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 polymer composition comprising an ethylene / α - olefin / non-conjugated polyene polymer (L) satisfying specific requirements, a trans-polyoctenylene (M), and silica (S) having a specific surface area of 140 to 300m2 / g as measured by the BET method.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

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

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

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

[0007] 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.

[0008] 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]

[0009] As a result of investigations aimed at solving the above-mentioned problems, the present inventors have found that by using a composition containing an ethylene-propylene-non-conjugated polyene copolymer, trans-polyoctenylene, and silica, which contains silica having a specific surface area of ​​a certain level or more, the adhesion between the composition and a layer containing a fibrous material, in particular the adhesion between the composition and a layer containing synthetic fibers, is improved, and have completed the present invention.

[0010] The present invention relates to the following [1] to

[10] . [1] an ethylene-α-olefin-non-conjugated polyene copolymer (L) containing structural units derived from ethylene [A], structural units derived from an α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [C], and satisfying the following requirements (1) to (4); trans polyoctenylene (M), The specific surface area measured by the BET method is 140 to 300 m 2 / g of silica (S) an ethylene copolymer composition comprising: (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from an α-olefin [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % relative to 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C is 5 to 100, (4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the 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].] [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], further comprising an organic peroxide as a crosslinking agent. [4] The ethylene copolymer composition according to any one of [1] to [3], comprising 0.5 to 50 parts by mass of the trans-polyoctenylene (M) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L). [5] The ethylene copolymer composition according to any one of [1] to [4], comprising 0.5 to 80 parts by mass of the silica (S) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L). [6] A laminate comprising a layer [I] containing the ethylene copolymer composition according to any one of [1] to [5] and a layer [II] containing a fiber material, wherein the layer [I] and the layer [II] are in contact with each other. [7] The laminate according to [6], wherein the layer [I] is formed by crosslinking the ethylene copolymer composition. [8] The laminate according to [6] or [7], wherein the fiber material of the layer [II] contains resorcinol-formaldehyde-latex treated (RFL treated) fibers. [9] The laminate according to any one of [6] to [8], wherein the fiber material of the layer [II] is canvas.

[10] An industrial belt comprising the laminate according to any one of [6] to [9]. [Effects of the Invention]

[0011] The ethylene copolymer composition of the present invention has excellent adhesive strength (peel strength) with layers containing other materials, such as fiber materials (especially synthetic fibers), and is therefore suitable for laminates such as industrial belts. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. In this specification, the terms "(co)polymer" and "polymer" are used to mean both homopolymers and copolymers.

[0013] In addition, in this specification, the expression "x to y" (where x and y are numerical values and 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.

[0014] In addition, in this specification, the "structural unit derived from ethylene" means a structural unit corresponding to ethylene, that is, a structural unit represented by -CH2-CH2-. The "structural unit derived from α-olefin" is interpreted in the same way, meaning a structural unit corresponding to α-olefin, that is, a structural unit represented by -CH2-CRR' - (where R and R' are each independently hydrogen or an alkyl group). Also, the "structural unit derived from non-conjugated polyene" means a structural unit corresponding to non-conjugated polyene, that is, a structural unit having one or more pairs of bonds formed by cleavage of the π bond constituting the double bond among the double bonds of non-conjugated polyene.

[0015] 《Ethylene·α-olefin·Non-conjugated polyene copolymer (L)》 The ethylene·α-olefin·non-conjugated polyene copolymer (L), which is one of the components constituting the ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition forming layer [I] of the laminate of the present invention, contains 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]. In this specification, the ethylene·α-olefin·non-conjugated polyene copolymer (L) is also referred to as the "ethylene-based copolymer (L)", and may be abbreviated as the "ethylene-based copolymer (L)" or simply the "copolymer (L)".

[0016] The α-olefin [B] and non-conjugated polyene [C] having 4 to 20 carbon atoms that can be used in the present invention may each be used alone or in combination of two or more. That is, the ethylene-α-olefin-non-conjugated polyene copolymer (L) according to the present invention contains structural units derived from ethylene [A], structural units derived from at least one type of α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [C].

