene / α-olefin / non-conjugated polyene copolymer composition having excellent adhesive strength with a saponified layer.
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. Ethylene propylene diene copolymer (EPDM) having good ozone resistance, weather resistance, and heat resistance is used for these hoses.
[0003]
　The non-conjugated diene copolymer a vulcanized rubber to a rubber component, 30% of volume resistivity at the time of compression is 10 - For example, Patent Document 1, the ethylene · alpha-olefin 5 with Omega · cm or more A radiator hose using a certain vulcanized rubber as the outermost layer has been proposed.
[0004]
　On the other hand, olefin-based polymers such as ethylene / α-olefin / non-conjugated polyene copolymer are inferior in permeability to volatile substances such as gasoline. Therefore, for example, ethylene / propylene / diene copolymer (EPDM) and ethylene -A laminated resin tubular body for hose inner tubes having a composition layer with a vinyl acetate copolymer saponified product (also referred to as an ethylene / vinyl alcohol copolymer) (Patent Document 2), or an ethylene / vinyl alcohol layer on a thermoplastic elastomer layer. A laminated fuel-based hose (Patent Document 3) or the like in which a copolymer layer is laminated has been proposed.
[0005]
　However, in the laminate described in Patent Document 2, an ethylene-propylene-diene copolymer having an inferior gas barrier property is mixed with an ethylene-vinyl acetate copolymer saponified product having an excellent gas barrier property. There is a risk that the gas barrier property of the vinyl copolymer saponified product will be impaired.
[0006]
　On the other hand, the laminated fuel system hose in which the thermoplastic elastomer layer and the ethylene / vinyl alcohol copolymer layer are laminated has a gas barrier property, but since the thermoplastic elastomer layer is a non-polar polymer, the ethylene / vinyl alcohol co-weight Poor adhesion to the coalesced layer.
Prior art literature
Patent documents
[0007]
Patent Document 1: Japanese Patent Application Laid-Open No. 9-0253774
Patent Document 2: Japanese Patent Application Laid-Open No. 2009-143003
Patent Document 3: Japanese Patent Application Laid-Open No. 2000-329266
Outline of the invention
Problems to be solved by the invention
[0008]
　The present inventors have conducted various studies for the purpose of obtaining an ethylene / α-olefin / non-conjugated polyene copolymer composition having excellent adhesive strength with the ethylene / vinyl acetate copolymer saponified layer.
Means to solve problems
[0009]
　The present invention relates to the following [1] to [7].
[0010]
　[1] Ethylene / α-olefin / non-conjugated polyene copolymer (A), the ethylene / α-olefin / non-conjugated polyene copolymer (A): (1) to (3) with respect to 100 parts by mass. A laminate obtained by laminating a copolymer composition layer containing one or more additives selected from the above and an ethylene / vinyl acetate copolymer saponified product (B) layer.
(1) 1.7 to 20 parts by mass of dicumylperoxide, 2 to 20 parts by mass of metal oxide
(2) 20 to 120 parts by mass of hydrophilic fumed silica
(3) Ethylene / vinyl acetate copolymer (3) 5 to 50 parts by mass
　[2] ethylene / α-olefin / non-conjugated polyene copolymer (A), the ethylene / α-olefin / non-conjugated polyene copolymer (A): 100 parts by mass , 1.7 to 20 parts by mass of dicumylperoxide, and 2 to 20 parts by mass of metal oxide, a copolymer composition layer and an ethylene / vinyl acetate copolymer saponified product (B) layer are laminated. [1] is a laminate.
[0011]
　[3] The laminate according to item [2], wherein the metal oxide is zinc oxide or magnesium oxide.
[0012]
　[4] Ethylene / α-olefin / non-conjugated polyene copolymer (A), the ethylene / α-olefin / non-conjugated polyene copolymer (A): 20 parts by mass of hydrophilic fumed silica. Item 3. The laminate according to Item [1], wherein the copolymer composition layer containing up to 120 parts by mass and the ethylene / vinyl acetate copolymer saponified product (B) layer are laminated.
[0013]
　[5] Item [4] The copolymer composition forming the copolymer composition layer according to the item [4] is a copolymer composition further containing 1.7 to 20 parts by mass of dicumyl peroxide. The laminate described in.
[0014]
　[6] Ethylene / α-olefin / non-conjugated polyene copolymer (A), the ethylene / α-olefin / non-conjugated polyene copolymer (A): an ethylene / vinyl acetate copolymer based on 100 parts by mass. A copolymer composition containing 5 to 50 parts by mass of (C).
[0015]
　[7] Ethylene / α-olefin / non-conjugated polyene copolymer (A), the ethylene / α-olefin / non-conjugated polyene copolymer (A): an ethylene / vinyl acetate copolymer based on 100 parts by mass. Item 3. The laminate according to item [1], wherein a layer composed of a copolymer composition containing 5 to 50 parts by mass of (C) and a layer composed of an ethylene-vinyl acetate copolymer saponified product (B) are laminated.
Effect of the invention
[0016]
　The laminate of the present invention comprises an ethylene-vinyl acetate copolymer saponified (B) layer having excellent gas barrier properties and an ethylene / α-olefin / non-conjugated polyene copolymer (A) having good ozone resistance, weather resistance and heat resistance. ) Is firmly adhered to the copolymer composition layer, so that it can be suitably used for hoses and the like.
[0017]
　Further, the copolymer composition containing the ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention has excellent adhesive strength with the ethylene / vinyl acetate copolymer saponified product (B) layer.
Mode for carrying out the invention
[0018]
　Hereinafter, modes for carrying out the present invention will be described.
[0019]
　<< Ethylene / α-olefin / non-conjugated polyene copolymer (A) >>
　Ethylene / α-olefin / non-conjugated polyene copolymer composition (hereinafter, "copolymer composition" ) forming the laminate of the present invention Ethylene / α-olefin / non-conjugated polyene copolymer (A) constituting (may be abbreviated.) [Hereinafter, it may be abbreviated as "copolymer (A)". ] Is an ethylene / α-olefin / non-conjugated polyene copolymer obtained by randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
[0020]
　The α-olefin is usually an α-olefin having 3 to 20 carbon atoms, and among them, α having 3 to 10 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. -Olefins are preferable, and propylene and 1-butene are particularly preferable.
