Ethylene-based copolymer composition and its use

Abstract

To provide an ethylene-based copolymer composition which can improve productivity by improving adhesiveness with a layer containing a fiber material, have excellent adhesiveness with a layer containing the fiber material, and moreover can maintain mechanical properties of a laminate obtained.SOLUTION: Provided is an ethylene-based copolymer composition comprising the following (L) and (M): (L) is an ethylene / α-olefin / nonconjugated polyene copolymer containing ethylene [A], a C4-20 α-olefin [B], and a nonconjugated polyene [C], which satisfies the following requirements (1) to (4); and (M) is trans-polyoctenylene: (1) a molar ratio of structural units derived from ethylene [A] to structural units derived from the α-olefin [B], [[A] / [B]], is 40 / 60-90 / 10; (2) a content of structural units derived from the nonconjugated polyene [C] is 0.1-6.0 mole%; (3) a Mooney viscosity, ML(1+4)125°C at 125°C is 5-100; and (4) a B value represented by a specific formula is 1.20 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a crosslinkable ethylene copolymer composition, a laminate using the composition and a layer containing a fibrous material, and uses thereof. [Background technology]

[0002] Ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM generally have excellent weather resistance, heat resistance, and ozone resistance, and are used in industrial automotive parts, industrial rubber products, electrical insulation materials, civil engineering and construction materials, rubberized fabrics, and more.

[0003] Conventional ethylene-α-olefin-non-conjugated polyene copolymers have the disadvantage of inferior adhesion to synthetic fibers compared to polar rubbers such as nitrile rubber, chloroprene rubber, and chlorosulfonated polyethylene. To overcome this drawback, an adhesive solution of a chlorosulfonated copolymer has been disclosed that improves the adhesion between ethylene-α-olefin-non-conjugated polyene copolymers and synthetic fibers (Patent Document 1).

[0004] However, in today's world where environmental issues such as non-halogenation are a major concern, this type of bonding technology that utilizes the polarity of halogenation is hardly optimal. A conventional bonding method involves subjecting synthetic fibers to resorcinol-formaldehyde latex treatment (RFL treatment), then embedding them in rubber for cross-linking and bonding. More specifically, a method using isocyanates or isocyanuric acid derivatives for RFL treatment is known. However, even when these methods are applied to rubbers made from ethylene-α-olefin-non-conjugated polyene copolymers, it is difficult to achieve sufficient adhesion.

[0005] Furthermore, in order to improve compression set resistance, it has been proposed to compound a sulfur-vulcanized ethylene propylene rubber compound in which zinc oxide is compounded with ethylene-α-olefin-diene copolymer and trans-polyoctenylene rubber (Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 42-23632 [Patent Document 2] Patent No. 2528033 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to obtain an ethylene copolymer composition that can improve productivity by improving adhesion to a layer containing a fiber material, has excellent adhesion to a layer containing a fiber material, and can maintain the mechanical properties of the resulting laminate. [Means for solving the problem]

[0008] The present invention relates to an ethylene copolymer composition containing the following (L) and (M), and uses thereof:

[0009] (L) An ethylene-α-olefin-non-conjugated polyene copolymer containing ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C], which satisfies the following requirements (1) to (4): (M) trans polyoctenylene. (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from an α-olefin [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % relative to 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125℃ is 5 to 100, (4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively, and [EX] represents the dyad sequence fraction of ethylene [A] and α-olefin [B] having 4 to 20 carbon atoms.] [Effects of the Invention]

[0010] The ethylene copolymer composition of the present invention has improved adhesion to a layer containing a fiber material when used to produce a laminate, thereby enabling the production rate to be increased. Furthermore, the laminate obtained by crosslinking has excellent adhesive strength, making it suitable for a wide range of uses including hoses, belts, etc. DETAILED DESCRIPTION OF THE INVENTION

[0011] Ethylene-α-olefin-non-conjugated polyene copolymer (L) The ethylene-α-olefin-non-conjugated polyene copolymer (L), which is one of the components constituting the ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition that forms layer [I] of the laminate of the present invention, is an ethylene-α-olefin-non-conjugated polyene copolymer that contains structural units derived from ethylene [A], structural units derived from an α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [C] and satisfies the following requirements (1) to (4). Such a specific ethylene-α-olefin-non-conjugated polyene copolymer is also referred to as "ethylene-based copolymer (L)" and may be abbreviated as "ethylene-based copolymer (L)".

