Ethylene copolymer composition and use thereof

Abstract

An object of the present invention is to obtain an ethylene-based copolymer composition which can improve productivity by improving tackiness with a layer containing a fiber material, is excellent in adhesiveness with a layer containing a fiber material, and can maintain mechanical properties of a laminate to be obtained.SOLUTION: An ethylene-based copolymer composition contains a specific ethylene / α - olefin / non-conjugated polyene copolymer (L) containing a structural unit derived from ethylene [A], a structural unit derived from an α - olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C] containing a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II) in a molecule, a trans-polyoctenylene (M), and a crosslinking aid (N) that is an unsaturated carboxylic acid metal salt.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).

[0006] On the other hand, when using a rubber composition containing an ethylene-α-olefin-non-conjugated polyene copolymer such as EPDM for a transmission belt, various attempts have been made to compound this rubber composition with an unsaturated carboxylic acid metal salt in order to enable high-load transmission. For example, Patent Document 3 discloses a rubber composition containing an ethylene-α-olefin elastomer such as EPDM and an unsaturated carboxylic acid metal salt such as zinc dimethacrylate, and also discloses the use of this rubber composition for a transmission belt. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 42-23632 [Patent Document 2] Patent No. 2528033 [Patent Document 3] International Publication No. 2014 / 064879 Summary of the Invention [Problem to be solved by the invention]

[0008] One application of ethylene-α-olefin-non-conjugated polyene copolymers is industrial belts. In industrial belts, ethylene-α-olefin-non-conjugated polyene copolymers are often used in the form of laminates, with a layer containing an ethylene-α-olefin-non-conjugated polyene copolymer and a layer containing a fibrous material in direct contact with each other. Synthetic fibers tend to be used more frequently as the fibrous material. However, the carcass layer of industrial belts (conveyor belts) for this application requires even higher adhesive strength. Therefore, there is a demand for improved adhesive strength between the ethylene-α-olefin-non-conjugated polyene copolymer layer and the fibrous material layer.

[0009] 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]

[0010] As a result of investigations conducted by the present inventors to solve the above-mentioned problems, they found that by using a composition containing an ethylene-propylene-non-conjugated polyene copolymer and trans-polyoctenylene that also contains an unsaturated carboxylic acid metal salt, the adhesion between the composition and a layer containing a fiber material, in particular the adhesion between the composition and a layer containing synthetic fibers, is improved, and they have completed the present invention.

[0011] The present invention relates to the following [1] to

[13] . [1] an ethylene-α-olefin-non-conjugated polyene copolymer (L) comprising 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] containing in the molecule a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II), and satisfying the following requirements (1) to (3); trans polyoctenylene (M), Crosslinking aid (N), which is an unsaturated carboxylic acid metal salt An ethylene-based copolymer composition comprising: [ka] Requirement (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; Requirement (2): The content of the 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 derived from [A], [B], and [C]; Requirement (3): The B value represented by the following formula (i) is 1.20 or more. B value = ([EX] + 2[Y]) / (2 × [E] × ([X] + [Y])) ... Formula (i) [Here, [E], [X], and [Y] represent the molar fractions of structural units derived from 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.] [2] The ethylene copolymer composition according to [1], wherein the α-olefin [B] having 4 to 20 carbon atoms is 1-butene. [3] The ethylene copolymer composition according to [1] or [2], wherein the non-conjugated polyene [C] contains 5-vinyl-2-norbornene. [4] The ethylene copolymer composition according to [1], further comprising an ethylene-α-olefin copolymer (P) (excluding those corresponding to the ethylene-α-olefin-non-conjugated polyene copolymer (L)) containing structural units derived from ethylene [A] and structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms. [5] The ethylene copolymer composition according to [4], comprising 0.1 to 50 parts by mass of the trans-polyoctenylene (M) relative to 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin copolymer (P). [6] The ethylene copolymer composition according to any one of [1] to [5], further comprising an organic peroxide as a crosslinking agent. [7] The ethylene copolymer composition according to [6], wherein the mass ratio of the content of the organic peroxide to the content of the crosslinking aid (N) is 1:10 to 10:1. [8] The ethylene copolymer composition according to any one of [1] to [7], wherein the crosslinking coagent (N) is zinc dimethacrylate. [9] A laminate comprising a layer [I] containing an ethylene-based copolymer composition according to any one of [1] to [8] and a layer [II] containing a fiber material, wherein the layer [I] and the layer [II] are in contact with each other.

[10] The laminate according to [9], wherein the layer [I] is a layer formed by crosslinking the ethylene-based copolymer composition.

[11] The laminate according to [9] or

[10] , wherein the fiber material of the layer [II] contains fibers treated with resorcinol formaldehyde latex (RFL treatment).

[12] The laminate according to any one of [9] to

[11] , wherein the fiber material of the layer [II] is canvas.

[13] An industrial belt comprising the laminate according to any one of [9] to

[12] . [Advantages of the Invention]

[0012] The ethylene-based copolymer composition of the present invention is excellent in adhesion strength (peel strength) to other materials, for example, a layer containing a fiber material (particularly, a synthetic fiber), and thus is suitable as a laminate such as an industrial belt. [Modes for Carrying Out the Invention]

[0013] Hereinafter, the present invention will be described in detail. Here, in this specification, the terms "(co)polymer" and "polymer" are used in a meaning that includes homopolymers and copolymers.

[0014] Also, in this specification, the expression "x to y" (x and y are numerical values. However, x ≠ y) representing a numerical range means "x or more and y or less" when x < y and "x or less and y or more" when x > y, unless otherwise specified.

[0015] In this specification, the term "structural unit derived from ethylene" refers to a structural unit corresponding to ethylene, i.e., a structural unit represented by -CH-CH. The term "structural unit derived from an α-olefin" is similarly interpreted and refers to a structural unit corresponding to an α-olefin, i.e., a structural unit represented by -CH-CRR'- (R and R' are each independently hydrogen or an alkyl group). The term "structural unit derived from a non-conjugated polyene" refers to a structural unit corresponding to a non-conjugated polyene, i.e., a structural unit having one or more pairs of bonds formed by cleavage of the π bond constituting one or more double bonds of the non-conjugated polyene.

[0016] 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 copolymer composition of the present invention, 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]. Here, the non-conjugated polyene [C] contains, in the molecule, a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II). The ethylene-α-olefin-non-conjugated polyene copolymer (L) satisfies the requirements (1) to (3) described below. [ka] Furthermore, the ethylene-α-olefin-non-conjugated polyene copolymer (L) may contain, in addition to the structural units derived from ethylene [A], the structural units derived from the α-olefin [B] having 4 to 20 carbon atoms, and the structural units derived from the non-conjugated polyene [C], a structural unit derived from a non-conjugated polyene [C'] that does not fall under the category of the non-conjugated polyene (C). In this specification, the ethylene-α-olefin-non-conjugated polyene copolymer (L) is also referred to as "ethylene-based copolymer (L)" and may be abbreviated as "copolymer (L)". In addition, in this specification, the α-olefin [B] having 4 to 20 carbon atoms may be abbreviated as "α-olefin [B]". In addition, in this specification, a non-conjugated polyene [C] containing a total of two or more partial structures selected from the group consisting of the general formulas (I) and (II) in the molecule may be abbreviated as "non-conjugated polyene [C]", and a non-conjugated polyene [C'] that does not fall under the category of the non-conjugated polyene (C) may be abbreviated as "non-conjugated polyene [C']".

[0017] 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) used in the present invention contains structural units derived from ethylene [A], structural units derived from at least one α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from at least one non-conjugated polyene [C]. The ethylene-α-olefin-non-conjugated polyene copolymer (L) used in the present invention may further contain structural units derived from at least one non-conjugated polyene [C'].