[0017] 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. Examples of biomass-derived α-olefins having 4 to 20 carbon atoms include biomass-derived 1-butene. Examples of biomass-derived non-conjugated polyenes include biomass-derived 5-ethylidene-2-norbornene and biomass-derived 5-vinyl-2-norbornene. The monomers used as the raw material 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 material, including fungi, yeast, algae, and bacteria, and their residues, such as plant- or animal-derived raw materials. 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.

[0018] 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 14 It 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 a structural unit derived from a biomass-derived monomer.

[0019] 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.

[0020] It is preferable that the ethylene copolymer (L) contains a structural unit derived from a chemically recycled monomer 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].

[0021] The ethylene-α-olefin-non-conjugated polyene copolymer (L) satisfies the following requirements (1) to (4): (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from an α-olefin [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % relative to 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C is 5 to 100, (4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the 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].]

[0022] 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.

[0023] 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.

[0024] Non-conjugated polyenes [C] Specific examples of the non-conjugated polyene [C] constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, and 5-methylene-2-norbornene. Examples of suitable cyclic non-conjugated dienes include 2,3-diisopropylidene-5-norbornene, 5-isopropylidene-2-norbornene, and 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadiene.

[0025] 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-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferred, and cyclic non-conjugated dienes are more preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being even more preferred, and 5-ethylidene-2-norbornene being even more preferred.

[0026] 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-ethylidene-2-norbornene copolymer, Ethylene-1-pentene-5-ethylidene-2-norbornene copolymer, Ethylene-1-hexene-5-ethylidene-2-norbornene copolymer, Ethylene-1-heptene-5-ethylidene-2-norbornene copolymer, Ethylene-1-octene-5-ethylidene-2-norbornene copolymer, Ethylene-1-nonene-5-ethylidene-2-norbornene copolymer, Ethylene-1-decene-5-ethylidene-2-norbornene copolymer, Ethylene-1-butene-1-octene-5-ethylidene-2-norbornene copolymer, Ethylene-1-butene-5-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.

[0027] In one preferred exemplary embodiment of the present invention, the ethylene copolymer (L) is an ethylene-1-butene-5-ethylidene-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.

[0028] The ethylene copolymer (L) according to the present invention satisfies the following requirements (1) to (4). <Requirement (1)> The ethylene copolymer (L) has 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 has 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 55 / 45, even more preferably 60 / 40, and particularly preferably 65 / 35. The upper limit of the molar ratio [A] / [B] is preferably 90 / 10, more preferably 85 / 15, even more preferably 80 / 20, and particularly preferably 75 / 25. The molar ratio [[A] / [B]] is 1 It can be measured using H-NMR.

[0029] <Requirement (2)> The ethylene copolymer (L) has a content of structural units derived from the 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 the 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], 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 the non-conjugated polyene [C] is preferably 0.5 mol %, and the upper limit of the content of the structural units derived from the non-conjugated polyene [C] is preferably 4.0 mol %, more preferably 3.5 mol %, and even more preferably 3.0 mol %. When the content of the structural unit derived from the non-conjugated polyene [C] is within the above range, an ethylene copolymer (L) having sufficient crosslinkability and flexibility can be obtained. The content of the structural unit derived from the non-conjugated polyene [C] is 1 It can be measured using H-NMR.

[0030] <Requirement (3)> The ethylene copolymer (L) has a Mooney viscosity of ML at 125°C. (1+4) The temperature at 125°C is in the range of 5 to 100, preferably 10 to 70, more preferably 15 to 40, and further preferably 20 to 30. 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).

[0031] <Requirement (4)> The ethylene copolymer (L) has a B value represented by the following formula (i) of 1.20 or more, preferably 1.20 to 1.80, particularly preferably in the range of 1.22 to 1.40. 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].]

[0032] 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.