[0012] The α-olefin [B] having 4 to 20 carbon atoms and the non-conjugated polyene [C] may each be used alone or in combination of two or more. That is, the ethylene-α-olefin-non-conjugated polyene copolymer (L) according to the present invention contains structural units derived from ethylene [A], structural units derived from at least one type of α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [C]. (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefin [B] is 40 / 60 to 90 / 10; (2) the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % relative to 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125℃ is 5 to 100, (4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively, and [EX] represents the ethylene [A]-α-olefin [B] having 4 to 20 carbon atoms dyad chain fraction.]

[0013] Examples of the α-olefin [B] having 4 to 20 carbon atoms include 1-butene having 4 carbon atoms, which has a linear structure without side chains, through 1-nonene having 9 carbon atoms and 1-decene having 10 carbon atoms, 1-nonadecene having 19 carbon atoms, and 1-eicosene having 20 carbon atoms, as well as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and the like, which have side chains.

[0014] These α-olefins [B] can be used alone or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferred, with 1-butene, 1-hexene, 1-octene, and the like being particularly preferred, with 1-butene being particularly preferred.

[0015] Specific examples of the non-conjugated polyene [C] include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropylidene-2-norbornene. cyclic non-conjugated dienes such as norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadiene.

[0016] These non-conjugated polyenes [C] can be used alone or in combination of two or more. Among these, linear non-conjugated dienes such as 1,4-hexadiene, and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferred, and cyclic non-conjugated dienes are more preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being particularly preferred.

[0017] Examples of the ethylene copolymer (L) include the following: ethylene-1-butene-1,4-hexadiene copolymer, ethylene-1-pentene-1,4-hexadiene copolymer, ethylene-1-hexene-1,4-hexadiene copolymer, ethylene-1-heptene-1,4-hexadiene copolymer, ethylene-1-octene-1,4-hexadiene copolymer, ethylene-1-nonene-1,4-hexadiene copolymer, ethylene-1-decene-1,4-hexadiene copolymer, and ethylene-1-butene-1-octene-1,4-hexadiene copolymer. , Ethylene·1-butene·5-ethylidene-2-norbornene copolymer, Ethylene·1-pentene·5-ethylidene-2-norbornene copolymer, Ethylene·1-hexene·5-ethylidene-2-norbornene copolymer, Ethylene·1-heptene·5-ethylidene-2-norbornene copolymer, Ethylene·1-octene·5-ethylidene-2-norbornene copolymer, Ethylene·1-nonene·5-ethylidene-2-norbornene copolymer, Ethylene·1-decene·5-ethylidene-2- Norbornene copolymer, ethylene-1-butene-1-octene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene copolymer Nonene-5-vinyl-2-norbornene copolymer, ethylene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-nonene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-decene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-butene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer. One or more types of ethylene copolymers (L) are used as needed.

[0018] The ethylene copolymer (L) according to the present invention satisfies the following requirements (1) to (4). Requirement (1) Component (A) has a molar ratio [[A1] / [A2]] of (1) structural units derived from ethylene [A1] to structural units derived from an α-olefin [A2] having 4 to 20 carbon atoms of 40 / 60 to 90 / 10. Component (A) having a molar ratio within this range exhibits an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature. The lower limit of [A1] / [A2] is preferably 45 / 55, more preferably 50 / 50, and particularly preferably 55 / 45. The upper limit of [A1] / [A2] is preferably 80 / 20, more preferably 75 / 25, and even more preferably 70 / 30.

[0019] Requirement (2) Component (A) contains (2) structural units derived from non-conjugated polyene [A3] in an amount of 0.1 to 6.0 mol %, where the total of the structural units derived from [A1], the structural units derived from [A2], and the structural units derived from [A3] is 100 mol %. Component (A) having this content in the above range has sufficient crosslinkability and flexibility. The lower limit of the content of the structural units derived from [A3] is preferably 0.5 mol %, and the upper limit of the content of the structural units derived from [A3] is preferably 4.0 mol %, more preferably 3.5 mol %, and even more preferably 3.0 mol %. When the content of the structural unit derived from the non-conjugated polyene [C] is within the above range, an ethylene copolymer (L) having sufficient crosslinkability and flexibility can be obtained.

