Resin composition, laminate, and industrial belt

Abstract

To provide a resin composition capable of giving a crosslinked product excellent in thermal aging resistance and adhesiveness to synthetic fibers.SOLUTION: The resin composition contains: an ethylene / α-olefin / nonconjugated polyene copolymer (L-1) satisfying specific requirements; an ethylene / α-olefin copolymer (L-2) other than (L-1); and trans-polyoctenylene (M).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a laminate, and an industrial belt.

Background Art

[0002] Ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM (ethylene propylene rubber) are generally excellent in weather resistance, heat resistance, and ozone resistance, and are used in automotive industrial parts, industrial rubber products, electrical insulating materials, civil engineering building materials, rubber-coated fabrics, and the like.

[0003] By improving the adhesiveness with a layer containing a fiber material, productivity can be improved, and an ethylene-based copolymer composition that is excellent in adhesiveness with a layer containing a fiber material and can maintain the mechanical properties of the resulting laminate is known. For example, Patent Document 1 discloses an ethylene-based copolymer composition containing an ethylene·α-olefin·non-conjugated polyene copolymer satisfying specific requirements, an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C], and trans-polyoctenylene (M). Further, for example, Patent Document 2 discloses an ethylene-based copolymer composition containing an ethylene·α-olefin·non-conjugated polyene copolymer satisfying specific requirements, an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C], and a modified polybutadiene (N).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the ethylene·α-olefin·non-conjugated polyene random copolymer rubber described in Patent Document 1 and Patent Document 2 above, further improvement is required in the adhesiveness to synthetic fibers as compared with polar rubbers such as nitrile rubber, chloroprene rubber, and chlorosulfonated polyethylene. Further, in the carcass layer of an industrial belt (conveyor belt) to which the above copolymer rubber is applied, further adhesive strength is required. As a result of intensive studies, the inventors have found that a resin composition containing trans-polyoctenylene (M) and two specific ethylene·α-olefin copolymers in a specific content ratio is excellent in heat aging resistance and adhesiveness to synthetic fibers.

[0006] An object to be solved by one embodiment of the present invention is to provide a resin composition from which a crosslinked product excellent in heat aging resistance and adhesiveness to synthetic fibers can be obtained. Another object to be solved by one embodiment of the present invention is to provide a laminate and an industrial belt excellent in heat aging resistance and adhesiveness to synthetic fibers.

Means for Solving the Problems

[0007] Means for solving the above problems include the following aspects. <1> An ethylene·α-olefin·non-conjugated polyene copolymer (L-1) that satisfies the following requirements (1) to (4) and 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], an ethylene·α-olefin copolymer (L-2) other than the above (L-1), trans-polyoctenylene (M), and a resin composition containing the same. (1) The molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] and the structural unit 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 derived from [A], [B] and [C]; (3) The Mooney viscosity ML (1+4) at 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] respectively represent the molar fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], and [EX] represents the dyad chain fraction of ethylene [A] - α-olefin [B] having 4 to 20 carbon atoms.] <2> The resin composition according to <1>, wherein the structural unit derived from the α-olefin [B] having 4 to 20 carbon atoms is a structural unit derived from 1-butene. <3> The resin composition according to <1> or <2>, wherein the content of the structural unit derived from ethylene in the ethylene·α-olefin copolymer (L-2) exceeds 50 mol% and is 80 mol% or less based on the total number of moles of the structural units constituting the copolymer (L-2). <4> The resin composition according to any one of <1> to <3>, further comprising a modified polybutadiene (N). <5> The resin composition according to <4>, wherein the content of the modified polybutadiene (N) is 0.1 to 50 parts by mass based on 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (L-1) and the ethylene·α-olefin copolymer (L-2). <6> The resin composition according to any one of <1> to <5>, wherein the content of the trans-polyoctenylene (M) is 0.5 to 50 parts by mass based on 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (L-1) and the ethylene·α-olefin copolymer (L-2). <7> The resin composition according to any one of <1> to <6>, further comprising an organic peroxide as a crosslinking agent. Layer [I] containing the resin composition according to any one of <8> <1> to <7>, and layer [II] containing a fiber material, provided with A laminate in which the layer [I] and the layer [II] are in contact with each other. <9> The laminate according to <8>, wherein the layer [I] is a layer formed by crosslinking the resin composition. <10> The laminate according to <8> or <9>, wherein the fiber material includes fibers treated with resorcinol formaldehyde latex (RFL treatment). <11> The laminate according to any one of <8> to <10>, wherein the fiber material is canvas. <12> An industrial belt comprising the laminate according to any one of <8> to <11>.