[0018] The ethylene-α-olefin-non-conjugated polyene copolymer (L) may contain structural units derived from at least one biomass-derived monomer. The biomass-derived monomer used as the raw material for the ethylene copolymer (L) may be biomass-derived ethylene, a biomass-derived α-olefin having 4 to 20 carbon atoms, or a biomass-derived non-conjugated polyene. An example of a biomass-derived α-olefin having 4 to 20 carbon atoms is biomass-derived 1-butene. Examples of biomass-derived non-conjugated polyenes include biomass-derived 5-vinyl-2-norbornene as the non-conjugated polyene [C] and biomass-derived 5-ethylidene-2-norbornene as the non-conjugated polyene [C']. The raw monomers for the ethylene copolymer (L) may contain only biomass-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers. Here, "biomass-derived" means that the monomers are obtained from any renewable natural raw materials, such as those derived from plants or animals, including fungi, yeast, algae, and bacteria, and their residues. Biomass-derived monomers, such as biomass-derived ethylene, biomass-derived α-olefins having 4 to 20 carbon atoms, and biomass-derived non-conjugated polyenes, can be obtained by known methods. For example, biomass-derived ethylene can be obtained by dehydrating ethanol obtained by fermenting a biomass raw material. Biomass-derived 1-butene can be obtained by dehydrating 1-butanol obtained by fermenting a biomass raw material, or by dehydrating 1-butanol obtained by dimerizing ethanol obtained by fermenting a biomass raw material.

[0019] Here, biomass-derived monomers such as biomass-derived ethylene and biomass-derived 1-butene are used as carbon. 14 C isotope 10 -12 ~10 -14 While the corresponding fossil fuel-derived monomers contain 14 Due to the radioactive decay of C 14It is known that biomass-derived monomers do not contain C. Therefore, the difference between biomass-derived monomers and fossil fuel-derived monomers is 14 They can be distinguished by whether or not they contain the C isotope. It is preferable from the viewpoint of reducing the environmental load that the ethylene copolymer (L) contains structural units derived from a biomass-derived monomer.

[0020] The ethylene-α-olefin-non-conjugated polyene copolymer (L) may contain at least one structural unit derived from chemically recycled monomers. The chemically recycled monomers used as raw materials for the ethylene copolymer (L) may be ethylene derived from chemically recycled, α-olefins having 4 to 20 carbon atoms derived from chemically recycled, or non-conjugated polyenes derived from chemically recycled. Furthermore, the raw materials for the ethylene copolymer (L) may contain only chemically recycled monomers, or may contain both chemically recycled monomers and fossil fuel-derived monomers. Here, "chemically recycled" means that the copolymer is obtained by depolymerizing or pyrolyzing a polymer such as waste plastic, or by converting a polymer such as waste plastic into an intermediate by depolymerizing or pyrolyzing, and then using this intermediate as a raw material for production. Chemically recycled monomers, such as ethylene derived from chemically recycled, α-olefins having 4 to 20 carbon atoms derived from chemically recycled, and non-conjugated polyenes derived from chemically recycled, can be obtained by known methods.

[0021] It is preferable that the ethylene copolymer (L) contains structural units derived from chemically recycled monomers from the viewpoint of reducing the environmental load (mainly reducing waste). The ethylene [A] constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) may be only one selected from the group consisting of biomass-derived ethylene, chemically recycled ethylene, and fossil fuel-derived ethylene, or may contain two or more selected from this group. The same applies to the α-olefin [B] having 4 to 20 carbon atoms and the non-conjugated polyene [C].

[0022] The ethylene-α-olefin-non-conjugated polyene copolymer (L) satisfies the following requirements (1) to (3): (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) 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 molar fractions of structural units derived from 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.]

[0023] α-olefins with 4 to 20 carbon atoms [B] Examples of the α-olefins [B] having 4 to 20 carbon atoms that constitute the ethylene-α-olefin-non-conjugated polyene copolymer (L) 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.

[0024] These α-olefins [B] can be used alone or in combination of two or more. That is, the α-olefins [B] having 4 to 20 carbon atoms constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) may be one or more selected from these α-olefins. Among these, α-olefins having 4 to 10 carbon atoms are preferred, with 1-butene, 1-hexene, 1-octene, etc. being particularly preferred, and 1-butene being particularly preferred.

[0025] In a preferred exemplary embodiment of the present invention, the α-olefin [B] includes 1-butene. In this embodiment, the α-olefin [B] is preferably 1-butene. However, the α-olefin [B] may further include, in addition to 1-butene, an α-olefin having 4 to 20 carbon atoms other than 1-butene. Among the "α-olefins having 4 to 20 carbon atoms other than 1-butene," α-olefins having 4 to 10 carbon atoms are preferred, and 1-hexene and 1-octene are more preferred. The α-olefin [B] more preferably consists of 1-butene alone.

[0026] Ethylene-propylene-non-conjugated polyene copolymers in which the α-olefin is propylene have insufficient rubber elasticity at low temperatures, which may limit their applications. On the other hand, the ethylene-α-olefin-non-conjugated polyene copolymer (L) has structural units derived from the α-olefin [B] having 4 to 20 carbon atoms, and therefore has excellent rubber elasticity at low temperatures.

[0027] Non-conjugated polyenes [C] The non-conjugated polyene [C] constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) contains a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II) in the molecule: [ka] That is, the non-conjugated polyene [C] may have two or more partial structures represented by the above general formula (I), may have two or more partial structures represented by the above general formula (II), or may have one or more partial structures represented by the above general formula (I) and one or more partial structures represented by the above general formula (II). In a first preferred exemplary embodiment of the present invention, the non-conjugated polyene [C] contains a total of two or more partial structures selected from the group consisting of the partial structure represented by the above general formula (I) and the partial structure represented by the following general formula (II-1): [CH2=CH-C * H<] …(II-1) (In the above general formula (II-1), C * are carbon atoms that make up the hydrocarbon ring.) In this embodiment, the non-conjugated polyene (C) may have two or more partial structures represented by the above general formula (I), or may have one or more partial structures represented by the above general formula (I) and one or more partial structures represented by the above general formula (II-1). Also, the non-conjugated polyene (C) may have two or more partial structures represented by the above general formula (II-1). In a second preferred exemplary embodiment of the present invention, the non-conjugated polyene [C] has two or more partial structures represented by the above general formula (II). Specific examples of such non-conjugated polyenes [C] include linear non-conjugated dienes such as 1,4-hexadiene and 1,6-octadiene; cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, 5-vinyl-2-norbornene (VNB) and norbornadiene; and trienes such as 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene and 1,4,9-decatriene.

[0028] These non-conjugated polyenes [C] can be used singly or in combination of two or more kinds, that is, the non-conjugated polyene [C] constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) may be one or more kinds selected from these non-conjugated polyenes. Among these, linear non-conjugated dienes such as 1,4-hexadiene and cyclic non-conjugated dienes such as 5-vinyl-2-norbornene (VNB) are preferred, and cyclic non-conjugated dienes are more preferred, with 5-vinyl-2-norbornene (VNB) being particularly preferred.