[0021]
　Specific examples of the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention are preferably an ethylene / propylene / non-conjugated polyene copolymer and an ethylene / 1-butene / non-conjugated polyene copolymer. Used.
[0022]
　The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention usually has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 40/60 to 90/10, preferably 40/60 to 90/10. Those in the range of 50/50 to 80/20, particularly preferably 55/45 to 70/30 are desirable.
[0023]
　As the non-conjugated polyene, a cyclic or chain non-conjugated polyene is used. Examples of the cyclic non-conjugated polyene include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, and methyltetrahydroindene. Examples of chain-like non-conjugated polyenes include 1,4-hexadiene, 7-methyl-1,6-octadene, 8-methyl-4-ethylidene-1,7-nonadien, and 4-ethylidene-1,7-undecadien. And so on. These non-conjugated polyenes are used alone or in admixture of two or more, and the copolymerization amount thereof is preferably 1 to 40, preferably 2 to 35, and more preferably 3 to 30 in terms of iodine value.
[0024]
　The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention usually has an intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C. of 0.8 to 4 dl / g, preferably 1 to 1. It is in the range of 3.5 dl / g, more preferably 1.1 to 3 dl / g.
[0025]
　The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention may be a modified product obtained by graft-copolymerizing an unsaturated carboxylic acid or a derivative thereof, for example, an acid anhydride.
[0026]
　As the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention, an ethylene / propylene / non-conjugated diene copolymer is most preferable.
[0027]
　The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention may be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer (A) having the above-mentioned properties is described in "Polymer Production Process (Published by Industrial Research Council, P.309-330)" and the like. It can be prepared by such a known method.
[0028]
　<< Metal Oxide >> The metal oxide
　contained in the copolymer composition according to the present invention is preferably zinc oxide or magnesium oxide, and the metal oxide may be surface-treated.
[0029]
　<< Dikmyl Peroxide >> Dikmyl peroxide
　contained in the copolymer composition according to the present invention is a kind of organic peroxide used as a cross-linking agent for a polymer.
[0030]
　<< Hydrophilic fumed silica >> The hydrophilic fumed silica
　blended in the copolymer (A) according to the present invention is a kind of dry silica, and the surface thereof is hydrophilic such as siloxane and silanol groups. .. Such hydrophilic fumed silica is manufactured and sold by, for example, Fumed Silica AEROSIL Co., Ltd. under the trade names of AEROSIL 900, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 255, AEROSIL 255, AEROSIL 300, AEROSIL 380, and AEROSILOX 50. There is.
[0031]
　<< Ethylene-vinyl acetate copolymer (C) >>
　The ethylene-vinyl acetate copolymer (C) according to the present invention is a copolymer of ethylene and vinyl acetate, and vinyl acetate present in the copolymer. The content is usually in the range of 5 to 50 parts by weight, preferably 5 to 40 parts by weight. When the vinyl acetate content is within this range, a laminate having excellent adhesive strength with the ethylene-vinyl acetate copolymer saponified product (B) layer can be obtained by blending with the copolymer (A). ..
[0032]
　The melt flow rate (MFR) of the ethylene-vinyl acetate copolymer (C) according to the present invention is usually 1.6 to 6 as measured in accordance with JIS K7210 [190 ° C., 2.16 kg load]. It is in the range of 4 g / 10 minutes, preferably 1.6 to 4.0 g / 10 minutes.
[0033]
　
　The ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention is the ethylene / α-olefin / non-conjugated polyene copolymer (the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer composition. A), The ethylene / α-olefin / non-conjugated polyene copolymer (A): A copolymer composition containing one or more additives selected from (1) to (3) with respect to 100 parts by mass. Is.
(1) 1.7 to 20 parts by mass of dicumylperoxide, 2 to 20 parts by mass of metal oxide
(2) 20 to 120 parts by mass of hydrophilic fumed silica
(3) Ethylene / vinyl acetate copolymer (3) 5 to 50 parts by mass of C) In
　the above-mentioned copolymer composition, the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A): a copolymer containing (1) with respect to 100 parts by mass. The composition is a copolymer composition (1), the copolymer composition containing (2) is a copolymer composition (2), and the copolymer composition containing (3) is a copolymer composition ( When it is referred to as 3) and the whole is shown, it may be referred to as a copolymer composition.
[0034]
　
　The ethylene / α-olefin / non-conjugated polyene copolymer composition forming the laminate of the present invention contains 1.7 to 20 parts by mass of the above dicumylperoxide and a metal oxide. In the case of the composition (1) containing 2 to 20 parts by mass, the dicumylperoxide is 1.7 to 20 parts by mass, preferably 3.4 to 3 parts by mass with respect to 100 parts by mass of the copolymer (A). It contains 10.2 parts by mass and 2 to 20 parts by mass, preferably 2 to 15 parts by mass of the metal oxide.
[0035]
　Since the copolymer composition (1) according to the present invention contains dicumyl peroxide and metal oxide in the above ranges, a laminate having excellent adhesive strength with the saponified ethylene / vinyl acetate copolymer (B) layer can be obtained. Obtainable.
[0036]
　In addition to the above-mentioned dicumyl peroxide and metal oxide, the copolymer composition (1) according to the present invention may be blended with other components according to a desired purpose within a range not impairing the effects of the present invention. it can. 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.
[0037]
　
　The filler constituting the copolymer composition (1) according to the present invention is a known rubber reinforcing agent blended in the rubber composition, and is an inorganic substance usually called carbon black or an inorganic reinforcing agent. Is.
[0038]
　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.
[0039]
　These fillers may be used alone or as a mixture of two or more kinds.
[0040]
　As the filler according to the present invention, carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay and the like are preferably used.
[0041]
　When the copolymer composition (1) according to the present invention contains a filler, it is usually in the range of 100 to 300 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the copolymer (A). It may be mixed with.