[0020] Requirement (3) Mooney viscosity ML at 125°C (1+4) The temperature at 125°C is in the range of 5 to 100, preferably 20 to 95, and particularly preferably 50 to 90. When the Mooney viscosity is within the above range, the ethylene copolymer (L) has good processability and flowability, and exhibits good post-treatment quality (ribbon handling property), and the ethylene copolymer (L) has excellent physical properties.

[0021] Requirement (4) The B value is 1.20 or more, preferably in the range of 1.20 to 1.80, and particularly preferably in the range of 1.22 to 1.40. An ethylene copolymer having a B value of less than 1.20 has a large compression set at low temperatures, and there is a risk that an ethylene copolymer having an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature cannot be obtained.

[0022] <Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (L)> The ethylene-α-olefin-non-conjugated polyene copolymer (L) according to the present invention can be obtained by various known production methods, for example, a conventionally known production method using a metallocene catalyst. Examples of metallocene catalysts and production methods using such catalysts include those described in WO 2015 / 122415, particularly paragraphs

[0249] to

[0320] of the same publication.

[0023] <<Trans-polyoctenylene (M)>> The trans polyoctenylene (M), which is one of the components constituting the ethylene copolymer composition of the present invention and the ethylene copolymer composition that forms the layer [I] of the laminate of the present invention, is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond. The trans-polyoctenylene (M) according to the present invention is manufactured and sold by Evonik Industries under the trade name VESTENAMER.

[0024] <Ethylene-based copolymer composition> The ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition forming layer [I] of the laminate of the present invention are compositions containing the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymer (L) and the above-mentioned trans-polyoctenylene (M), and preferably contains 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 10 parts by mass of trans-polyoctenylene (M) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0025] The ethylene copolymer composition of the present invention contains trans-polyoctenylene (M) in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L), and therefore has good adhesion to other materials, for example, layers containing fibrous materials such as industrial belts, and the crosslinked laminate has excellent adhesive strength to layers containing fibrous materials.

[0026] In addition to the ethylene copolymer (L) and the trans-polyoctenylene (M), the ethylene copolymer composition of the present invention may contain other components depending on the desired purpose, within the range that does not impair the effects of the present invention. Examples of other components include at least one selected from the group consisting of crosslinking agents, crosslinking aids, vulcanization accelerators, vulcanization aids, fillers, softeners, antioxidants, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. Each of these additives may be used alone, or two or more may be used in combination.

[0027] <Crosslinking Agents, Crosslinking Coagents, Vulcanization Accelerators, and Vulcanization Coagents> Examples of crosslinking agents include those commonly used in crosslinking rubber, such as organic peroxides, phenolic resins, sulfur-based compounds, hydrosilicone-based compounds, amino resins, quinone or its derivatives, amine-based compounds, azo-based compounds, epoxy-based compounds, isocyanate-based compounds, etc. Among these, organic peroxides and sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred.

[0028] Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0029] When an organic peroxide is used as the crosslinking agent, the amount thereof in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the ethylene copolymer (L). When the amount of the organic peroxide is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article, which is preferable.

[0030] When an organic peroxide is used as the crosslinking agent, it is preferable to use a crosslinking aid in combination. Examples of crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; divinylbenzene; and metal oxides such as zinc oxide (e.g., ZnO#1 / zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name, manufactured by Inoue Lime Industry Co., Ltd.)).

[0031] When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, more preferably 1 to 6 mol, per 1 mol of the organic peroxide.

[0032] Examples of sulfur-based compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0033] When a sulfur-based compound is used as a crosslinking agent, the blending amount thereof in the copolymer composition is usually 0.1 to 10 parts by mass, preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass, per 100 parts by mass of the ethylene-based copolymer (L). When the blending amount of the sulfur-based compound is within the above range, there is no blooming on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties.