[0029] In a preferred exemplary embodiment of the present invention, the non-conjugated polyene [C] includes 5-vinyl-2-norbornene. In this embodiment, the non-conjugated polyene [C] may be 5-vinyl-2-norbornene, or may further include, in addition to 5-vinyl-2-norbornene, a non-conjugated polyene other than 5-vinyl-2-norbornene (e.g., cyclohexadiene) that contains a total of two or more partial structures selected from the group consisting of the general formulas (I) and (II) above. For example, the non-conjugated polyene [C] may include 5-vinyl-2-norbornene and a non-conjugated polyene other than 5-vinyl-2-norbornene (e.g., cyclohexadiene) that contains a total of two or more partial structures selected from the group consisting of the partial structure represented by the general formula (I) above and the partial structure represented by the general formula (II-1) above. However, 5-vinyl-2-norbornene is readily available, crosslinks well with organic peroxides, and tends to improve the heat resistance of the copolymer composition, so it is preferable that the non-conjugated polyene [C] consists solely of 5-vinyl-2-norbornene.

[0030] Ethylene-propylene-non-conjugated polyene copolymers in which the α-olefin is propylene have insufficient rubber elasticity at low temperatures, which may limit their applications. On the other hand, the ethylene-α-olefin-non-conjugated polyene copolymer (L) has structural units derived from the α-olefin [B] having 4 to 20 carbon atoms, and therefore has excellent rubber elasticity at low temperatures.

[0031] Non-conjugated polyene [C'] The ethylene-α-olefin-non-conjugated polyene copolymer (L) may contain, in addition to 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 the non-conjugated polyene [C], structural units derived from a non-conjugated polyene [C'] that does not fall under the category of the non-conjugated polyene (C). In an exemplary embodiment of the present invention, the non-conjugated polyene [C'] contains only one partial structure selected from the group consisting of the general formulas (I) and (II) per molecule. However, in a typical embodiment of the present invention, the non-conjugated polyene [C'] contains only one partial structure represented by the general formula (I) per molecule and does not contain a partial structure represented by the general formula (II-1). Alternatively, the non-conjugated polyene [C'] may contain only one partial structure represented by the general formula (II) per molecule and does not contain a partial structure represented by the general formula (I).

[0032] Examples of such non-conjugated polyenes [C'] include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene,

[0033] Examples of such methyl-5-hexenyl-2-norbornene include 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene.

[0033] Among these, 5-ethylidene-2-norbornene (ENB) is preferred because it is readily available, the crosslinking rate during crosslinking with an organic peroxide is easily controlled, and good mechanical properties are easily obtained. The non-conjugated polyene [C'] can be used alone or in combination of two or more. That is, the non-conjugated polyene [C'] that can constitute the ethylene-α-olefin-non-conjugated polyene copolymer (L) may be one or more selected from these non-conjugated polyenes.

[0034] Example of ethylene-α-olefin-non-conjugated polyene copolymer (L) Examples of the ethylene-α-olefin-non-conjugated polyene 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, Ethylene-1-butene-1-octene-1,4-hexadiene copolymer, Ethylene-1-butene-5-vinyl-2-norbornene copolymer, Ethylene-1-pentene-5-vinyl-2-norbornene copolymer, Ethylene-1-hexene-5-vinyl-2-norbornene copolymer, Ethylene-1-heptene-5-vinyl-2-norbornene copolymer, Ethylene-1-octene-5-vinyl-2-norbornene copolymer, Ethylene-1-nonene-5-vinyl-2-norbornene copolymer, Ethylene-1-decene-5-vinyl-2-norbornene copolymer, Ethylene-1-butene-1-octene-5-vinyl-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-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.

[0035] In one preferred exemplary embodiment of the present invention, the ethylene copolymer (L) is an ethylene-1-butene-5-vinyl-2-norbornene copolymer. The ethylene copolymer (L) may be used alone or in combination of two or more types, as required. That is, the ethylene copolymer (L) constituting the ethylene copolymer composition of the present invention may be a single type or a combination of two or more types.

[0036] The ethylene copolymer (L) used in the present invention satisfies the following requirements (1) to (3). <Requirement (1)> The ethylene copolymer (L) has (1) a 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 of 40 / 60 to 90 / 10. The ethylene copolymer (L) having the molar ratio [[A] / [B]] within the above range exhibits an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature. The lower limit of the molar ratio [A] / [B] is preferably 45 / 55, more preferably 50 / 50, even more preferably 55 / 45, and particularly preferably 60 / 40. The upper limit of the molar ratio [A] / [B] is preferably 85 / 15, more preferably 80 / 20, even more preferably 75 / 25, and particularly preferably 70 / 30. The molar ratio [[A] / [B]] is 1 It can be measured using H-NMR.

[0037] <Requirement (2)> The ethylene copolymer (L) (2) has a content of structural units derived from non-conjugated polyene [C] of 0.1 to 6.0 mol % relative to the total of the structural units [A], [B], and [C], i.e., the total of the structural units derived from [A], the structural units derived from [B], and the structural units derived from [C], taken as 100 mol %. The ethylene copolymer (L) having this content in the above range has sufficient crosslinkability and flexibility. The lower limit of the content of the structural units derived from [C] is preferably 0.2 mol%, more preferably 0.3 mol%, and the upper limit of the content of the structural units derived from [C] is preferably 4.0 mol%, more preferably 3.0 mol%, even more preferably 2.0 mol%, and particularly preferably 1.0 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. The content of the structural unit derived from the non-conjugated polyene [C] is 1 It can be measured using H-NMR.

[0038] <Requirement (3)> The ethylene copolymer (L) has a B value represented by the following formula (i) of 1.20 or more, preferably in the range of 1.20 to 1.80, more preferably 1.30 to 1.60, and even more preferably 1.35 to 1.50. B value = ([EX] + 2[Y]) / (2 × [E] × ([X] + [Y])) ... Formula (i) [Here, [E], [X], and [Y] represent the molar fractions of structural units derived from 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.] When the ethylene copolymer (L) has a B value of a certain level or more (for example, 1.20 or more), the compression set at low temperatures tends to be small, and the balance between rubber elasticity at low temperatures and tensile strength at room temperature tends to be excellent. An ethylene copolymer having a B value of less than 1.20 tends to have a large compression set at low temperatures, and there is a risk that an ethylene copolymer having a good balance between rubber elasticity at low temperatures and tensile strength at room temperature will not be obtained. The B value is 13 It can be measured using C-NMR.

[0039] The ethylene copolymer (L) used in the present invention preferably satisfies the following requirement (4) in addition to the above requirements (1) to (3). <Requirement (4)> The ethylene copolymer (L) has a Mooney viscosity of ML at 125°C. (1+4) The temperature at 125°C is preferably in the range of 5 to 100°C, more preferably 10 to 50°C, and even more preferably 15 to 30°C. Mooney viscosity ML (1+4) When the temperature at 125°C 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. Mooney viscosity ML (1+4) The 125°C can be measured at a measurement temperature of 125°C in accordance with JIS K6300 (1994).

[0040] <Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (L)> The ethylene-α-olefin-non-conjugated polyene copolymer (L) used in 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 that publication.

[0041] <<Trans-polyoctenylene (M)>> The trans-polyoctenylene (M), which is one of the components constituting the ethylene copolymer composition 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. Here, cyclooctene can be obtained by dimerizing 1,3-butadiene to obtain cycloocta-1,5-diene, and then hydrogenating this cycloocta-1,5-diene. The ethylene copolymer composition of the present invention contains the trans-polyoctenylene (M), which improves compatibility with fibrous materials, thereby improving tackiness and adhesion to fibrous materials. The trans-polyoctenylene (M) used in the present invention is manufactured and sold by Evonik Industries under the trade name VESTENAMER®.

[0042] Crosslinking aid (N) The ethylene copolymer composition of the present invention contains, in addition to the ethylene copolymer (L) and the trans polyoctenylene (M), a crosslinking aid (N) which is an unsaturated carboxylic acid metal salt (hereinafter referred to as "crosslinking aid (N)"). Here, examples of the unsaturated carboxylic acid metal salt used as the crosslinking aid (N) in the present invention include α,β-unsaturated carboxylic acid metal salts. The α,β-unsaturated carboxylic acid metal salt is preferably at least one compound selected from the group consisting of acrylic acid metal salt, methacrylic acid metal salt, and maleic acid metal salt.