[0042]
　
　Examples of the crosslinking aids include sulfur; quinonedioxime-based crosslinking aids such as p-quinonedioxime; acrylics such as ethylene glycol dimethacrylate and trimethylpropantrimethacrylate. Cross-linking aids; allyl-based cross-linking aids such as diallyl phthalate and triallyl isocyanurate; maleimide-based cross-linking aids; divinylbenzene and the like.
[0043]
　Examples of the vulcanization accelerator 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.
[0044]
　When a vulcanization accelerator is used, the blending amount of these vulcanization accelerators in the copolymer composition (1) is generally 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A). It is preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. When the blending amount of the vulcanization accelerator is within the above range, the copolymer composition exhibits excellent cross-linking properties without blooming on the surface of the obtained molded product. When a sulfur-based compound is used as the cross-linking agent, a vulcanization aid can be used in combination.
[0045]
　
　Examples of the softening agent include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; coultal-based softeners such as coltal; Fatty oil-based softeners such as rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or derivatives thereof; Molecular substances; ester-based softeners such as dioctylphthalate and dioctyl adipate; Other examples include microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon synthetic lubricating oil, tall oil, and sub (factis). , Petroleum-based softeners are preferable, and process oils are particularly preferable.
[0046]
　When the copolymer composition (1) according to the present invention contains a softener, the blending amount of the softener is generally 2 to 100 parts by mass, preferably 2 to 100 parts by mass with respect to 100 parts by mass of the copolymer (A). Is 10 to 100 parts by mass.
[0047]
　
　By blending an anti-aging agent (stabilizer) with the copolymer composition 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.
[0048]
　Examples of the anti-aging agent 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] sulfides, etc. Thioether-based anti-aging agent; dithiocarbamate-based anti-aging agent such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, distearyl There are sulfur-based antioxidants such as thiodipropionate.
[0049]
　When the copolymer composition (1) according to the present invention contains an anti-aging agent, the blending amount of the anti-aging agent is usually 0.3 to 0.3 to 100 parts by mass of the copolymer (A). It is 10 parts by mass, preferably 0.5 to 7.0 parts by mass. When the blending amount of the anti-aging agent is within the above range, there is no bloom from the copolymer composition layer of the obtained laminate, and the occurrence of vulcanization inhibition can be further suppressed.
[0050]
　 As the
　processing aid, those generally blended with rubber as a processing aid 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.
[0051]
　When the copolymer composition (1) 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 the copolymer (A). .. 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.
[0052]
　The processing aid may be used alone or in combination of two or more.
[0053]
　
　Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine and monoeranolamine; of diethylene glycol, polyethylene glycol, lecithin, trialilute melilate, aliphatic carboxylic acid or aromatic carboxylic acid. Activators such as zinc compounds; zinc peroxide modifiers; kutadecyltrimethylammonium bromide, synthetic hydrotalcites, special quaternary ammonium compounds.
[0054]
　
　The ethylene / α-olefin / non-conjugated polyene copolymer composition (2) forming the laminate of the present invention is based on 100 parts by mass of the copolymer (A). , A copolymer composition containing 20 to 120 parts by mass, preferably 20 to 100 parts by mass of the above-mentioned hydrophilic fumed silica.
[0055]
　When the copolymer composition (2) contains hydrophilic fumed silica in the above range, a laminate having excellent adhesive strength with the ethylene-vinyl acetate copolymer saponified product (B) layer can be obtained.
[0056]
　In addition to the above-mentioned hydrophilic fumed silica, hydrophobic fumed silica is manufactured and sold as the silica for the reinforcing agent. However, the hydrophobic fumed silica is blended in place of the hydrophilic fumed silica. However, the adhesive strength with the ethylene / vinyl acetate copolymer silica product (B) layer is not improved.
[0057]
　In the copolymer composition (2) according to the present invention, in addition to the above-mentioned hydrophilic fumed silica, other components can be blended according to a desired purpose within a range that does not impair the effects of the present invention. Examples of other components include fillers other than the above-mentioned hydrophilic fumed silica (referred to as other fillers), cross-linking aids, vulcanization accelerators, vulcanization aids, softeners, antistatic agents, processing aids, and the like. It may contain at least one selected from activators, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, colorants, lubricants, thickeners, foaming agents and foaming aids. Also. Each additive may be used alone or in combination of two or more.
[0058]
　The additive contained in the copolymer composition (2) according to the present invention is the same as the compound blended in the copolymer composition (1).
[0059]
　
　Fillers other than the constituent hydrophilic fumed silica to which the copolymer composition (2) of the present invention is blended are known rubber reinforcing agents to be blended in the rubber composition, and are usually carbon black. , It is an inorganic substance called an inorganic reinforcing agent.
[0060]
　When the copolymer composition (2) according to the present invention contains a filler, it is usually in the range of 100 to 300 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the copolymer (A). It may be mixed with.
[0061]
　When a vulcanization accelerator is used, the blending amount of these vulcanization accelerators in the copolymer composition (2) is generally 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A). It is preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. When the blending amount of the vulcanization accelerator is within the above range, the copolymer composition exhibits excellent cross-linking properties without blooming on the surface of the obtained molded product. When a sulfur-based compound is used as the cross-linking agent, a vulcanization aid can be used in combination.
[0062]
　When a vulcanization aid is used, the blending amount of the vulcanization aid in the copolymer composition (2) is usually 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A). ..
[0063]
　When the copolymer composition (2) 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 the copolymer (A). It is a mass part.
[0064]
　When the copolymer composition (2) contains an anti-aging agent, the blending amount of the anti-aging agent is usually 0.3 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A). It is preferably 0.5 to 7.0 parts by mass. When the blending amount of the anti-aging agent is within the above range, there is no bloom on the surface of the obtained molded product, and the occurrence of vulcanization inhibition can be further suppressed.
[0065]
　When the copolymer composition (2) 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 the copolymer (A). 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.
[0066]
　The processing aid may be used alone or in combination of two or more.
[0067]
　When the copolymer composition (2) contains an activator, the blending amount of the activator is usually 0.2 to 10 parts by mass, preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the copolymer (A). It is 0.3 to 5 parts by mass.