[0034] When a sulfur-based compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator in combination. Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N'-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (e.g., Suncerer M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noccelaer MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-dinitrophenyl)mercaptobenzothiazole, Thiazole-based vulcanization accelerators such as ethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (e.g., Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, and diorthotolylguanidine; aldehyde-amine-based vulcanization accelerators such as acetaldehyde-aniline condensation product and butyraldehyde-aniline condensation product; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; tetramethylthiuram monosulfide (e.g., Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); thiuram-based vulcanization accelerators such as Sancerer TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (e.g., Sancerer TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (e.g., Sancerer TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutylthiuram disulfide (e.g., Sancerer TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Sancerer TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, diethyldithio Examples of such vulcanization accelerators include dithioacid salt vulcanization accelerators such as zinc carbamate, zinc dibutyldithiocarbamate (for example, Sancerar PZ, Sancerar BZ, and Sancerar EZ (trade names; manufactured by Sanshin Chemical Industry Co., Ltd.)) and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators such as ethylenethiourea (for example, Sancerar BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sancerar 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea; and xanthate-based vulcanization accelerators such as zinc dibutylxatogenate.

[0035] When a vulcanization accelerator is used, the blending amount of the vulcanization accelerator in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the ethylene-based copolymer (L). When the blending amount of the vulcanization accelerator is within the above range, the copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article. When a sulfur-based compound is used as the crosslinking agent, a vulcanization aid can be used in combination.

[0036] Examples of vulcanization aids include zinc oxide (e.g., ZnO#1 / Zinc Oxide Type 2, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)). When a vulcanization aid is used, the amount of the vulcanization aid blended in the ethylene copolymer composition is usually 1 to 20 parts by mass per 100 parts by mass of the ethylene copolymer (L).

[0037] Filler The filler constituting the ethylene copolymer composition of the present invention is a known rubber reinforcing agent compounded in a rubber composition, and is usually an inorganic substance called carbon black or an inorganic reinforcing agent.

[0038] Specific examples of fillers used in the present invention include Asahi #55G and Asahi #60UG (both manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, etc.) carbon black (manufactured by Tokai Carbon Co., Ltd.), these carbon blacks surface-treated with a silane coupling agent or the like, silica, activated calcium carbonate, finely divided talc, finely divided silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, etc.

[0039] These fillers may be used alone or in combination of two or more. As the filler according to the present invention, carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are preferably used.

[0040] When the copolymer composition of the present invention contains a filler, it may be blended in an amount of usually 50 to 300 parts by mass, preferably 80 to 250 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0041] <Softener> Examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic polymeric substances such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others, such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub(factice). Of these, petroleum-based softeners are preferred, and process oil is particularly preferred.

[0042] When the ethylene copolymer composition contains a softener, the amount of the softener is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0043] <Anti-aging agent (stabilizer)> The life of a seal packing formed from the ethylene copolymer composition of the present invention can be extended by blending an antioxidant (stabilizer). Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0044] Examples of antioxidants include aromatic secondary amine antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate antioxidants such as nickel dibutyldithiocarbamate; and sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0045] When the ethylene copolymer composition contains an antioxidant, the amount of the antioxidant is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, per 100 parts by mass of the ethylene copolymer (L). When the amount of the antioxidant is within the above range, no bloom occurs on the surface of the obtained molded article, and furthermore, the occurrence of vulcanization inhibition can be suppressed.

[0046] <Processing aids> As the processing aid, a wide variety of processing aids that are generally compounded in rubber can be used. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters thereof. Of these, stearic acid is preferred.

[0047] When the copolymer composition contains a processing aid, it can be blended in an amount of usually 1 to 3 parts by mass per 100 parts by mass of the ethylene copolymer (L). When the blending amount of the processing aid is within the above range, it is preferable because it provides excellent processability such as kneading processability, extrusion processability, and injection moldability. The processing aid may be used alone or in combination of two or more kinds.

[0048] <Activator> Examples of the surfactant include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triaryl methylate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0049] When the copolymer composition contains an activator, the amount of the activator added is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0050] <Laminate> The laminate of the present invention is a laminate in which a layer [I] made of the ethylene copolymer composition of the present invention is in contact with a layer [II] containing a fibrous material.

[0051] <<Layer [I] Made of Ethylene-Based Copolymer Composition>> The layer [I] made of the ethylene copolymer composition constituting the laminate of the present invention is a layer obtained by crosslinking the above ethylene copolymer composition.

[0052] <Layer containing fibrous material [II]> The layer [II] containing a fibrous material that constitutes the laminate of the present invention contains a fibrous material in at least a portion of the layer.