Advantages of the Invention

[0008] According to one embodiment of the present invention, a resin composition excellent in heat aging resistance and adhesiveness to synthetic fibers is provided. Also, according to one embodiment of the present invention, a laminate and an industrial belt excellent in heat aging resistance and adhesiveness to synthetic fibers are provided.

Modes for Carrying Out the Invention

[0009] Hereinafter, the content of the present invention will be described in detail. The description of the content of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the expression "polymer" is used in the sense of including homopolymers and copolymers unless otherwise specified. Also, in this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Also, in this specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, unless otherwise specified, each component in the composition or each structural unit in the polymer may be included alone or in combination of two or more. Hereinafter, the details of the present invention will be described.

[0010] <<Resin Composition>> The resin composition according to the present invention satisfies the following requirements (1) to (4), and includes an ethylene·α-olefin·non-conjugated polyene copolymer (L-1) 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], an ethylene·α-olefin copolymer (L-2) other than the above (L-1), and trans-polyoctenylene (M). By having the above configuration, the resin composition can obtain a crosslinked product excellent in heat aging resistance and adhesiveness to synthetic fibers. The ethylene·α-olefin copolymer (L-2) other than (L-1) has a smaller amount of double bonds than the ethylene·α-olefin·non-conjugated polyene copolymer (L-1) having a non-conjugated polyene, so that the heat aging resistance is good. In addition, non-conjugated polyenes have high reactivity with peroxides. Therefore, when comparing the copolymer (L-1) and the copolymer (L-2), the reaction rate of the copolymer (L-2) is slower. In the resin composition according to the present invention, by containing the copolymer (L-2) having a slower reaction rate than the copolymer (L-1), when crosslinking is carried out using a peroxide, the lifetime of the radicals of the cleaved peroxide becomes longer. As a result, when a laminate in which the resin composition is in contact with synthetic fibers is formed, the amount of radicals used in the reaction with the synthetic fibers increases, increasing the amount of chemical bonds between the resin composition and the synthetic fibers, and it is presumed that the adhesive strength between the resin composition of the present invention and the synthetic fibers is improved. Hereinafter, each component of the resin composition will be described.

[0011] 〔Ethylene·α-olefin·non-conjugated polyene copolymer (L-1)〕 The ethylene·α-olefin·non-conjugated polyene copolymer (L-1) (hereinafter, may also be simply referred to as "copolymer (L-1)") satisfies the following requirements (1) to (4) and includes 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].

[0012] <<Structural units derived from an α-olefin [B] having 4 to 20 carbon atoms>> The α-olefin [B] having 4 to 20 carbon atoms is not particularly limited, and may be, for example, a linear or branched α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include linear α-olefins such as 1-butene having 4 carbon atoms, 1-nonene having 9 carbon atoms, 1-decene having 10 carbon atoms, 1-nonadecene having 19 carbon atoms, 1-eicosene having 20 carbon atoms, or branched α-olefins such as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene.

[0013] Among these, as the α-olefin [B] having 4 to 20 carbon atoms, α-olefins having 4 to 10 carbon atoms are preferred, 1-butene, 1-hexene or 1-octene are more preferred, and 1-butene is particularly preferred. The above α-olefin [B] may be used alone or in combination of two or more.

[0014] <<Non-conjugated polyene [C]>> Examples of the non-conjugated polyene [C] include chain non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 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, 4-ethylidene-8-methyl-1,7-nonadiene.

[0015] Among these, as the non-conjugated polyene [C], a chain non-conjugated diene or a cyclic non-conjugated diene is preferred, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, or 5-vinyl-2-norbornene is more preferred, and 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene is even more preferred. The non-conjugated polyene [C] may be used alone or in combination of two or more.