[0068]
　
　The ethylene / α-olefin / non-conjugated polyene copolymer composition (3) of the present invention has ethylene / vinyl acetate based on 100 parts by mass of the copolymer (A). A copolymer composition containing 5 to 50 parts by mass, preferably 5 to 40 parts by mass of the copolymer (C).
[0069]
　The ethylene / α-olefin / non-conjugated polyene copolymer composition (3) of the present invention contains an ethylene / vinyl acetate copolymer (C) in the above range to produce an ethylene / vinyl acetate copolymer saponified product (3). B) A laminated body having excellent adhesive strength with the layer can be obtained.
[0070]
　In the copolymer composition (3) according to the present invention, in addition to the above-mentioned ethylene-vinyl acetate copolymer (C), other components are blended according to a desired purpose within a range that does not impair the effects of the present invention. can do. Other components include, for example, fillers, cross-linking agents, cross-linking aids, vulcanization accelerators, vulcanization aids, softeners, anti-aging agents, processing aids, activators, heat-resistant stabilizers, weather-resistant stabilizers, and antistatic agents. It may contain at least one selected from inhibitor, colorant, lubricant, thickener, foaming agent and foaming aid. Also. Each additive may be used alone or in combination of two or more.
[0071]
　The additive contained in the copolymer composition (3) according to the present invention is the same as the compound compounded in the above-mentioned copolymer composition (1) or copolymer composition (2).
[0072]
　When the copolymer composition (3) of the present invention contains a filler, it is usually in the range of 100 to 300 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the copolymer (A). It may be mixed.
[0073]
　When an organic peroxide is used as the cross-linking agent, the blending amount in the copolymer composition (3) is generally 0.1 to 20 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A). Is 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass. When the blending amount of the organic peroxide is within the above range, the copolymer composition (3) exhibits excellent cross-linking properties without blooming on the surface of the obtained molded product, which is preferable.
[0074]
　When a cross-linking aid is used, the blending amount of the cross-linking aid in the copolymer composition (3) is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, based on 1 mol of the organic peroxide. It is mol, more preferably 1-6 mol.
[0075]
　When a sulfur-based compound is used as the cross-linking agent, the blending amount in the copolymer composition (3) is usually 0.3 to 10 parts by mass, preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A). It is 0.5 to 7.0 parts by mass, more preferably 0.7 to 5.0 parts by mass. When the blending amount of the sulfur-based compound is within the above range, there is no bloom on the surface of the obtained molded product, and the copolymer composition (3) exhibits excellent cross-linking characteristics.
[0076]
　When a vulcanization accelerator is used, the blending amount of these vulcanization accelerators in the copolymer composition (3) is generally 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A). It is preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. When the blending amount of the vulcanization accelerator is within the above range, the copolymer composition exhibits excellent cross-linking properties without blooming on the surface of the obtained molded product. When a sulfur-based compound is used as the cross-linking agent, a vulcanization aid can be used in combination.
[0077]
　When a vulcanization aid is used, the blending amount of the vulcanization aid in the copolymer composition (3) is the ethylene / α-olefin / non-conjugated polyene copolymer (A) and, if necessary, blended. It is usually 1 to 20 parts by mass with respect to a total of 100 parts by mass of other polymers (crosslinkable rubber, etc.) that need to be crosslinked.
[0078]
　When the copolymer composition (3) of the present invention contains a softener, the blending amount of the softener is generally 2 to 100 parts by mass, preferably 2 to 100 parts by mass with respect to 100 parts by mass of the copolymer (A). It is 10 to 100 parts by mass.
[0079]
　When the copolymer composition (3) of the present invention contains an anti-aging agent, the blending amount of the anti-aging agent is usually 0.3 to 10 with respect to 100 parts by mass of the copolymer (A). It is by mass, preferably 0.5 to 7.0 parts by mass. When the blending amount of the anti-aging agent is within the above range, there is no bloom on the surface of the obtained molded product, and the occurrence of vulcanization inhibition can be further suppressed.
[0080]
　When the copolymer composition (3) of 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 the copolymer (A). 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.
[0081]
　The processing aid may be used alone or in combination of two or more.
[0082]
　When the copolymer composition (3) of the present invention contains an activator, the blending amount of the activator is usually 0.2 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A). It is preferably 0.3 to 5 parts by mass.
[0083]
　When the copolymer composition (3) of the present invention contains a foaming agent, the blending amount of the foaming agent is appropriately selected depending on the performance required for the molded product produced from the copolymer composition. However, it is usually used in a ratio of 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A).
[0084]
　When the copolymer composition (3) of the present invention contains a foaming aid, the blending amount of the foaming aid is usually 1 to 100 parts by mass, preferably 2 with respect to 100 parts by mass of the foaming agent. It is used in a proportion of up to 80 parts by mass.
[0085]
　 As a method for producing the copolymer composition according to the
　present invention, for example, an internal mixer (sealed mixer) such as a rubbery mixer, a kneader, or an intermix may be used to obtain ethylene. In addition to α-olefin / non-conjugated polyene copolymer rubber (A) and dicumylperoxide and metal oxide, or hydrophilic fumed silica, or ethylene / vinyl acetate copolymer (C), if necessary, a filler. , Softener, processing aid, cross-linking aid, etc. are kneaded at a temperature of 80 to 170 ° C. for 2 to 20 minutes. Next, in the obtained blend, additives such as a cross-linking agent, a softening agent, and a cross-linking aid vulcanization accelerator are added to the obtained blend by using rolls such as open rolls or a kneader, and if necessary, a vulcanization accelerator. , Crosslinking aid can be additionally mixed, kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensed.
[0086]
　When the kneading temperature in the internal mixers is low, dicumyl peroxide may be kneaded at the same time together with ethylene, α-olefin, non-conjugated polyene copolymer rubber (A) and the like.
[0087]
　
　The ethylene-vinyl acetate copolymer saponified product (B) forming the laminate of the present invention is ethylene-vinyl acetate, which is also called an ethylene-vinyl alcohol copolymer. It is a copolymer of ethylene and vinyl alcohol obtained by saponifying a vinyl acetate copolymer.