[0033] <Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (L)> The ethylene-α-olefin-non-conjugated polyene copolymer (L) according to the present invention can be obtained by various known production methods, for example, a conventionally known production method using a metallocene catalyst. Examples of metallocene catalysts and production methods using such catalysts include those described in WO 2015 / 122415, particularly paragraphs

[0249] to

[0320] of the same publication.

[0034] <<Trans-polyoctenylene (M)>> The trans-polyoctenylene (M), which is one of the components constituting the ethylene copolymer composition of the present invention and the ethylene copolymer composition that forms the layer [I] of the laminate of the present invention, is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond. 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) according to the present invention is manufactured and sold by Evonik Industries under the trade name VESTENAMER®.

[0035] Silica (S) Silica (S), which is one of the components constituting the ethylene copolymer composition of the present invention and the ethylene copolymer composition forming the layer [I] of the laminate of the present invention, has a specific surface area measured by the BET method of 140 to 300 m 2 / g. In the ethylene copolymer composition of the present invention, the silica (S) has a hydroxyl group, which is thought to improve the tackiness of the composition itself and the tackiness and adhesiveness with fibrous materials. In the present invention, the silica (S) has a specific surface area of ​​a certain level or more, which tends to improve the tackiness when made into an ethylene copolymer composition, and the tackiness and adhesiveness between the ethylene copolymer composition and fibrous materials. The lower limit of the specific surface area is preferably 150 m 2 / g or more, more preferably 160m 2 / g or more, more preferably 170m 2 / g or more, particularly preferably 180m 2 On the other hand, the upper limit of the specific surface area is 300 m 2 / g or less, preferably 280m 2 / g or less, more preferably 260m 2 / g or less, more preferably 240m 2 / g or less, particularly preferably 220m 2 / g or less. Specifically, the specific surface area is a specific surface area measured by the BET method based on the amount of N 2 gas adsorbed, and more specifically, can be measured based on ISO 5794-1 Annex D.

[0036] <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 silica (S). The ethylene copolymer composition of the present invention contains preferably 0.5 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 of trans-polyoctenylene (M) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L). The ethylene copolymer composition of the present invention contains preferably 0.5 to 80 parts by mass, more preferably 3 to 60 parts by mass, even more preferably 5 to 40 parts by mass, and particularly preferably 10 to 20 parts by mass of silica (S) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0037] The ethylene copolymer composition of the present invention contains, in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L), trans-polyoctenylene (M) and silica (S) having a specific specific surface area, 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 with layers containing fibrous materials.

[0038] In addition to the ethylene copolymer (L), the trans-polyoctenylene (M), and the silica (S), the ethylene copolymer composition of the present invention may further contain, as additives according to the desired purpose, other components (hereinafter referred to as "other components") that do not fall under the category of the ethylene copolymer (L), the trans-polyoctenylene (M), or the silica (S), to the extent that the effects of the present invention are not impaired. Examples of additives that may be the "other components" include crosslinking agents, crosslinking aids, vulcanization accelerators, vulcanization aids, fillers, softeners, antioxidants, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. Furthermore, other resins (hereinafter referred to as "other resins") that do not fall under the category of the ethylene copolymer (L) or the trans-polyoctenylene (M) may also be included as additives that may be the "other components." The ethylene copolymer composition of the present invention may contain at least one selected from these additives. Furthermore, these additives that can be contained in the ethylene copolymer composition of the present invention may each be used alone or in combination of two or more.

[0039] <Crosslinking Agents, Crosslinking Coagents, Vulcanization Accelerators, and Vulcanization Coagents> In a typical and preferred embodiment of the present invention, the ethylene-based copolymer composition of the present invention further contains a crosslinking agent. The ethylene-based copolymer composition containing the crosslinking agent may further contain a crosslinking coagent, a vulcanization accelerator, or a vulcanization coagent. 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.

[0040] 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.

[0041] When an organic peroxide is used as the crosslinking agent, the amount thereof in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1.0 to 5 parts by mass, and particularly preferably 1.5 to 3.0 parts by mass, relative to 100 parts by mass of the ethylene copolymer (L). When the amount of the organic peroxide is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article, which is preferable.