[0053] <Textile materials> Examples of fiber materials that can form layer [II] according to the present invention include various known fiber materials, such as natural fibers such as cotton and wood cellulose fibers; organic fiber materials such as fibers made of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymers; and inorganic fiber materials such as glass fiber, PAN-based carbon fiber, pitch-based carbon fiber, alumina fiber, silicon carbide fiber, aluminum borate fiber, and potassium titanate whiskers.

[0054] These fiber materials may be long fibers (filaments) or short fibers (staples), and may be cord yarns, spun yarns, woven fabrics, knitted fabrics, canvas, nonwoven fabrics, etc.

[0055] Examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 6,6, and nylon 6,10; semi-aromatic polyamides such as polymetaxylylene adipamide (MXD6), polyhexamethylene terephthalamide (6T), and copolymer polyamides containing these units; and wholly aromatic polyamides such as polybenzamide, poly-p-phenylene terephthalamide, and poly-m-phenylene isophthalamide.

[0056] Furthermore, these fiber materials may be surface-treated by a known method such as RFL treatment in order to improve adhesion between the fiber materials themselves or with the layer [I] made of the ethylene copolymer composition.

[0057] <RFL treatment> RFL treatment involves the adhesive treatment of textile materials using a treatment liquid (RFL liquid) containing resorcinol, formalin, and latex. This RFL liquid is a mixture of the initial condensation product of resorcinol and formalin and rubber latex. Rubber latex can be styrene-butadiene-vinylpyridine terpolymer (VP), styrene-butadiene copolymer (SBR), chloroprene (CR), acrylonitrile-butadiene copolymer (NBR), hydrogenated NBR (H-NBR), chlorosulfonated ethylene (CSM), natural rubber, etc. These can be used alone or in a blend of two or more.

[0058] <Method of manufacturing laminate> The laminate of the present invention can be produced by various known methods for producing laminates. For example, a method of laminating a layer [I] made of an uncrosslinked ethylene copolymer composition produced (molded) in advance by a known method with a layer [II] containing a fibrous material, and then crosslinking the layer [I] made of the ethylene copolymer composition, a method of laminating a layer [I] made of a crosslinked ethylene copolymer composition with a layer [II] containing a fibrous material, or a method of extrusion coating a layer [I] made of an ethylene copolymer composition onto a layer [II] containing a fibrous material, and then crosslinking the layer [I] made of the ethylene copolymer composition, The layer [I] made of the ethylene copolymer composition can be produced by various known methods.

[0059] The ethylene copolymer composition can be obtained by kneading the ethylene-α-olefin-non-conjugated polyene copolymer (L) with the trans-polyoctenylene (M), a crosslinking agent, and, if necessary, additives such as a filler, a softener, an antioxidant, and a processing aid, using any of various known kneading and mixing devices, for example, a Banbury mixer, a kneader, an internal mixer (internal mixer) such as an Intermix, or a roll.

[0060] The uncrosslinked ethylene copolymer composition obtained by kneading may be molded into an intended shape by various molding methods such as an extruder, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then crosslinked to form a layer [I] made of the ethylene copolymer composition, which may then be laminated (bonded) with a layer [II] containing a fiber material; alternatively, the uncrosslinked ethylene copolymer composition may be molded into an intended shape by the above-mentioned method, and then laminated (bonded) with a layer [II] containing a fiber material, followed by crosslinking.

[0061] The layer [I] made of the ethylene copolymer composition may be crosslinked by either a method of heating using a crosslinking agent or a method of irradiating with light, γ rays or electron beams.

[0062] Furthermore, crosslinking may be performed using a mold or without a mold. When a mold is not used, the molding and crosslinking steps are usually performed continuously. Heating methods that can be used in the crosslinking tank include hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, and other heating tanks.

[0063] <<Uses of laminates>> A laminate in which a layer [I] made of the ethylene copolymer composition of the present invention is in contact with a layer [II] containing a fibrous material is suitably used for automobile hoses, water hoses, gas hoses; industrial belts such as transmission belts and conveyor belts; and escalator handrails.

[0064] Examples of the automotive hose include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the transmission belt include a V-belt, a flat belt, a toothed belt, etc. Examples of the conveyor belt include a light conveyor belt, a cylindrical belt, a rough-top belt, a flanged conveyor belt, a U-shaped guided conveyor belt, a V-guided conveyor belt, etc. [Example]

[0065] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The ethylene-α-olefin-non-conjugated polyene copolymer (L) used in the examples of the present invention is shown below.