[0088]
　The ethylene-vinyl acetate copolymer saponified product (B) 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 (B) 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 not limited. It is in the range of 0.5 to 6.4 g / 10 minutes.
[0089]
　Specifically, the ethylene-vinyl acetate copolymer saponified product (B) 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.
[0090]
　<< Laminated product >>
　The laminated body of the present invention is a laminated body in which a layer made of the copolymer composition and a layer made of the saponified ethylene / vinyl acetate copolymer (B) are laminated.
[0091]
　The thickness of the copolymer composition layer of the laminate of the present invention can be appropriately determined depending on the use of the laminate, but is usually 0.03 to 30 mm, preferably 0.05 to 10 mm, more preferably 0.05 to. It is in the range of 5 mm.
[0092]
　The thickness of the ethylene-vinyl acetate copolymer saponified product (B) layer of the laminate of the present invention can be appropriately determined depending on the use of the laminate, but is usually 0.03 to 30 mm, preferably 0.05 to 30 mm. More preferably, it is in the range of 0.05 to 5 mm.
[0093]
　The laminate of the present invention is made of various known materials depending on the use of the laminate, in addition to the layer composed of the copolymer composition and the layer composed of the ethylene-vinyl acetate copolymer saponified product (B). It may have a layer.
[0094]
　Examples of the layer laminated on the layer made of the copolymer composition of the laminate of the present invention or the layer made of the saponified ethylene / vinyl acetate copolymer (B) include NBR and ECO having excellent oil resistance. And so on.
[0095]
　The laminate of the present invention is obtained by coextruding various known molding methods, specifically, for example, a copolymer composition and an ethylene-vinyl acetate copolymer saponified product (B) to obtain a laminate. Method, After extrusion molding or press molding of the copolymer composition and the ethylene / vinyl acetate copolymer sachet (B), respectively, the copolymer composition layer and the ethylene / vinyl acetate copolymer saute (B) ) Layers can be laminated, or by various molding methods such as injection molding, calendar molding, and hollow molding.
[0096]
　By cross-linking the obtained laminate, the cross-linked copolymer composition layer and the ethylene-vinyl acetate copolymer saponified product (B) layer are firmly bonded.
[0097]
　As a method for cross-linking the laminate of the present invention, various known methods can be adopted. For example, the crosslinkable rubber composition according to the present invention is molded into an intended shape by various molding methods such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, and a transfer molding machine, and at the same time as molding or The laminate can be introduced into the cross-linking tank and cross-linked. A crosslinked laminate can be obtained by heating at a temperature of 130 to 250 ° C. for 5 to 60 minutes, or by irradiating with light, γ-rays, or electron beams by the method described above. A mold may be used for this cross-linking step, or the cross-linking may be performed without using a mold. When a mold is not used, the molding and cross-linking steps are usually carried out continuously. As a heating method in the cross-linked tank, a heating tank such as hot air, a fluidized bed of glass beads, UHF (ultra high frequency electromagnetic wave), or steam can be used.
[0098]
　The laminate of the present invention is suitably used for manufacturing, for example, an automobile hose, a water supply hose, a gas hose; Examples of the automobile hose include a brake hose, a radiator hose, a heater hose, and an air cleaner hose.
Example
[0099]
　Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0100]
　The physical characteristics of the copolymers used in Examples and Comparative Examples were measured by the following methods.
[0101]
　(Measurement / evaluation method)
　(Composition of ethylene / α-olefin / non-conjugated polyene copolymer and B value)
　Mass fraction (mass percentage) of each structural unit of ethylene / α-olefin / non-conjugated polyene copolymer ) And B value were determined by the measured values ​​by 13 C-NMR. The measured values ​​were measured using an ECX400P type nuclear magnetic resonance device (manufactured by JEOL Ltd.) at a measurement temperature of 120 ° C., a measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, and an integration number of 8000 times. It was obtained by measuring the 13 C-NMR spectrum of the polymer .
[0102]
　(Ultimate Viscosity [η])
　The ultimate viscosity [η] (dl / g) of ethylene / α-olefin / non-conjugated polyene copolymer is determined by using a fully automatic ultimate viscometer manufactured by Rigo Co., Ltd. ℃, measurement solvent: Measured with decalin.
[0103]
　(Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn))
　Weight average molecular weight (Mw) of ethylene / α-olefin / non-conjugated polyene copolymer, number average molecular weight (Mn), The molecular weight distribution (Mw / Mn) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). The measuring device and conditions are as follows. The molecular weight was calculated based on a conversion method by preparing a calibration curve using commercially available monodisperse polystyrene.
[0104]
　Equipment: Gel permeation chromatograph Alliance GP2000 type (manufactured by Waters),
　Analyst: Emporer2 (manufactured by Waters),
　Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (7.5 mm ID x 30 cm, Tosoh) ,
　Column temperature: 140 ° C.,
　mobile phase: o-dichlorobenzene (containing 0.025% BHT),
　detector: differential refractometer (RI), flow velocity: 1.0 mL / min,
　injection volume: 400 μL ,
　sampling time Interval: 1s,
　Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation),
　Molecular weight conversion: Old method EPR conversion / Calibration method considering viscosity.
(1) Production of Ethylene / α-olefin / Non-conjugated Polyene Copolymer
　[Production Example 1]
　Using a polymerizer having a volume of 300 L equipped with a stirring blade, ethylene, propylene, 5-vinyl-2- The polymerization reaction of norbornene (VNB) was carried out at 87 ° C.
[0105]
　As the polymerization solvent, hexane (feed amount: 32.6 L / h) was used, and the ethylene feed amount was 3.6 kg / h, the propylene amount was 6.1 kg / h, the VNB feed amount was 290 g / h, and so on. The hydrogen feed amount was continuously supplied to the polymerizer so as to be 6.3 NL / h.
[0106]
　Feed amount using di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as the main catalyst while maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 87 ° C. It was continuously supplied to the polymerizer so as to be 0.0015 mmol / h. In addition, (C 6 H 5 ) 3 CB (C 6 F 5 ) 4 (CB-3) as a cocatalyst has a feed amount of 0.0075 mmol / h, and triisobutylaluminum (TIBA) as an organoaluminum compound has a feed amount of 20 mmol / h. Each was continuously supplied to the polymerizer so as to be.