[0042] Crosslinking aid When an organic peroxide is used as the crosslinking agent, it is preferable to use a crosslinking aid in combination. That is, when the ethylene-based copolymer composition contains an organic peroxide as the crosslinking agent, it is preferable that the ethylene-based copolymer composition further contains a crosslinking aid. Examples of crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; divinylbenzene; and metal oxides such as zinc oxide and magnesium oxide. Examples of zinc oxide include zinc oxide types 1 and 2 specified in JIS K1410 and activated zinc oxide (e.g., "META-Z 102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)). The zinc oxide that can be used as a crosslinking aid may be in the form of a complex of zinc oxide and a metal salt other than zinc oxide, such as a complex activated zinc oxide having a calcium carbonate core and a zinc oxide coating covering the core (e.g., "META-Z L40" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0043] When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 0.2 to 12 mol, preferably 0.4 to 10 mol, more preferably 1.2 to 9.2 mol, and even more preferably 2.0 to 8.0 mol, per mol of the organic peroxide. When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 0.4 to 8 parts by mass, preferably 0.6 to 6.0 parts by mass, more preferably 0.8 to 4.0 parts by mass, still more preferably 1.0 to 3.2 parts by mass, and particularly preferably 1.2 to 2.8 parts by mass, relative to 100 parts by mass of the ethylene copolymer (L).

[0044] 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.

[0045] When a sulfur-based compound is used as a crosslinking agent, the blending amount thereof in the copolymer composition is usually 0.1 to 10 parts by mass, preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass, per 100 parts by mass of the ethylene-based copolymer (L). When the blending amount of the sulfur-based compound is within the above range, there is no blooming on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties.

[0046] 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.

[0047] When a vulcanization accelerator is used, the blending amount of the vulcanization accelerator in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the ethylene-based copolymer (L). When the blending amount of the vulcanization accelerator is within the above range, no blooming occurs on the surface of the obtained molded article, and the copolymer composition exhibits excellent crosslinking properties.

[0048] 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. Examples of vulcanization aids include zinc oxide (e.g., zinc oxide types 1 and 2 specified in JIS K1410, activated zinc oxide (e.g., "META-Z 102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)), complex activated zinc oxide (e.g., "META-Z L40" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)), and magnesium oxide. When a vulcanization aid is used, the amount of the vulcanization aid blended in the ethylene copolymer composition is usually 1 to 20 parts by mass per 100 parts by mass of the ethylene copolymer (L).

[0049] Filler The ethylene copolymer composition of the present invention may further contain a filler. The filler constituting the ethylene copolymer composition of the present invention is a known rubber reinforcing agent blended into a rubber composition, and is usually an inorganic substance called carbon black or an inorganic reinforcing agent.

[0050] Specific examples of fillers that can be used in the present invention include Asahi #55G and Asahi #60UG (both manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, etc.) carbon black (manufactured by Tokai Carbon Co., Ltd.), these carbon blacks that have been surface-treated with a silane coupling agent or the like, activated calcium carbonate, finely powdered talc, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like.

[0051] The filler that can be contained in the ethylene copolymer composition of the present invention may be one type alone or a mixture of two or more types. The filler used in the present invention is preferably carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay, or the like.

[0052] When the copolymer composition of the present invention contains a filler, the filler may be blended in an amount of usually 0.5 to 300 parts by mass, preferably 1.0 to 200 parts by mass, more preferably 3.0 to 150 parts by mass, even more preferably 5.0 to 100 parts by mass, and particularly preferably 10 to 50 parts by mass, relative to 100 parts by mass of the ethylene copolymer (L).

[0053] <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.

[0054] When the ethylene copolymer composition contains a softener, the amount of the softener is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0055] <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.

[0056] Examples of antioxidants include aromatic secondary amine antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate]methane (also known as pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]); bis[2 Examples of the antioxidant include thioether-based antioxidants such as [3-n-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 antioxidant 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.