[0016] Specific examples of the copolymer (L-1) include 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 (ENB) copolymer, ethylene·1-pentene·5-ethylidene-2-norbornene (ENB) copolymer, ethylene·1-hexene·5-ethylidene-2-norbornene (ENB) copolymer, ethylene·1-heptene·5-ethylidene-2-norbornene (ENB) copolymer, ethylene·1-octene·5-ethylidene-2-norbornene copolymer, ethylene·1-nonene·5-ethylidene-2-norbornene (ENB) copolymer, ethylene·1-decene·5-ethylidene-2-norbornene (ENB) copolymer, ethylene·1-butene·1-octene·5-ethylidene-2-norbornene (ENB) copolymer, ethylene·1-butene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-pentene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-hexene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-heptene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-octene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-nonene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-decene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, ethylene·1-butene·1-octene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer, etc. The copolymer (L-1) may be included in the resin composition alone or in combination of two or more.

[0017] The copolymer (L-1) satisfies the following requirements (1) to (4). <<Requirement (1)>> The molar ratio [A] / [B] of the structural unit derived from ethylene [A] and the structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. When the molar ratio [A] / [B] of the copolymer (L) is within the above range, the balance between rubber elasticity at low temperature and tensile strength at normal temperature is excellent. The lower limit of the molar ratio [A] / [B] is preferably 55 / 45, more preferably 60 / 40, and particularly preferably 65 / 35. Also, the upper limit of the molar ratio [[A] / [B]] is preferably 85 / 15, more preferably 80 / 20, and still more preferably 75 / 25.

[0018] <<Requirement (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 unit derived from the [A], the structural unit derived from the [B], and the structural unit derived from the [C]. The copolymer (L-1) in which the content ratio of the structural unit derived from the non-conjugated polyene [C] is within the above range has sufficient crosslinkability and flexibility. The lower limit of the content of the structural unit derived from the non-conjugated polyene [C] is preferably 0.5 mol%, more preferably 1.0 mol%. The upper limit of the content ratio of the structural unit derived from the non-conjugated polyene [C] is preferably 4.0 mol%, more preferably 3.5 mol%, and still more preferably 3.0 mol%. When the content of the structural unit derived from the non-conjugated polyene [C] is within the above range, a copolymer (L-1) having sufficient crosslinkability and flexibility can be obtained.

[0019] <<Requirement (3)>> The copolymer (L-1) has a Mooney viscosity ML at 125 °C (1+4)It is in the range of 5 to 100, preferably 10 to 80, more preferably 12 to 60, still more preferably 15 to 40, and particularly preferably 20 to 25 at 125 °C. When the Mooney viscosity of the copolymer (L-1) is in the above range, the copolymer (L-1) has good processability and fluidity, and also shows good post-treatment quality (ribbon handling property) and excellent physical properties, and a copolymer (L-1) can be obtained.

[0020] The copolymer (L-1) has a Mooney viscosity ML at 100 °C (1+4) It is preferably 10 to 200, more preferably 15 to 100, still more preferably 20 to 50, and particularly preferably 25 to 35 at 100 °C.

[0021] <<Requirement (4)>> The copolymer (L-1) has a B value represented by the following formula (i) of 1.20 or more. B value = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] ··· (i) [Here, [E], [X], and [Y] represent the molar fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A] - α-olefin [B] having 4 to 20 carbon atoms.] The B value is preferably in the range of 1.20 to 1.80, particularly preferably 1.22 to 1.40. When the B value is 1.20 or more, it is easy to obtain a copolymer (L-1) in which the compression set at low temperature is suppressed and the balance between the rubber elasticity at low temperature and the tensile strength at normal temperature is excellent.

[0022] The copolymer (L-1) may contain, as a structural unit derived from at least one monomer selected from the group consisting of the aforementioned ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], a unit derived from a biomass-derived monomer and / or a unit derived from a chemically recycled monomer.

[0023] The copolymer (L-1) may contain at least one structural unit derived from a biomass-derived monomer. The biomass-derived monomer used as a raw material for the copolymer (L-1) may be biomass-derived ethylene, biomass-derived α-olefin, or biomass-derived non-conjugated polyene. Examples of the biomass-derived α-olefin include biomass-derived propylene. Examples of the biomass-derived non-conjugated polyene include biomass-derived 5-ethylidene-2-norbornene and biomass-derived 5-vinyl-2-norbornene. The monomer used as a raw material for the copolymer (L-1) may contain only biomass-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers. Note that biomass-derived monomers such as biomass-derived ethylene, biomass-derived α-olefin, and biomass-derived non-conjugated polyene can be obtained by known methods. It is preferable from the viewpoint of reducing the environmental load that the copolymer (L-1) contains a structural unit derived from a biomass-derived monomer.