[0107]
　In this way, a solution containing 15.2% by mass of an ethylene / propylene / VNB copolymer formed from ethylene, propylene and VNB was obtained. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, the ethylene / propylene / VNB copolymer was separated from the solvent by steam stripping treatment, and then the pressure was reduced at 80 ° C. for 24 hours. It was dry.
[0108]
　By the above operation, an ethylene / propylene / VNB copolymer (A-1) formed from ethylene, propylene and VNB was obtained at a rate of 4.7 kg / h.
[0109]
　The physical characteristics of the obtained copolymer (A-1) were measured by the method described above. The results are shown in Table 1.
[0110]
[Table 1] In

　Example 3 and Comparative Example 3, the following ethylene / propylene / ENB copolymer [copolymer (A-2)] was used instead of the copolymer (A-1). There was.
[0111]
　(Ethylene / propylene / ENB copolymer)
　Mitsui EPT 2060M: Ethylene / propylene / ENB copolymer, ML (1 + 4) 125 ° C (ASTM D 1646) = 40, ethylene / propylene [molar ratio] = 66/34, ENB Content [% by weight] = 2.3, ultimate viscosity [η] [dl / g] = 2.2.
[0112]
　(Ethylene-vinyl acetate copolymer saponified layer) The
　ethylene-vinyl acetate copolymer saponified layer has an ethylene content of 32 mol% and an MFR of 1.6 g / 10 min. , EVAL (trademark) F101B [manufactured by Kuraray Co., Ltd.] with a thickness of 100 μm (EVOH film) was used.
[0113]
　The EVOH film was dried under reduced pressure at 100 ° C. for 3 hours before being laminated with the copolymer composition layer, and stored in a package container.
[0114]
　[Example 1]
　(Preparation of copolymer composition) As
　the first step, the copolymer (A-1) obtained in Production Example 1 was used using a BB-2 type Banbury mixer (manufactured by Kobe Steel). Is kneaded for 30 seconds, and then the copolymer (A-1): 80 parts by mass with respect to 100 parts by mass of FEF carbon black (Asahi # 60UG, manufactured by Asahi Carbon Co., Ltd.), 5 parts by mass. Zinchua (manufactured by HakusuiTech Co., Ltd.), 1 part by mass of stearic acid, and 50 parts by mass of Diana process oil PS-430 (manufactured by Idemitsu Kosan) were added and 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.
[0115]
　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. A masterbatch (trade name: DCP-40c) containing 40% by mass of dicumylperoxide as an organic peroxide component of 6.8 parts by mass by winding around (16 rpm, rear roll rotation number 18 rpm). (Manufactured by Kayaku Akzo Corporation) (2.72 parts by mass in terms of organic peroxide) was added and kneaded for 10 minutes to obtain an uncrosslinked copolymer composition (composition).
[0116]
　(Preparation and evaluation of laminate)
　( Preparation of laminate for T-type peeling test)
　The copolymer composition obtained by the preparation of the above copolymer composition was dispensed into a sheet. Next, 50 g of the separated copolymer composition sheet was sandwiched between the upper and lower sides of the copolymer composition sheet with a stretched polyethylene terephthalate film (trade name: Lumirror manufactured by Toray Industries, Inc.). A copolymer composition sheet sandwiched between the upper and lower sides of a rumirror film is pressed at 120 ° C. for 2 minutes using a 50-ton press molding machine, and a t (thickness) = 1 mm, 20 cm square copolymer composition sheet. Was produced.
[0117]
　Next, after the press was performed, the copolymer composition sheet (layer 1) was cut into the present press dimensions (15 cm × 15 cm × t = 1 mm). After cutting, the upper and lower Lumirror films were peeled off.
[0118]
　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 sheets and films are laminated with the Lumilar film sandwiched between a part of the copolymer composition sheet (width 3 cm, length 15 cm: gripping margin during peeling test), and then The sheet and the film having the Lumirror film sandwiched in a part thereof are pressed (main press) at 180 ° C. for 10 minutes using a 100-ton press molding machine, and the copolymer composition sheet is crosslinked to a thickness of 2 mm. A laminate was obtained.
[0119]
　The Lumirer film is removed from the obtained laminate, and the layers between the copolymer composition sheet and the EVOH film are manually peeled off, and the peelability (adhesiveness) is set to 1 without adhesion and firmly adhered. The state in which the film could not be peeled off by hand was set to 5, and the evaluation was performed on a scale of 1 to 5.
[0120]
　The evaluation results are shown in Table 2.
[0121]
　[Example 2]
　Instead of the copolymer composition used in Example 1, 5 parts by mass of zinc white (manufactured by HakusuiTech Co., Ltd.) and 5 parts by mass of magnesium oxide (Kyowa Mag 150 (manufactured by Kyowa Chemical Co., Ltd.)) ) Was carried out in the same manner as in Example 1 to obtain a copolymer composition and a laminate.
[0122]
　Table 2 shows the evaluation results of the obtained laminate.
[0123]
　[Example 3] The same
　procedure as in Example 1 was carried out except that the copolymer (A-2) was used in place of the copolymer (A-1) used in Example 1. And a laminate was obtained. Table 2 shows the evaluation results of the obtained laminate.
[0124]
　[Comparative Example 1]
　Instead of the master batch containing 40% by mass of dicumylperoxide used in Example 2, 2,5-Dimethyl-2,5- (t-butylperoxy) hexane: perhexa 25B was used as a cross-linking agent. The same procedure as in Example 1 was carried out except that 3 parts by mass of (manufactured by Nippon Oil & Fats Co., Ltd.) and 3 parts by mass of trimethylolpropane trimethacrylate: Hicross M (manufactured by Seiko Kagaku Co., Ltd.) were used. And a laminate was obtained.
[0125]
　Table 2 shows the evaluation results of the obtained laminate.