[0043] Examples of the metal acrylates, metal methacrylates, and metal maleates include alkali metal salts (e.g., lithium, sodium, and potassium salts), alkaline earth metal salts (e.g., magnesium and calcium salts), heavy metal salts (e.g., zinc salts), and aluminum salts of acrylic acid, methacrylic acid, and maleic acid, specifically lithium acrylate, sodium acrylate, potassium acrylate, magnesium diacrylate, calcium diacrylate, zinc diacrylate, aluminum triacrylate, lithium methacrylate, sodium methacrylate, potassium methacrylate, zinc methacrylate, magnesium dimethacrylate, calcium dimethacrylate, zinc dimethacrylate, aluminum trimethacrylate, lithium maleate, sodium maleate, potassium maleate, magnesium maleate, zinc maleate, and aluminum maleate. As the α,β-unsaturated carboxylic acid metal salt, zinc methacrylate and zinc dimethacrylate are particularly preferred, with zinc dimethacrylate being most preferred. The α,β-unsaturated carboxylic acid metal salt may be one type alone or a combination of two or more types.

[0044] Ethylene-α-olefin copolymer (P) The ethylene copolymer composition of the present invention may further contain, in addition to the ethylene copolymer (L), the trans-polyoctenylene (M), and the crosslinking coagent (N), an ethylene-α-olefin copolymer (P) (excluding those falling under the ethylene-α-olefin-non-conjugated polyene copolymer (L)) containing structural units derived from ethylene [A] and structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms. In the present invention, this ethylene-α-olefin copolymer (P) can constitute a polymer component together with the ethylene copolymer (L). In the present invention, an ethylene-α-olefin copolymer containing structural units derived from ethylene [A] and structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms, which also falls under the category of the ethylene-α-olefin-non-conjugated polyene copolymer (L), is treated as the ethylene-α-olefin-non-conjugated polyene copolymer (L) and is not treated as the ethylene-α-olefin copolymer (P).

[0045] In this specification, the ethylene-α-olefin copolymer (P) is also referred to as "ethylene-based copolymer (P)" and may be abbreviated as "copolymer (P)".

[0046] Similarly to the ethylene-α-olefin-non-conjugated polyene copolymer (L), the ethylene-α-olefin copolymer (P) may also contain structural units derived from at least one biomass-derived monomer. Similarly, the ethylene-α-olefin copolymer (P) may also contain structural units derived from at least one chemically recycled monomer.

[0047] α-olefins having 3 to 20 carbon atoms [B'] The ethylene-α-olefin copolymer (P) contains, as the α-olefin, an α-olefin [B'] having 3 to 20 carbon atoms (hereinafter, sometimes abbreviated as "α-olefin [B']").

[0048] From the viewpoint of excellent abrasion resistance and adhesive strength, the α-olefin [B'] is preferably an α-olefin having 3 to 12 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms. Specific examples of the α-olefin [B'] include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc. Among these, propylene, 1-butene, 1-hexene, and 1-octene are preferred as the α-olefin [B'], and propylene is more preferred. These α-olefins [B'] may be used singly or in combination of two or more kinds, that is, the ethylene-α-olefin copolymer (P) usable in the present invention may contain one or more kinds of structural units derived from the α-olefin [B'].

[0049] Structure of ethylene-α-olefin copolymer (P) The ethylene-α-olefin copolymer (P) contains structural units derived from ethylene [A] and structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms. The ethylene-α-olefin copolymer (P) may contain other structural units that do not fall under the category of either structural units derived from ethylene [A] or structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms, as long as it does not fall under the category of the ethylene-based copolymer (L). However, the ethylene-α-olefin copolymer (P) does not contain structural units derived from a non-conjugated polyene that fall under the category of the non-conjugated polyene [C] described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)." In a typical embodiment of the present invention, the ethylene-α-olefin copolymer (P) consists solely of structural units derived from ethylene [A] and structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms. In one preferred exemplary embodiment of the present invention, the ethylene-α-olefin copolymer (P) is an ethylene-propylene copolymer.

[0050] In the ethylene-α-olefin copolymer (P), the content of structural units derived from ethylene [A] is preferably 30 to 85 mass%, more preferably 30 to 70 mass%, even more preferably 40 to 60 mass%, and particularly preferably 45 to 55 mass%, based on the total amount of all structural units constituting the ethylene-α-olefin copolymer (P). When the content of structural units derived from ethylene [A] is within the above range, the ethylene-α-olefin copolymer (P) tends to have excellent compatibility with the ethylene copolymer (L) in the resulting ethylene copolymer composition.

[0051] Ethylene-α-olefin copolymer (P) has a Mooney viscosity of ML at 100°C. (1+4) The temperature is preferably in the range of 5 to 100°C, more preferably 20 to 75°C, and even more preferably 30 to 50°C. Mooney viscosity ML (1+4) The 100°C measurement can be performed at a measurement temperature of 100°C in accordance with JIS K6300 (1994).

[0052] When the ethylene-based copolymer composition of the present invention contains an ethylene-α-olefin copolymer (P), the ethylene-α-olefin copolymer (P) that can be contained in the ethylene-based copolymer composition may be one type alone or two or more types.

[0053] <Ethylene-based copolymer composition> The ethylene copolymer composition of the present invention is a composition containing the ethylene-α-olefin-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the crosslinking coagent (N).

[0054] The ethylene-based copolymer composition may further contain the ethylene-α-olefin copolymer (P) in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the crosslinking coagent (N). When the ethylene-based copolymer composition further contains the ethylene-α-olefin copolymer (P), the adhesive strength (peel strength) and abrasion resistance tend to be higher than those of an ethylene-based copolymer composition that does not contain the ethylene-α-olefin copolymer (P). When the ethylene-based copolymer composition of the present invention contains the ethylene-α-olefin copolymer (P), from the viewpoint of excellent abrasion resistance, adhesive strength, etc., the ethylene-based copolymer composition preferably contains the ethylene-α-olefin-non-conjugated polyene copolymer (L) in an amount of 90 to 10 parts by mass, preferably 80 to 20 parts by mass, more preferably 70 to 30 parts by mass, and particularly preferably 60 to 40 parts by mass, and the ethylene-α-olefin copolymer (P) in an amount of 10 to 90 parts by mass, preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and particularly preferably 40 to 60 parts by mass, per 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin copolymer (P).

[0055] The ethylene-based copolymer composition of the present invention contains the trans-polyoctenylene (M) in an amount of preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 2 to 10 parts by mass, and particularly preferably 3 to 8 parts by mass per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin copolymer (P). When the ethylene-based copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass. The ethylene-based copolymer composition of the present invention contains a cross-linking coagent (N) in an amount of typically 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 14 parts by mass, and even more preferably 2 to 12 parts by mass per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin copolymer (P). When the cross-linking coagent (N) is a combination of two or more types, the total amount of all components constituting the cross-linking coagent (N) falls within the aforementioned range. When the ethylene-based copolymer composition does not contain the ethylene-α-olefin copolymer (P), the basis for the 100 parts by mass is the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0056] The ethylene-based copolymer composition of the present invention contains trans-polyoctenylene (M) in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin copolymer (P), 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. Furthermore, since the ethylene copolymer composition of the present invention also contains a cross-linking aid (N), the vulcanization rate tends to be improved and the physical properties of the resulting molded article tend to be good. Specifically, since the ethylene copolymer composition of the present invention contains the cross-linking aid (N), the composition tends to have excellent abrasion resistance and heat aging resistance, and also tends to have a high modulus when vulcanized. Furthermore, since the ethylene copolymer composition of the present invention contains the cross-linking aid (N), the composition tends to have improved tackiness, and for example, improved tackiness and adhesion to fiber materials.