[0024] The copolymer (L-1) may contain at least one structural unit derived from a monomer derived from chemical recycling. The monomer derived from chemical recycling used as a raw material for the copolymer (L-1) may be chemical recycling-derived ethylene, chemical recycling-derived α-olefin, or chemical recycling-derived non-conjugated polyene. Furthermore, the monomer used as a raw material for the copolymer (L-1) may contain only monomers derived from chemical recycling, or may contain both monomers derived from chemical recycling and fossil fuel-derived monomers. Note that monomers derived from chemical recycling such as chemical recycling-derived ethylene, chemical recycling-derived α-olefin, and chemical recycling-derived non-conjugated polyene can be obtained by known methods. It is preferable from the viewpoint of reducing the environmental load (mainly waste reduction) that the copolymer (L-1) contains a structural unit derived from a monomer derived from chemical recycling.

[0025] <<Method for Producing Ethylene·α-Olefin·Non-Conjugated Polyene Copolymer (L-1)>> The copolymer (L-1) can be obtained by various known production methods, for example, by the conventionally known production methods using metallocene catalysts. As the metallocene catalysts and the production methods using such catalysts, for example, the examples described in International Publication No. 2015 / 122415 pamphlet, particularly the examples described in paragraphs

[0249] to

[0320] of the said publication, can be adopted.

[0026] The content of the copolymer (L-1) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and still more preferably 45 to 55% by mass. However, the total content of the copolymer (L-1) and the copolymer (L-2) described later is 100% by mass. The copolymer (L-1) may be contained in the resin composition alone or in combination of two or more.

[0027] 〔Ethylene·α-Olefin Copolymer (L-2)〕 The ethylene·α-olefin copolymer (L-2) (hereinafter, may also be simply referred to as "copolymer (L-2)") is an ethylene·α-olefin copolymer other than the above (L-1). The copolymer (L-2) contains structural units derived from ethylene and structural units derived from α-olefin. Examples of the above α-olefin include α-olefins having 3 to 20 carbon atoms. The α-olefins having 3 to 20 carbon atoms are not particularly limited, and examples 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, and the like. Among these, as the α-olefin, from the viewpoint of obtaining a conveyor belt having excellent mechanical strength, etc., it is preferably an α-olefin having 3 to 12 carbon atoms, more preferably an α-olefin having 3 to 9 carbon atoms, still more preferably propylene, 1-butene or 1-pentene, and particularly preferably propylene. These α-olefins may be used alone or in combination of two or more.

[0028] The content of the structural unit derived from the α-olefin in the ethylene·α-olefin copolymer (L-2) (when there are two or more structural units derived from the α-olefin, the total content thereof) is preferably 20 mol% or more and less than 50 mol%, more preferably 30 to 45 mol%, still more preferably 35 to 40 mol% with respect to the total number of moles constituting the copolymer (L-2). The content of the structural unit derived from the α-olefin is determined by the measurement method described in the examples below. The above α-olefin may be used alone or in combination of two or more.

[0029] The copolymer (L-2) preferably satisfies the following requirements (i) to (ii). (i) Mooney viscosity The Mooney viscosity ML of the copolymer (L-2) at 100 °C (1+4) 100 °C is preferably 10 to 100, more preferably 20 to 80, still more preferably 25 to 60, and particularly preferably 30 to 50. The Mooney viscosity ML at 100 °C (1+4) When 100 °C is within the above range, a resin composition having a small molding shrinkage rate and excellent processability can be obtained. The Mooney viscosity ML at 100 °C (1+4) 100 °C can be measured and determined by the method described in JIS K6300.

[0030] (ii) Density The density of the copolymer (L-2) is preferably 840 to 920 kg / m 3 and more preferably 850 to 915 kg / m 3and more preferably 860 to 915 kg / m 3 is. When the density is within the above range, a conveyor belt with a small molding shrinkage rate and excellent strength characteristics and wear resistance can be obtained. The density can be measured and determined by the method described in ASTM D1505.