[0057] When the ethylene copolymer composition contains an antioxidant, the blending amount of the antioxidant is usually 0.3 to 15 parts by mass, preferably 1.0 to 12 parts by mass, more preferably 2.0 to 10 parts by mass, even more preferably 3.0 to 8.0 parts by mass, and particularly preferably 4.0 to 7.0 parts by mass, per 100 parts by mass of the ethylene copolymer (L). When the blending amount of the antioxidant is within the above range, there is no bloom on the surface of the obtained molded article, and furthermore, the occurrence of vulcanization inhibition can be suppressed.

[0058] 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.

[0059] <Processing aids> The ethylene copolymer composition of the present invention may further contain a processing aid. A wide variety of processing aids that are generally compounded in rubber as processing aids can be used as the processing aid. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters thereof. Among these, stearic acid is preferred.

[0060] When the ethylene copolymer composition contains a processing aid, it can be appropriately blended in an amount of usually 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, relative to 100 parts by mass of the ethylene copolymer (L). When the blending amount of the processing aid is within the above range, it is preferable because it provides excellent processability such as kneading processability, extrusion processability, and injection moldability. The processing aid that can be contained in the ethylene copolymer composition of the present invention may be one type alone or a combination of two or more types.

[0061] <Activator> The ethylene copolymer composition of the present invention may further contain an activator, such as amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; 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.

[0062] When the ethylene copolymer composition contains an activator, the amount of the activator added is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0063] <Other resins> The ethylene copolymer composition of the present invention may further contain other resins ("other resins") that do not fall under the category of the above ethylene copolymer (L) or the above trans polyoctenylene (M). Examples of the other resins include polyethylene, polypropylene, and ethylene-α-olefin copolymers. Examples of the α-olefins constituting the ethylene-α-olefin copolymers include propylene, 1-butene, 1-hexene, and 1-octene. When the ethylene copolymer composition contains "other resins," the blending amount of the "other resins" is, for example, 1 to 100 parts by mass per 100 parts by mass of the ethylene copolymer (L).

[0064] <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), the silica (S), and, if necessary, a processing aid, a crosslinking aid, an antioxidant, a filler, the "other resins," and the like, using an internal mixer (internal mixer) such as a Banbury mixer, a kneader, or an intermix, at 80 to 160°C for 1 to 3 minutes, for example. Here, the ethylene copolymer composition containing the crosslinking agent can be prepared by kneading components other than the crosslinking agent (e.g., the ethylene-propylene-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the silica (S), as well as optional crosslinking aids, optional processing aids, optional antioxidants, and optional fillers) at 80 to 160°C for 1 to 3 minutes, and then adding additives such as the crosslinking agent to the blend (compound) obtained by this step using rolls such as open rolls or a kneader, and optionally adding a vulcanization accelerator and a crosslinking aid. The mixture is kneaded typically at a roll surface temperature of 40 to 80°C for 5 to 30 minutes, preferably at 40 to 70°C for 6 to 25 minutes, more preferably at 45 to 65°C for 7 to 20 minutes, and even more preferably at 45 to 60°C for 8 to 15 minutes, followed by a separating step.

[0065] 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 silica (S).

[0066] <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.

[0067] <<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.

[0068] <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.

[0069] <Textile materials> The fiber material forming layer [II] used in the present invention includes various known fiber materials, such as natural fibers such as cotton, hemp, flax (linen), and wood cellulose fibers; organic fiber materials such as synthetic resin fibers of polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-containing 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. Among these, fibers made of synthetic resins (e.g., fibers made of polyamide) are known as synthetic fibers.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] Furthermore, these fiber materials may be surface-treated by a known method such as resorcinol-formaldehyde latex treatment (RFL treatment) in order to improve adhesion between the fiber materials themselves or between the fiber materials and the layer [I] made of the ethylene copolymer composition.

[0074] <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.

[0075] 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.