[0057] In addition to the ethylene copolymer (L), the trans-polyoctenylene (M), the crosslinking aid (N), and the optional ethylene copolymer (P), the ethylene copolymer composition of the present invention may contain other components depending on the desired purpose, provided that the effects of the present invention are not impaired. Examples of such other components include other polymers (hereinafter also referred to as "other polymers") that do not fall under the category of either the ethylene copolymer (L) or the ethylene copolymer (P), crosslinking agents, other 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 in combination of two or more.

[0058] <Other polymers> The ethylene copolymer composition of the present invention may contain, in addition to the ethylene copolymer (L), trans-polyoctenylene (M), crosslinking coagent (N), and optionally the ethylene copolymer (P), other polymers (other polymers) that do not fall under the category of the ethylene copolymer (L) or the ethylene copolymer (P). Here, the ethylene copolymer composition of the present invention may contain one kind of such other polymer alone, or may contain two or more kinds of such other polymers.

[0059] <Crosslinking agents, other crosslinking aids, vulcanization accelerators and vulcanization aids> In a typical and preferred embodiment of the present invention, the ethylene-based copolymer composition of the present invention further contains a crosslinking agent in addition to the ethylene-based copolymer (L), trans-polyoctenylene (M), crosslinking coagent (N), and optionally the ethylene-α-olefin copolymer (P). The ethylene-based copolymer composition containing the crosslinking agent may further contain other crosslinking coagents, vulcanization accelerators, or 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, and isocyanate-based compounds. Among these, organic peroxides and sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred, with organic peroxides being more preferred. In the present invention, the ethylene copolymer composition preferably contains an organic peroxide as a crosslinking agent.

[0060] organic peroxide The crosslinking agent that can be contained in the ethylene copolymer composition of the present invention is preferably an organic peroxide. 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, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide. In one preferred exemplary embodiment of the present invention, the organic peroxide is dicumyl peroxide.

[0061] When an organic peroxide is used as a crosslinking agent, the amount of the organic peroxide in the ethylene copolymer composition of the present invention is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1.0 to 5.0 parts by mass, and particularly preferably 2.0 to 4.0 parts by mass, per 100 parts by mass of the total amount of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). 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 resulting molded article, which is advantageous. When the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass. When the ethylene copolymer composition of the present invention contains an organic peroxide, the mass ratio of the content of the organic peroxide to the content of the crosslinking aid (N) in the ethylene copolymer composition is preferably 1:10 to 10:1, more preferably 1:8 to 5:1, even more preferably 1:6 to 3:1, and particularly preferably 1:5 to 2:1. Furthermore, the mass ratio may be, for example, 1:5 to 5:1. When the mass ratio is within the above range, the crosslinking reaction of the ethylene copolymer composition tends to proceed uniformly, which is preferable.

[0062] Other crosslinking aids (crosslinking aids (N')) When an organic peroxide is used as the crosslinking agent, in addition to the crosslinking aid (N), other crosslinking aids (referring to crosslinking aids other than the crosslinking aid (N), also referred to as "crosslinking aid (N')") may be used in combination. Examples of the crosslinking aid (N') include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate (excluding those corresponding to unsaturated carboxylic acid metal salts); allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate (excluding those corresponding to unsaturated carboxylic acid metal salts); maleimide crosslinking aids; divinylbenzene; and metal oxides such as zinc oxide and magnesium oxide. Examples of zinc oxide include zinc oxide type 1 and type 2 specified in JIS K1410 (for example, ZnO#1 / zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), and activated zinc oxide (for example, "META-Z 102" (trade name, manufactured by Inoue Lime Industry Co., Ltd.)).

[0063] When the ethylene copolymer (L) contains the crosslinking aid (N'), the amount of the crosslinking aid (N') in the ethylene copolymer composition is usually 0.5 to 10 mol, preferably 1.0 to 8 mol, more preferably 2.0 to 7 mol, per 1 mol of the organic peroxide.

[0064] Sulfur compounds (vulcanizing agents) The crosslinking agent that can be contained in the ethylene copolymer composition of the present invention may be a sulfur-based compound (vulcanizing agent). Examples of sulfur-based compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0065] When a sulfur-based compound is used as a crosslinking agent, the amount of the sulfur-based compound 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 total amount of the ethylene-based copolymer (L) and the ethylene-α-olefin copolymer (P). When the amount of the sulfur-based compound is within the above range, no bloom occurs on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties. Note that when the ethylene-based copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass.

[0066] Vulcanization accelerators and vulcanization aids When a sulfur-based compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator in combination. That is, when the ethylene-based copolymer composition contains a sulfur-based compound as a crosslinking agent, it is preferable that the ethylene-based copolymer composition further contains a vulcanization accelerator. 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.

[0067] 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 total amount of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). 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. Note that when the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the basis for the 100 parts by mass is the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0068] When a sulfur-based compound is used as a crosslinking agent, a vulcanization aid can be used in combination. That is, when the ethylene-based copolymer composition contains a sulfur-based compound as a crosslinking agent, the ethylene-based copolymer composition may further contain a vulcanization aid.

[0069] An example of the vulcanization aid is activated zinc oxide (for example, "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)). When a vulcanization aid is used, the amount of the vulcanization aid in the ethylene copolymer composition is usually 1 to 20 parts by mass per 100 parts by mass of the total amount of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). When the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the basis for the 100 parts by mass is the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L). In the present invention, the ethylene copolymer composition preferably contains an organic peroxide as a crosslinking agent.

[0070] 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.

[0071] Specific examples of fillers that can be used in the present invention include Asahi #55G, Asahi #60UG, and Asahi #70 (all 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 that have been surface-treated with a silane coupling agent or the like, silica, activated calcium carbonate, finely powdered talc, finely powdered silicic acid, light calcium carbonate, heavy calcium carbonate, talc, and clay.

[0072] These fillers may be used alone or in combination of two or more. The filler used in the present invention preferably includes carbon black, silica, light calcium carbonate, heavy calcium carbonate, talc, and clay, and among these, carbon black and silica are more preferred. In one preferred exemplary embodiment of the present invention, the filler is a combination of carbon black and silica.

[0073] When the copolymer composition of the present invention contains a filler, the amount of the filler is usually 5 to 300 parts by mass, preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, even more preferably 20 to 100 parts by mass, and particularly preferably 30 to 70 parts by mass, per 100 parts by mass of the total amount of the ethylene-based copolymer (L) and the ethylene-α-olefin copolymer (P). When two or more fillers are used as the filler, the total amount of these fillers falls within the above-mentioned range. When the ethylene-based copolymer composition does not contain the ethylene-α-olefin copolymer (P), the basis for the 100 parts by mass is the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0074] <Softener> The ethylene copolymer composition of the present invention may further contain a softener. Examples of the softener 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 coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or derivatives thereof; synthetic polymers such as terpene resin, petroleum resin, and coumarone-indene resin; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factice). Among these, petroleum-based softeners are preferred, and process oil is particularly preferred.

[0075] When the ethylene copolymer composition contains a softener, the amount of the softener is generally 2 to 100 parts by mass, preferably 3 to 50 parts by mass, more preferably 4 to 30 parts by mass, even more preferably 5 to 25 parts by mass, and particularly preferably 6 to 23 parts by mass, per 100 parts by mass of the total amount of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). When the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass.