[0126]
　[Comparative Example 2] The same as in
　Example 1 except that, instead of the copolymer composition used in Example 1, a copolymer composition containing 40% by mass of dicumylperoxide and not containing a masterbatch is used. To obtain a copolymer composition and a laminate.
[0127]
　Table 2 shows the evaluation results of the obtained laminate.
[0128]
　[Comparative Example 3]
　Instead of the master batch containing 40% by mass of the dicumyl polymer used in Example 3, 1.5 parts by mass of powdered sulfur and tetramethylthium disulfide as a cross-linking agent and a cross-linking aid are used. Noxeller TT-P (TT) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 1 part by mass, and 2-mercaptobenzothiazole Brand name Noxeller MP (M) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 0. The same procedure as in Example 3 was carried out except that 5 parts by mass was used to obtain a copolymer composition and a laminate.
[0129]
　Table 2 shows the evaluation results of the obtained laminate.
[0130]
[Table 2]

　[Example 4]
　(Preparation of copolymer composition) As
　the first step, 30 of the above copolymer (A-1) was used using a BB-2 type Banbury mixer (manufactured by Kobe Steel). Kneading for seconds, then copolymer (A-1): 3 parts by mass of active zinc flower (Meta Z-102, Inoue Lime Industry Co., Ltd.) with respect to 100 parts by mass, 5 parts by mass of FEF. Carbon black (Asahi # 60UG, manufactured by Asahi Carbon Co., Ltd.), 86 parts by mass of hydrophilic fumed silica (AEROSIL200, manufactured by Nippon Aerosil Co., Ltd.), heavy calcium carbonate (Whiten SB red, Shiraishi Calcium Co., Ltd.) And 1 part by mass of stearic acid was 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.
[0131]
　Next, as the second step, the formulation 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). A master batch (trade name: DCP-40c) containing 40% by mass of dicumylperoxide as an organic peroxide component of 6.8 parts by mass by winding around (16 rpm, rear roll rotation number 18 rpm). (Manufactured by Kayaku Akzo) (2.72 parts by mass in terms of organic peroxide), 2-mercaptobenzimidazole (trade name: Nocrack MB, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) 2 parts by mass, pentaerythritol = tetrakis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] (trade name: Irganox1010, manufactured by BASF) 1 part by mass, and paraffin oil (trade name: PW-380, manufactured by Idemitsu Kosan) ) 51 parts by mass was added and kneaded for 10 minutes to obtain an uncrosslinked copolymer composition (copolymer mixture).
[0132]
　(Preparation and evaluation of laminate)
　( Preparation of laminate for T-type peeling test)
　The copolymer composition obtained in the preparation of the above copolymer composition was dispensed into a sheet. Next, 50 g of the separated copolymer composition sheet was sandwiched between the upper and lower sides of the copolymer composition sheet with a stretched polyethylene terephthalate film (trade name: Lumirror manufactured by Toray Industries, Inc.). A copolymer composition sheet sandwiched between the upper and lower sides of a rumirror film is pressed at 120 ° C. for 2 minutes using a 50-ton press molding machine, and a t (thickness) = 1 mm, 20 cm square copolymer composition sheet. Was produced.
[0133]
　Next, after the press was performed, the copolymer composition sheet (layer 1) was cut into the present press dimensions (15 cm × 15 cm × t = 1 mm). After cutting, the upper and lower rumirrors were peeled off.
[0134]
　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 sandwiched between a part of the copolymer composition sheet (width 3 cm, length 15 cm: gripping margin during peeling test) and a lumirror film (t = 0.2 mm). Then, the laminated sheet and film in which the Lumirror film was sandwiched in a part thereof were pressed (main press) at 180 ° C. for 10 minutes using a 100-ton press molding machine to obtain a copolymer. The composition sheet was crosslinked to obtain a laminate having a thickness of 2 mm.
[0135]
　The Lumirror film was removed from the obtained laminate, the interface between the copolymer composition sheet and the EVOH film was peeled off by hand, and the peelability (adhesiveness) was set to 1 without adhesion and firmly adhered. The state in which it could not be peeled off by hand was set to 5, and the evaluation was performed on a scale of 1 to 5.
[0136]
　The evaluation results are shown in Table 2.
[0137]
　[Comparative Example 4 and Comparative Example 5]
　Instead of the copolymer composition used in Example 4, the compounding agent shown in Table 2 is used in the compounding amount shown in Table 2. The following is carried out in the same manner as in Example 4. A laminate was obtained.
[0138]
　The SRF carbon (Asahi 50G) shown in Table 2 is SRF carbon black (Asahi # 50G, manufactured by Asahi Carbon Co., Ltd.), and Aerosil RX200 is hydrophobic fumed silica (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd.). ).
[0139]
　The evaluation results are shown in Table 3.
[0140]
[Table 3]

　(2) Ethylene-vinyl acetate copolymer (C) As
　ethylene-vinyl acetate copolymer (C), trade name EVAFLEC brand EVA150 MFR: 30 g / 10 minutes, VA content: 33% by weight and density. : 960 kg / m 3　Mitsui-DuPont Polychemical Co., Ltd. (EVA150) was used.
[0141]
　[Example 5]
　(Preparation of copolymer composition) As
　the first step, the above copolymer (A-1) is kneaded for 30 seconds using a BB-2 type Banbury mixer (manufactured by Kobe Steel). Then, the copolymer (A-1): 10 parts by mass of EVA-1 with respect to 100 parts by mass, and 3 parts by mass of zinc oxide (Meta Z-102, manufactured by Inoue Lime Industry Co., Ltd.). 1 part by mass of polyethylene glycol (PEG4000, manufactured by Nichiyu Co., Ltd.), 6 parts by mass of calcium oxide (Vesta 18, manufactured by Inoue Lime Industry Co., Ltd.), 3 parts by mass of pentaerythritol tristeer, paraffin wax mixture (d) Master 430W, manufactured by RIKEN Vitamin Co., Ltd., 5 parts by mass of FEF carbon black (Asahi # 60UG, manufactured by Asahi Carbon Co., Ltd.), 86 parts by mass of hexamethyldisilazane-treated silica (Aerodil RX200, EVONIK Co., Ltd.) ), Heavy calcium carbonate (Whiten SB Red, manufactured by Shiraishi Calcium Co., Ltd.) 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.