[0076] <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 to 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. As a method for producing the layer [I] made of the ethylene copolymer composition, various known production methods can be adopted.

[0077] The ethylene copolymer composition can be obtained by kneading the ethylene-α-olefin-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the silica (S), and, if necessary, a crosslinking agent, and, if necessary, additives such as a filler, a softener, an antioxidant, and a processing aid, using various known kneading and mixing devices, for example, a Banbury mixer, a kneader, an internal mixer (internal mixer) such as an Intermix, a roll, or the like.

[0078] 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.

[0079] The layer [I] made of the ethylene copolymer composition may be crosslinked by either a method of heating using a crosslinking agent or a method of irradiating with light, γ rays or electron beams.

[0080] 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.

[0081] <<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.

[0082] Examples of the automotive hose include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the transmission belt include a V-belt, a flat belt, a toothed belt, etc. Examples of the conveyor belt include a light conveyor belt, a cylindrical belt, a rough-top belt, a flanged conveyor belt, a U-shaped guided conveyor belt, a V-guided conveyor belt, etc. [Example]

[0083] 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.

[0084] [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.

[0085] (1) Physical properties of ethylene-α-olefin-non-conjugated polyene copolymer (L)

[0086] <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). 1 The 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.

[0087] <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.

[0088] 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].]

[0089] (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.

[0090] 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.

[0091] (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.

[0092] <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, and the tensile stress at break (TB) and tensile elongation at break (EB) were measured.

[0093] <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.

[0094] 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 pressure was applied using a 200-ton press molding machine at 170°C for 15 minutes to crosslink the uncrosslinked sheet and 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 performed three times, and the average value was taken as the peel strength.

[0095] [Major constituents used in the examples] In the examples and comparative examples, the ethylene-α-olefin-non-conjugated polyene copolymer (L), trans-polyoctenylene (M), and silica (S) used in the ethylene copolymer composition were as follows:

[0096] (1) Ethylene-α-olefin-non-conjugated polyene copolymer (L) The copolymer obtained in Production Example 1 below was used as the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0097] [Manufacturing Example 1] Ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer with the following properties was obtained according to the method described in [Synthesis Example C1] of WO 2015 / 122415. Specifically, the copolymer was prepared using bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 Ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) were polymerized in hexane at 95°C in the presence of (C6H5)3CB(C6F5)4 as a cocatalyst and triisobutylaluminum (TiBA) as an organoaluminum compound to obtain ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer (hereinafter referred to as "copolymer (L-1)"). The constitution and physical properties of the copolymer (L-1) are shown in Table 1 below.

[0098] [Table 1]

[0099] (2) trans-polyoctenylene (M) As the trans-polyoctenylene (M), VESTENAMER (registered trademark) 8012, a trade name of Evonik Industries, was used.

[0100] (3) Silica (S) As silica (S-1), Nipsil LP, a trade name of Tosoh Silica Corp., was used. The physical properties of silica (S-1) are shown below. Specific surface area (ISO 5794-1 Annex D): 216m 2 / g Secondary particle size: 8nm As silica (S-2), Nipsil AQ, a trade name of Tosoh Silica Corp., was used. The physical properties of silica (S-2) are shown below. Specific surface area (ISO 5794-1 Annex D): 216m 2 / g Secondary particle size: 200nm (3') Other Silica (S') As the silica (S'-1), ULTRASIL (registered trademark) VN2 (precipitated silica manufactured by EVONIK) was used. The physical properties of the silica (S'-1) are shown below. Specific surface area (ISO 5794-1 Annex D): 125m 2 / g