[0076] <Anti-aging agent (stabilizer)> The ethylene copolymer composition of the present invention often further contains an antioxidant (stabilizer). By blending an antioxidant (stabilizer) with the ethylene copolymer composition of the present invention, the life of the seal packing formed therefrom can be extended. Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0077] Examples of the antioxidant 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 (also known as pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]); Examples of antioxidants include thioether-based antioxidants such as methyl-4-(3-n-alkylthiopropionyloxy)-5-tert-butylphenyl]sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; and sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate. Suitable examples of the antioxidants include the phenol-based antioxidants (e.g., tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate]methane dicumyl peroxide) and the sulfur-based antioxidants (e.g., 2-mercaptobenzimidazole), as well as combinations thereof.

[0078] When the ethylene copolymer composition contains an antioxidant, the amount of the antioxidant is typically 0.3 to 10 parts by mass, preferably 0.5 to 9.0 parts by mass, more preferably 1.0 to 8.0 parts by mass, and even more preferably 2.0 to 7.0 parts by mass, per 100 parts by mass of the total amount of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). When the amount of the antioxidant is within the above range, the resulting molded article is free of bloom on the surface and vulcanization inhibition can be suppressed. When the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass.

[0079] The ethylene copolymer composition may contain one antioxidant alone or two or more antioxidants in combination. When two or more antioxidants are used, the total amount of these antioxidants falls within the range described above as the blending amount.

[0080] <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.

[0081] When the ethylene copolymer composition contains a processing aid, the amount of the processing aid is typically 0.01 to 10 parts by mass, preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, even more preferably 0.3 to 2.0 parts by mass, and particularly preferably 0.4 to 1.5 parts by mass, per 100 parts by mass of the combined total of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). When the amount of the processing aid is within the above range, excellent processability, such as kneading processability, extrusion processability, and injection moldability, is achieved, which is advantageous. When the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass. The processing aid may be used alone or in combination of two or more kinds.

[0082] <Activator> Examples of the surfactant include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0083] When the copolymer composition contains an activator, the amount of the activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the total amount of the ethylene copolymer (L) and the ethylene-α-olefin copolymer (P). When the ethylene copolymer composition does not contain the ethylene-α-olefin copolymer (P), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) is used as the basis for the 100 parts by mass.

[0084] <Method for producing ethylene copolymer composition> The ethylene copolymer composition of the present invention can be obtained by a production method including a step of kneading the ethylene-propylene-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and, if necessary, a processing aid, other crosslinking aid (crosslinking aid (N')), an antioxidant, a filler, and the like, for example, at 80 to 160°C for 1 to 3 minutes using an internal mixer (internal mixer) such as a Banbury mixer, kneader, or intermix. The ethylene copolymer composition containing the crosslinking agent can be obtained by kneading components that do not fall under the category of either the crosslinking aid (N) or the crosslinking agent (for example, the ethylene-propylene-non-conjugated polyene copolymer (L) and the trans-polyoctenylene (M), and optional other crosslinking aid (crosslinking aid (N')), optional processing aid, optional antioxidant, and optional filler) at 80 to 160°C for 1 to 3 minutes in the kneading step, and then kneading the blend obtained by this step. The crosslinking aid (N) and additives such as the crosslinking agent are added to the compound (compound) using rolls such as open rolls or a kneader, and if necessary, a vulcanization accelerator and other crosslinking aids (crosslinking aid (N')) are added and mixed, and the mixture is kneaded usually at a roll surface temperature of 40 to 80°C for 5 to 30 minutes, preferably at a temperature of 40 to 70°C for 6 to 25 minutes, more preferably at a temperature of 45 to 65°C for 7 to 20 minutes, and even more preferably at a temperature of 45 to 60°C for 8 to 15 minutes, and then a separating step is further carried out to prepare the compound.

[0085] In addition, when the kneading temperature in an internal mixer is low, the crosslinking agent may be kneaded simultaneously with components other than the crosslinking agent, such as the ethylene-propylene-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the crosslinking aid (N).

[0086] <Laminate> The laminate of the present invention is a laminate in which a layer [I] containing the ethylene-based copolymer composition of the present invention is in contact with a layer [II] containing a fibrous material. That is, the laminate of the present invention includes a layer [I] containing the ethylene-based copolymer composition and a layer [II] containing a fibrous material, and the layer [I] and the layer [II] are in contact with each other.

[0087] <<Layer [I] Containing Ethylene-Based Copolymer Composition>> Layer [I] constituting the laminate of the present invention contains the above-mentioned ethylene-based copolymer composition. In a typical embodiment of the present invention, the layer [I] is a layer made of the ethylene-based copolymer composition. The layer [I] is preferably a layer made by crosslinking the above-mentioned ethylene-based copolymer composition, i.e., a layer made of a crosslinked product of the above-mentioned ethylene-based copolymer composition.

[0088] <Layer containing fibrous material [II]> The layer [II] constituting the laminate of the present invention contains a fibrous material. This layer [II] contains a fibrous material in at least a part of the layer.

[0089] <Textile materials> Examples of the fiber material forming the layer [II] used in the present invention include various known fiber materials, such as natural fibers such as cotton, hemp, flax (linen), 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 whisker.

[0090] 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.

[0091] 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.

[0092] In one preferred and exemplary embodiment of the present invention, the fiber material forming the layer [II] is canvas. Canvas is a thick, plain-woven fabric, often made from cotton, hemp, or linen. In another preferred and exemplary embodiment of the present invention, the fiber material forming the layer [II] is a woven fabric of nylon fibers.

[0093] 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.

[0094] <RFL treatment> The fiber material forming the layer [II] used in the present invention may contain fibers that have been treated with resorcinol formaldehyde latex (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.

[0095] A textile material containing resorcinol-formaldehyde latex-treated (RFL-treated) fibers can be obtained by subjecting a corresponding textile material that has not yet been RFL-treated to an RFL treatment.

[0096] <Method of manufacturing laminate> The laminate of the present invention can be produced by various known methods for producing laminates, such as the following methods (a) to (e): (a) A method of laminating a layer [I] made of an uncrosslinked ethylene copolymer composition previously produced (molded) by a known method with a layer [II] containing a fibrous material; (b) A method in which a layer [I] made of an uncrosslinked ethylene copolymer composition previously produced (molded) by a known method is laminated with a layer [II] containing a fiber material, and then the layer [I] made of the ethylene copolymer composition is crosslinked; (c) a method of laminating a layer [I] made of a crosslinked ethylene copolymer composition and a layer [II] containing a fibrous material; (d) a method of extrusion coating a layer [I] comprising an ethylene copolymer composition onto a layer [II] comprising a fibrous material; (e) A method in which a layer [I] made of an ethylene-based copolymer composition is extrusion coated onto a layer [II] containing a fiber material, and then the layer [I] made of an ethylene-based copolymer composition is crosslinked. The layer [I] made of the ethylene copolymer composition can be produced by various known methods.

[0097] 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.

[0098] 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 fibrous 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 fibrous material, followed by crosslinking.

[0099] The layer [I] made of the ethylene copolymer composition may be crosslinked by heating using a crosslinking agent or by irradiating with light, gamma rays or electron beams.

[0100] 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.

[0101] <<Uses of laminates>> The laminate of the present invention is suitable for use in automobile hoses, water hoses, gas hoses, industrial belts such as transmission belts and conveyor belts, and escalator handrails. In a preferred exemplary embodiment of the present invention, the laminate of the present invention is used in an industrial belt. In this embodiment, the industrial belt comprises the laminate.

[0102] 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 guide conveyor belt, a V-guide conveyor belt, etc. [Example]

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" means "parts by mass" unless otherwise specified.