[0142]
　Next, as the second step, the compound obtained in the first step is subjected to an 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). 2 parts by mass of 2-mercaptobenzimidazole (Nocrack MB, manufactured by Ouchi Shinko Co., Ltd.), and 1 part by mass of pentaerythritol = tetrakis ( 3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate) (Irganox1010, manufactured by BASF Co., Ltd.), 51 parts by mass of Diana Process PW-380 (manufactured by Idemitsu Kosan Co., Ltd.) , 6.8 parts by mass Master batch containing 40% by mass of dicumyl peroxide as an organic peroxide component (trade name: DCP-40c, manufactured by Kayaku Akzo Corporation) (2.72% by mass in terms of organic peroxide) Part) was added and kneaded for 10 minutes to obtain an uncrosslinked copolymer composition (copolymer mixture).
[0143]
　(Preparation and evaluation of laminate)
　( Preparation of laminate for T-type peeling test)
　The copolymer composition obtained in the preparation of the above copolymer composition was dispensed into a sheet. Next, 50 g of the separated copolymer composition sheet was sandwiched between the upper and lower sides of the copolymer composition sheet with a stretched polyethylene terephthalate film (trade name: Lumirror manufactured by Toray Industries, Inc.). A copolymer composition sheet sandwiched between the upper and lower sides of a rumirror film is pressed at 120 ° C. for 2 minutes using a 50-ton press molding machine, and a t (thickness) = 1 mm, 20 cm square copolymer composition sheet. Was produced.
[0144]
　Next, after the press was performed, the copolymer composition sheet (layer 1) was cut into the present press dimensions (15 cm × 15 cm × t = 1 mm). After cutting, the upper and lower rumirrors were peeled off.
[0145]
　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 sandwiched between a part of the copolymer composition sheet (width 3 cm, length 15 cm: gripping margin during peeling test) and a lumirror film (t = 0.2 mm). Then, the laminated sheet and film in which the Lumirror film was sandwiched in a part thereof were pressed (main press) at 180 ° C. for 10 minutes using a 100-ton press molding machine to obtain a copolymer. The composition sheet was crosslinked to obtain a laminate having a thickness of 2 mm.
[0146]
　The Lumirror film was removed from the obtained laminate, the interface between the copolymer composition sheet and the EVOH film was peeled off by hand, and the peelability (adhesiveness) was set to 1 without adhesion and firmly adhered. The state in which it could not be peeled off by hand was set to 5, and the evaluation was performed on a scale of 1 to 5.
[0147]
　The evaluation results are shown in Table 4.
[0148]
　[Example 6] A
　laminate was obtained in the same manner as in Example 5 except that hydrophilic fumed silica (Aerosil 200, manufactured by EVONIK Co., Ltd.) was used instead of Aerosil RX200 used in Example 5. The evaluation results are shown in Table 4.
[0149]
　[Comparative Example 7] A
　laminate was obtained in the same manner as in Example 5 except that Aerosil RX200 and EVA150 were not blended in place of the copolymer composition used in Example 5. The evaluation results are shown in Table 4.
[0150]
　[Comparative Example 8] A
　laminate was obtained in the same manner as in Example 6 except that EVA150 was not blended in place of the copolymer composition used in Example 6. The evaluation results are shown in Table 4.
[0151]
[Table 4]

The scope of the claims
[Claim 1]
　Ethylene / α-olefin / non-conjugated polyene copolymer (A), ethylene / α-olefin / non-conjugated polyene copolymer (A): selected from (1) to (3) with respect to 100 parts by mass. A laminate obtained by laminating a copolymer composition layer containing one or more kinds of additives and an ethylene / vinyl acetate copolymer saponified product (B) layer.
(1) 1.7 to 20 parts by mass of dicumyl peroxide, 2 to 20 parts by mass of metal oxide
(2) 20 to 120 parts by mass of hydrophilic fumed silica
(3) Ethylene-vinyl acetate copolymer (3) C) 5 to 50 parts by mass
[Claim 2]
　Ethylene / α-olefin / non-conjugated polyene copolymer (A), ethylene / α-olefin / non-conjugated polyene copolymer (A): 1.7 to 20 mass by mass of dicumylperoxide with respect to 100 parts by mass. The laminate according to claim 1, wherein the copolymer composition (1) layer containing 2 to 20 parts by mass of parts and a metal oxide and the ethylene / vinyl acetate copolymer saponified product (B) layer are laminated.
[Claim 3]
　The laminate according to claim 2, wherein the metal oxide is zinc oxide or magnesium oxide.
[Claim 4]
　Ethylene / α-olefin / non-conjugated polyene copolymer (A), ethylene / α-olefin / non-conjugated polyene copolymer (A): 20 to 120 parts by mass of hydrophilic fumed silica with respect to 100 parts by mass. The laminate according to claim 1, wherein the copolymer composition (2) layer containing a portion and the ethylene / vinyl acetate copolymer saponified product (B) layer are laminated.
[Claim 5]
　The fourth aspect of the present invention, wherein the copolymer composition (2) forming the copolymer composition layer according to claim 4 is a copolymer composition further containing 1.7 to 20 parts by mass of dicumyl peroxide. Laminated body.
[Claim 6]
　Ethylene / α-olefin / non-conjugated polyene copolymer (A), the ethylene / α-olefin / non-conjugated polyene copolymer (A): ethylene / vinyl acetate copolymer (C) with respect to 100 parts by mass. The copolymer composition (3), which comprises 5 to 50 parts by mass of.
[Claim 7]
　Ethylene / α-olefin / non-conjugated polyene copolymer (A), ethylene / α-olefin / non-conjugated polyene copolymer (A): ethylene / vinyl acetate copolymer (C) with respect to 100 parts by mass. The laminate according to claim 1, wherein a layer composed of the copolymer composition (3) containing 5 to 50 parts by mass and a layer composed of an ethylene-vinyl acetate copolymer saponified product (B) are laminated.