[0066] [Ethylene-α-olefin-non-conjugated polyene copolymer] An ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer having the following properties was obtained according to the method described in [Synthesis Example C1] of WO 2015 / 122415. Hereinafter, this copolymer will be referred to as "ethylene copolymer (L-1)". The constitution and physical properties of the ethylene copolymer (L-1) are as follows: Structural units derived from ethylene: 67.7 mol% Structural units derived from 1-butene: 30.0 mol% Structural units derived from ENB: 2.3 mol% Mooney Viscosity ML (1+4) 100℃:30 Mooney Viscosity ML (1+4) 125℃:22 B value: 1.3

[0067] [Physical properties of ethylene copolymer (L-1)] <Molar Amounts of Structural Units Derived from Ethylene, Structural Units Derived from α-olefins, and Structural Units Derived from Non-conjugated Polyenes> The molar amount is 1 The intensity was determined by measuring the intensity using a H-NMR spectrometer. Details of the measurement conditions are described in WO 2015 / 122415.

[0068] <Mooney viscosity> Mooney viscosity (ML (1+4) The viscosity at temperatures of 100°C and 125°C was measured using a Mooney viscometer (Shimadzu Corporation, Model SMV202) in accordance with JIS K6300 (1994).

[0069] The measurement solvent was o-dichlorobenzene-d4 / benzene-d6 (4 / 1 [v / v]) at a measurement temperature of 120°C. 13 A C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured, and the value was calculated based on the following formula (i). B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the molar fractions of structural units derived from ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] represents the ethylene [A1]-α-olefin [A2] having 4 to 20 carbon atoms dyad chain fraction.]

[0070] The ethylene-α-olefin-non-conjugated polyene copolymers used in the comparative examples of the present invention are shown below.

[0071] [Ethylene-α-olefin-non-conjugated polyene copolymer] The ethylene-α-olefin-non-conjugated polyene copolymer used was the ethylene-propylene-ENB copolymer (copolymer-2) shown below. Ethylene-Propylene-ENB Copolymer Product name: Mitsui EPT 4045M: Mooney viscosity ML(1+4)100℃=45, ethylene content=45% by weight, diene (ENB) content=7.6% by weight.

[0072] [Trans-polyoctenylene (M)] As the trans-polyoctenylene (M), VESTENAMER 8031, a trade name of Evonik Industries, was used.

[0073] <Physical Properties of Ethylene-Based Copolymer Composition (Cross-Linked Product)> <Durometer A hardness> In accordance with JIS K 6253, the sheet hardness (Type A durometer, HA) was measured using six 2 mm cross-linked sheets with smooth surfaces, stacked on top of each other at the flat part to a thickness of approximately 12 mm. However, specimens containing foreign matter, bubbles, or scratches were not used. The dimensions of the measurement surface of the specimen were such that measurements could be made with the tip of the indenter at a position at least 12 mm away from the edge of the specimen.

[0074] <Tensile stress at break, tensile elongation at break> The tensile stress at break and the tensile elongation at break of the sheet were measured by the following method. The sheet was punched to prepare No. 3 dumbbell test pieces as described in JIS K 6251 (1993). Using these test pieces, tensile tests were carried out according to the method specified in JIS K6251, paragraph 3, at a measurement temperature of 25°C and a tensile speed of 500 mm / min, and the modulus at 100% elongation (M100), tensile stress at break (TB), and tensile elongation at break (EB) were measured.

[0075] <<Physical Properties of Crosslinked Ethylene-Based Copolymer Composition>> (peel strength) The peel strength (adhesion strength) between the layer [I] made of the crosslinked ethylene copolymer composition and the layer [II] containing a fibrous material was measured by the following method.

[0076] A 3 mm thick uncrosslinked sheet was placed on top of an RFL-treated nylon fiber woven fabric (manufactured by Ayaha Kogyo Co., Ltd.), and the uncrosslinked sheet was crosslinked by applying pressure at 170°C for 15 minutes using a 200-ton press molding machine to obtain a laminate. A 25 mm wide test piece was punched out from the laminate, and a T-peel test was performed at a tensile speed of 200 mm / min.