[0104] [Measurement and evaluation method] In the following examples and comparative examples, the methods for measuring and evaluating the various physical properties and characteristics are as follows.

[0105] (1) Physical properties of ethylene-α-olefin-non-conjugated polyene copolymer (L) <Composition of ethylene-α-olefin-non-conjugated polyene copolymer (L)> The molar amount of each structural unit constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) is 1 The intensity was measured using a H-NMR spectrometer (400 MHz, JEOL ECX400P). 1The intensity measurement using the H-NMR spectrometer was carried out under the measurement conditions described in International Publication No. 2015 / 122415, specifically, o-dichlorobenzene-d4 was used as the measurement solvent, the measurement temperature was 120°C, the spectral width was 20 ppm, the pulse repetition time was 7.0 seconds, and the pulse width was 6.15 μsec (45° pulse). 1 The molar amount of each structural unit was calculated based on the integrated value of the relevant peak observed in the H-NMR spectrum. The calculated content (mol%) was rounded to one decimal place.

[0106] <Mooney viscosity> Mooney viscosity (ML (1+4) 100℃ and ML (1+4) The viscosity (ML 125°C) was measured using a Mooney viscometer (Shimadzu Corporation, Model SMV202) in accordance with JIS K6300 (1994). (1+4) At 100°C, ML (1+4) At 125°C, the temperature was set to 125°C.

[0107] 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 [A], structural units derived from an α-olefin having 4 to 20 carbon atoms [B], and structural units derived from a non-conjugated polyene [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A]-α-olefin having 4 to 20 carbon atoms [B].]

[0108] (2) Physical Properties of Uncrosslinked Ethylene Copolymer Composition <Adhesion measurement (probe tack test)> The probe tack test was carried out using a probe tack tester as follows. A 1 mm thick uncrosslinked sheet was used as a test specimen and fixed to a probe tack tester. Next, the bottom surface of a cylindrical probe (a stainless steel probe with a diameter of 5 mm) was brought close to one side of the test specimen at a constant speed and kept in contact with it. The cylindrical probe was then pressed into the test specimen until a constant load was applied to the test specimen, which was then held for a certain time. Immediately thereafter, the cylindrical probe was peeled off from the test specimen at a constant speed while measuring the test force.

[0109] The process was carried out under the following conditions: Approach speed: 120mm / min. Pressure: 100g Pressurization time: 20 seconds. Peeling speed: 120mm / min. Temperature at which the probe and test piece (uncrosslinked sheet) are placed: 23°C In the curve showing the relationship between the test force and time measured during the above process, the peak value (gf) (corresponding to the maximum load required to peel the cylindrical probe from the test piece) was determined as the minimum value when the force on the pushing side was taken as positive. The tackiness was evaluated based on the absolute value of the peak value.

[0110] (3) Physical Properties of Ethylene-Based Copolymer Composition (Crosslinked 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.

[0111] <Modulus, 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 specified 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. The modulus at 200% elongation (M200), tensile stress at break (TB), and tensile elongation at break (EB) were measured.

[0112] <Heat aging resistance> The sheet was subjected to a heat aging test in which it was held at 180°C for 72 hours (hrs) in accordance with JIS K 6257. After the heat aging test, the hardness, tensile stress at break (MPa), and tensile elongation at break (%) of the sheet were measured in the same manner as in the above-mentioned [Durometer A hardness] and [Modulus, tensile stress at break, and tensile elongation at break] items.

[0113] AH (Duro-A) was calculated from the difference in hardness before and after the heat aging test, and Ac(TB) and Ac(EB) were calculated from the tensile stress at break (TB) and tensile elongation at break (EB) before and after the heat aging test, respectively, to determine the rate of change after the test relative to the values ​​before the heat aging test. Here, AH, Ac(TB), and Ac(EB) are specifically values ​​shown in the following formula: AH=HA1-HA0 HA1: Durometer A hardness measured after heat aging test HA0: Durometer A hardness measured before heat aging test Ac(TB)(%) = (TB1-TB0) / TB0 × 100 TB1: TB measured after heat aging test TB0: TB measured before heat aging test Ac(EB)(%) = (EB1-EB0) / EB0 × 100 EB1: EB measured after heat aging test EB0: EB measured before heat aging test

[0114] <DIN friction test (amount of wear)> In accordance with JIS-K6264-2:2005, three 2 mm thick crosslinked sheets were stacked to prepare a disc-shaped test piece with a diameter of 16.0 ± 0.2 mm and a thickness of 6 mm. The test piece was then subjected to a DIN abrasion test using a drum with a diameter of 150.0 ± 0.2 mm and a length of 500 mm, which was rotated at 40 rpm under a load of 1 kgf over an abrasion distance of 40.0 ± 0.2 m. The abrasion loss (DIN abrasion loss: unit: mm) was measured. 3 ) was measured.

[0115] <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.

[0116] 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 50 mm / min to determine the peel strength (adhesion strength) (N / cm). The peel test was carried out three times, and the average value was taken as the peel strength.

[0117] [Major constituents used in the examples] In the examples and comparative examples, the ethylene-based copolymer compositions were composed of the ethylene-α-olefin-non-conjugated polyene copolymer (L), trans-polyoctenylene (M), crosslinking aid (N), and optional ethylene-α-olefin copolymer (P), as shown below.

[0118] (1) Ethylene-α-olefin-non-conjugated polyene copolymer (L) As the ethylene-α-olefin-non-conjugated polyene copolymer (L), the copolymer (L-1) obtained in Production Example 1 below was used.

[0119] [Manufacturing Example 1] A copolymerization reaction of ethylene, 1-butene, and 5-vinyl-2-norbornene (VNB) was carried out continuously at 95°C using a 300 L volume polymerization vessel equipped with a stirring blade.

[0120] Hexane (feed rate: 30.5 L / h) was used as the polymerization solvent and continuously supplied to the polymerization reactor so that the ethylene feed rate was 5.3 kg / h, the 1-butene feed rate was 21.5 kg / h, the VNB feed rate was 566 g / h, and the hydrogen feed rate was 10 NL / h.

[0121] The polymerization pressure was maintained at 1.6 MPaG and the polymerization temperature at 95°C. Di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride was continuously fed to the polymerization reactor at a feed rate of 0.00903 mmol / h. The cocatalyst (C6H5)3CB(C6F5)4 was continuously fed at a feed rate of 0.045 mmol / h, and triisobutylaluminum (TIBA) was continuously fed to the polymerization reactor at a feed rate of 30 mmol / h.

[0122] In this way, a solution containing 20% ​​by mass of ethylene-1-butene-VNB copolymer formed from ethylene, 1-butene, and VNB was obtained. A small amount of methanol was added to the polymerization reaction mixture withdrawn from the bottom of the polymerization reactor to terminate the polymerization reaction. The ethylene-1-butene-VNB copolymer was separated from the solvent by steam stripping and then dried under reduced pressure at 80°C overnight.

[0123] By the above procedure, ethylene-1-butene-VNB copolymer (hereinafter referred to as "ethylene copolymer (L-1)" or "copolymer (L-1)") was obtained at a rate of 8.5 kg / h. The physical properties of the copolymer (L-1) obtained were measured by the method described above. The constitution and physical properties of the copolymer (L-1) are shown in Table 1 below.

[0124] [Table 1]

[0125] (2) trans-polyoctenylene (M) As the trans-polyoctenylene (M), VESTENAMER (registered trademark) 8012, a trade name of Evonik Industries, was used.

[0126] (3) Crosslinking aid (N) As the unsaturated carboxylic acid metal salt constituting the crosslinking aid (N), zinc dimethacrylate (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name: Actor ZMA) was used.