[0101] Example 1 100 parts by mass of the ethylene copolymer (L) is masticated for 30 seconds, and the masticated ethylene copolymer (L) is mixed with 5 parts by mass of VESTENAMER (registered trademark) 8012 as trans polyoctenylene (M), Silica (S) is 15 parts by mass of silica (S-1) (Nipsil LP), 5 parts by mass of complex activated zinc oxide (product name META-Z L40 manufactured by Inoue Lime Industry Co., Ltd., zinc oxide 40%, calcium carbonate 60%) as a crosslinking aid, 0.5 parts by mass of stearic acid as a processing aid (lubricant), As an antioxidant, 2 parts by mass of tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate]methane (trade name Irganox 1010, manufactured by BASF Japan Ltd.) and 4 parts by mass of 2-mercaptobenzimidazole (trade name Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.) were used. This was mixed with 15 parts by mass of carbon black (manufactured by Asahi Carbon Co., Ltd., product name Asahi #60UG) in a 1.7 liter Banbury mixer (manufactured by Kobe Steel, Ltd.) for 2 minutes. The ram was then raised and cleaned, and the mixture was mixed for another minute and then discharged at 150°C to obtain a compound (Compound 1). This mixing was carried out at a filling rate of 70%.

[0102] Next, 146.5 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), and 5.1 parts by mass of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP-40C: dicumyl peroxide content: 40% by mass) was added as a crosslinking agent and kneaded for 10 minutes to obtain a compound (Compound-2). This was then cut into sheets according to the test pieces, and uncrosslinked sheets with thicknesses of 2 mm and 3 mm were prepared.

[0103] The obtained 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 obtained crosslinked sheet were measured by the methods described above. The results are shown in Table 2. In Table 2, the values ​​shown in the upper row for the amount of DCP-40C used as the organic peroxide represent the total amount of DCP-40C, while the values ​​in parentheses and italics in the lower row represent the amount of the active ingredient as the organic peroxide contained in DCP-40C. Furthermore, the values ​​shown in the upper row for the amount of META-Z L40 used as the crosslinking coagent represent the total amount of META-Z L40, while the values ​​in parentheses and italics in the lower row represent the amount of the active ingredient as active zinc oxide contained in META-Z L40.

[0104] Example 2 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained in the same manner as in Example 1, except that S-1 (Nipsil LP) used in Example 1 was not used and S-2 (Nipsil AQ) was used in 15 parts by mass, and the physical properties thereof were evaluated by the methods described above. The results are shown in Table 2.

[0105] Comparative Example 1 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained in the same manner as in Example 1, except that S-1 (Nipsil LP) used in Example 1 was not used and S'-1 (ULTRASIL VN2) was used in 15 parts by mass, and the physical properties thereof were evaluated by the methods described above. The results are shown in Table 2.

[0106] [Table 2]

Claims

1. an ethylene / α-olefin / non-conjugated polyene copolymer (L) containing structural units derived from ethylene [A], structural units derived from an α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [C], and satisfying the following requirements (1) to (4): trans polyoctenylene (M), The specific surface area measured by the BET method is 140 to 300 m 2 / g of silica (S) an ethylene copolymer composition comprising: (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; (2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol %, based on 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C （１＋４） 125°C is 5 to 100, (4) The B value represented by the following formula (i) is 1.20 or more. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) [Here, [E], [X], and [Y] represent the 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 sequence fraction of ethylene [A]-α-olefin having 4 to 20 carbon atoms [B].]

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

4. 2. The ethylene copolymer composition according to claim 1, comprising 0.5 to 50 parts by mass of the trans polyoctenylene (M) per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (L).

5. 2. The ethylene copolymer composition according to claim 1, comprising 0.5 to 80 parts by mass of the silica (S) per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (L).

6. A laminate comprising a layer [I] containing the ethylene-based copolymer composition according to any one of claims 1 to 5 and a layer [II] containing a fibrous material, wherein the layer [I] and the layer [II] are in contact with each other.

7. The laminate according to claim 6 , wherein the layer [I] is formed by crosslinking the ethylene copolymer composition.

8. The laminate according to claim 6, wherein the fiber material of the layer [II] comprises resorcinol-formaldehyde-latex-treated (RFL-treated) fiber.

9. The laminate according to claim 6, wherein the fiber material of the layer [II] is canvas.

10. An industrial belt comprising the laminate of claim 6.

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