[0077] Example 1 The ethylene copolymer (L-1) was masticated for 30 seconds, and 100 parts by weight of the masticated ethylene copolymer (L-1) was mixed with 5 parts by weight of zinc oxide (ZnO#1) as a crosslinking aid, 1 part by weight of stearic acid as a lubricant, 2 parts by weight of tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane (trade name: Irganox 1010, manufactured by BASFF Japan Co., Ltd.) as an antioxidant, 4 parts by weight of 2-mercaptobenzimidazole (trade name: Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.), 50 parts by weight of carbon black (manufactured by Asahi Carbon Co., Ltd., trade name: Asahi #70), and 10 parts by weight of a softener (trade name: Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.) in a 1.7-liter Banbury mixer (manufactured by Kobe Steel, Ltd.) for 2 minutes. Thereafter, the ram was raised and cleaned, and the mixture was further kneaded for 1 minute and then discharged at about 150° C. to obtain a compound. This kneading was carried out at a filling rate of 70%.

[0078] Next, 172 parts by weight of this compound was wound around an 8-inch roll (surface temperature of front roll: 50°C, surface temperature of rear roll: 50°C, rotation speed of front roll: 16 rpm, rotation speed of rear roll: 18 rpm), and 6.8 parts by weight of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP-40C) and 5 parts by mass of trans-polyoctenylene (M-1) were added as crosslinking agents. The mixture was kneaded for 10 minutes, and then cut into sheets to prepare uncrosslinked sheets with thicknesses of 2 mm and 3 mm.

[0079] The adhesive strength (gf) of the resulting 2 mm thick uncrosslinked sheet was measured by the method described above. The results are shown in Table 1. Next, the resulting 2 mm-thick uncrosslinked sheet was pressed at 170°C for 15 minutes using a 100-ton press to produce a crosslinked sheet. The physical properties of the resulting crosslinked sheet were measured using the methods described above. The results are shown in Table 1.

[0080] [Examples 2 and 3] An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, except that the amount of trans polyoctenylene (M-1) used in Example 1 was changed to 10 parts by mass and 15 parts by mass, and the physical properties and the like were evaluated by the methods described above. The results are shown in Table 1.

[0081] Comparative Example 1 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained in the same manner as in Example 1, except that copolymer-2 was used instead of copolymer (L-1) used in Example 1, and the types and amounts of the compounding agents (additives) were changed to the compounding agents and amounts shown in Table 1, and the physical properties thereof were evaluated by the methods described above. The results are shown in Table 1.

[0082] Comparative Example 2 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, except that the trans-polyoctenylene (M-1) used in Example 1 was not used, and the physical properties thereof were evaluated by the methods described above. The results are shown in Table 1.

[0083] [Table 1]

Claims

1. An ethylene copolymer composition comprising the following (L) and (M), wherein the amount of (M) is 0.5 to 5 parts by mass per 100 parts by mass of (L): (L) An ethylene-α-olefin-non-conjugated polyene copolymer containing ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C], which satisfies the following requirements (1) to (4): (M) trans polyoctenylene. (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from an α-olefin [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol %, based on 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C is 5 to 100, (4) The B value represented by the following formula (i) is 1.20 or more. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], the α-olefin [B] having 4 to 20 carbon atoms, and the non-conjugated polyene [C], respectively, and [EX] represents the dyad sequence fraction of ethylene [A]-α-olefin [B] having 4 to 20 carbon atoms.]

2. 2. The ethylene copolymer composition according to claim 1, wherein the α-olefin [B] having 4 to 20 carbon atoms constituting the ethylene / α-olefin / non-conjugated polyene copolymer (L) is 1-butene.

3. The ethylene copolymer composition according to claim 1 or 2, further comprising (B) an organic peroxide as a crosslinking agent.

4. A laminate comprising a layer [I] made of the ethylene copolymer composition according to any one of claims 1 to 3 and a layer [II] containing a fibrous material in contact with each other.

5. The laminate according to claim 4, wherein the ethylene copolymer composition is crosslinked.

6. The laminate according to claim 4 or 5, wherein the fiber material of the layer [II] comprises RFL-treated fiber.

7. The laminate according to any one of claims 4 to 6, wherein the fiber material of the layer [II] is canvas.

8. An industrial belt comprising the laminate according to any one of claims 4 to 7.

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