[0127] (4) Ethylene-α-olefin copolymer (P) The ethylene-α-olefin copolymer (P) used was the following ethylene-propylene copolymer (P-1) (hereinafter sometimes referred to as "ethylene copolymer (P-1)"). Ethylene-propylene copolymer (P-1) Product name: Mitsui EPT 0045: Mooney Viscosity ML (1+4) 100°C = 40, content (content) of structural units derived from ethylene = 51% by mass.

[0128] Example 1 100 parts by mass of the ethylene copolymer (L-1) was masticated for 30 seconds, and the masticated ethylene copolymer (L-1) was 5 parts by mass of VESTENAMER (registered trademark) 8012 (manufactured by Evonik) as trans polyoctenylene (M), As other cross-linking aids (cross-linking aids (N')), 5 parts by mass of zinc oxide (ZnO#1, zinc oxide type 2, manufactured by Hakusui Tech Co., Ltd.) 1 part by mass of stearic acid (product name: Powdered Stearic Acid Sakura, manufactured by NOF Corporation) as a processing aid (lubricant), As antioxidants, 2 parts by mass of tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane (trade name Irganox 1010, manufactured by BASF Japan Ltd.; hereinafter referred to as "antioxidant 1") and 4 parts by mass of 2-mercaptobenzimidazole (trade name Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.; hereinafter referred to as "antioxidant 2") were used. 40 parts by mass of carbon black (trade name Asahi #70 manufactured by Asahi Carbon Co., Ltd.; hereinafter referred to as "Carbon Black 1"), 10 parts by mass of silica (ULTRASIL VN2 manufactured by Evonik), As a softener, 10 parts by mass of paraffin oil (trade name: Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.; hereinafter referred to as "softener 1") was used. The mixture was mixed for 2 minutes in a 1.7-liter Banbury mixer (manufactured by Kobe Steel, Ltd.). The ram was then raised and cleaned, and the mixture was mixed for another minute and discharged at approximately 150°C to obtain a compound (Compound 1). This mixing was carried out at a filling rate of 70%.

[0129] Next, 177 parts by mass 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). As a crosslinking agent, 6.8 parts by mass of an organic peroxide (dicumyl peroxide (40% masterbatch, manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP-40C)) As a crosslinking aid (N), 2.4 parts by mass of zinc dimethacrylate (manufactured by Kawaguchi Chemical Industry Co., Ltd., product name Actor ZMA) was added and kneaded for 10 minutes to obtain a blend (blending-2). This blend (blending-2) corresponds to an uncrosslinked ethylene copolymer composition. Thereafter, the blend (blending-2) was cut into sheets according to the test pieces, and uncrosslinked sheets with thicknesses of 2 mm and 3 mm were prepared. Meanwhile, as a sample for the probe tack test described above in the "Physical properties of uncrosslinked ethylene copolymer composition" above, the blend (blending-2) was cut into sheets and uncrosslinked sheets with a thickness of 1 mm were prepared.

[0130] The resulting uncrosslinked sheet having a thickness of 2 mm was pressed at 170°C for 15 minutes using a 100-ton press molding machine to produce a crosslinked sheet. The physical properties of the resulting crosslinked sheet were measured by the methods described above in "Physical properties of ethylene copolymer composition (crosslinked product)". The results are shown in Tables 2 and 3. In Table 2, with respect to the blending amount of DCP-40C used as an organic peroxide, the value shown in the upper row represents the total amount of DCP-40C, and the value shown in italics in parentheses in the lower row represents the amount of the active ingredient as an organic peroxide contained in DCP-40C.

[0131] Comparative Example 1 An uncrosslinked sheet and a crosslinked sheet were obtained in the same manner as in Example 1, except that only the crosslinking agent was added to the formulation (formulation-1) and no crosslinking aid (N) was added to obtain a formulation (formulation-2). The physical properties, etc. were evaluated by the methods described above. The results are shown in Tables 2 and 3.

[0132] Example 2 An uncrosslinked sheet and a crosslinked sheet were obtained in the same manner as in Example 1, except that the 100 parts by mass of the ethylene copolymer (L-1) used in Example 1 was changed to 50 parts by mass of the ethylene copolymer (L-1) and 50 parts by mass of the ethylene-α-olefin copolymer (P-1), and the amounts of carbon black 1, softener 1, organic peroxide, and crosslinking aid (N) were changed to 31 parts by mass, 19 parts by mass, 6.3 parts by mass, and 5.0 parts by mass, and the physical properties, etc. were evaluated by the methods described above. The results are shown in Tables 2 and 3.

[0133] Example 3 An uncrosslinked sheet and a crosslinked sheet were obtained in the same manner as in Example 2, except that the amount of carbon black 1 was changed to 28 parts by mass, the amount of softener 1 to 22 parts by mass, and the amount of crosslinking aid (N) to 10.0 parts by mass, and the physical properties were evaluated by the methods described above. The results are shown in Tables 2 and 3.

[0134] [Table 2]

[0135] Table 3

Claims

1. an ethylene / α-olefin / non-conjugated polyene copolymer (L) comprising a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C] containing in the molecule a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II), and satisfying the following requirements (1) to (3): trans polyoctenylene (M), a crosslinking aid (N) which is an unsaturated carboxylic acid metal salt; An ethylene-based copolymer composition comprising: 【Chemistry 1】 Requirement (1): The molar ratio [[A] / [B]] of the structural units derived from ethylene [A] to the structural units derived from an α-olefin [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; Requirement (2): The content of the 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 derived from [A], [B], and [C]; Requirement (3): The B value represented by the following formula (i) is 1.20 or more. B value = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] ... formula (i) [Here, [E], [X], and [Y] represent the molar fractions of structural units derived from ethylene [A], an α-olefin having 4 to 20 carbon atoms [B], and a non-conjugated polyene [C], respectively, and [EX] represents the ethylene [A]-α-olefin having 4 to 20 carbon atoms [B] dyad chain fraction.]

2. 2. The ethylene copolymer composition according to claim 1, wherein the α-olefin [B] having 4 to 20 carbon atoms is 1-butene.

3. The ethylene copolymer composition according to claim 1, wherein the non-conjugated polyene [C] comprises 5-vinyl-2-norbornene.

4. The ethylene-based copolymer composition according to claim 1, further comprising an ethylene-α-olefin copolymer (P) (excluding those falling under the ethylene-α-olefin-non-conjugated polyene copolymer (L)) containing structural units derived from ethylene [A] and structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms.

5. 5. The ethylene-based copolymer composition according to claim 4, wherein the trans-polyoctenylene (M) is contained in an amount of 0.1 to 50 parts by mass per 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin copolymer (P).

6. The ethylene-based copolymer composition according to claim 1, further comprising an organic peroxide as a crosslinking agent.

7. 7. The ethylene copolymer composition according to claim 6, wherein a mass ratio of the content of the organic peroxide to the content of the crosslinking aid (N) is 1:10 to 10:

1.

8. The ethylene copolymer composition according to claim 1, wherein the crosslinking coagent (N) is zinc dimethacrylate.

9. A laminate comprising a layer [I] containing the ethylene-based copolymer composition according to any one of claims 1 to 8 and a layer [II] containing a fibrous material, wherein the layer [I] and the layer [II] are in contact with each other.

10. The laminate according to claim 9 , wherein the layer [I] is a layer formed by crosslinking the ethylene copolymer composition.

11. The laminate according to claim 9, wherein the fibrous material of the layer [II] comprises resorcinol-formaldehyde-latex-treated (RFL-treated) fibers.

12. The laminate according to claim 9, wherein the fiber material of the layer [II] is canvas.

13. An industrial belt comprising the laminate of claim 9.

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