[0031] The copolymer (L-2) is preferably solid at room temperature to about 100°C, more preferably at a temperature around 90°C.

[0032] The copolymer (L-2) can be produced, for example, by copolymerizing ethylene and an α-olefin by a conventionally known method using a vanadium-based catalyst, a Ziegler-Natta catalyst or a metallocene catalyst. From the viewpoint of easily obtaining the copolymer (L-2) that satisfies the above physical properties, etc., the copolymer (L-2) is preferably synthesized by a method using a metallocene catalyst. Specifically, it is more preferably synthesized by a catalyst containing a metallocene compound and an aluminum-containing compound described in International Publication No. 2008 / 152935 or a catalyst composed of a metallocene compound and an organoaluminum oxy compound or an ionizing ionic compound described in JP-A-9-40586.

[0033] The content of the structural unit derived from ethylene in the ethylene-α-olefin copolymer (L-2) is preferably more than 50 mol% and 80 mol% or less, more preferably 55 to 70 mol%, and still more preferably 60 to 65 mol% based on the total number of moles constituting the copolymer (L-2). The content of the structural unit derived from ethylene is determined by the measurement method described in the examples described later.

[0034] The content of the copolymer (L-2) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and still more preferably 45 to 55% by mass. However, the total content of the above copolymer (L-1) and copolymer (L-2) is 100% by mass. The copolymer (L-2) may be contained in the resin composition alone or in combination of two or more.

[0035] The copolymer (L-2) may contain a structural unit derived from a biomass-derived monomer and / or a chemical recycling-derived monomer as a structural unit derived from at least one monomer selected from the group consisting of ethylene and α-olefin described above. The biomass-derived monomer in the copolymer (L-2) has the same meaning as the biomass-derived monomer in the above-described copolymer (L-1). Similarly, the chemical recycling-derived monomer in the copolymer (L-2) has the same meaning as the chemical recycling-derived monomer in the above-described copolymer (L-1).

[0036] <<Trans-Polyoctenylene (M)>> Trans-Polyoctenylene (M) is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond. The metathesis polymer means a polymer obtained by a metathesis polymerization method of trans double bond cyclooctene using a metal atom as a polymerization catalyst. By including Trans-Polyoctenylene (M), the resin composition has good adhesiveness to other materials, such as a layer containing a fiber material such as an industrial belt, and the laminated body formed by crosslinking has excellent adhesive strength to the layer containing the fiber material.

[0037] Trans-Polyoctenylene (M) may be synthesized or may be a commercially available product. Examples of commercially available products include VESTENAMER (trade name) of Evonik Industries.

[0038] The content of Trans-Polyoctenylene (M) is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (L-1) and the above copolymer (L-2).

[0039] <<Modified polybutadiene (N)>> The resin composition may further contain modified polybutadiene (N). When modified polybutadiene (N) is included, it has excellent adhesiveness and the adhesive strength to synthetic fibers is further improved. As the modified polybutadiene (N), polybutadiene modified with an unsaturated carboxylic acid or its derivative is preferably mentioned. Examples of the unsaturated carboxylic acid or its derivative include unsaturated carboxylic acids or unsaturated dicarboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (nadic acid (trademark)), and derivatives such as acid halides, amides, imides, acid anhydrides, and esters of these acids. Among these, as the modified polybutadiene (N), an unsaturated dicarboxylic acid or its acid anhydride is preferable, maleic acid, nadic acid, and their acid anhydrides are more preferable, and maleic anhydride is particularly preferable.

[0040] Commercially available products may be used as the modified polybutadiene (N). For example, commercially available products of maleic anhydride-modified polybutadiene include Ricon130MA8, Ricon130MA13, Ricon130MA20, Ricon131MA5, Ricon131MA10, Ricon131MA17, Ricon131MA20, Ricon184MA6, etc. (above are trade names, manufactured by Cray Valley).

[0041] The content of the modified polybutadiene (N) is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 10 parts by mass, still more preferably 0.4 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass with respect to 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2). The modified polybutadiene (N) may be contained in the composition alone or in combination of two or more.

[0042] The resin composition may contain, within a range not impairing the effects of the present invention, the above-mentioned copolymer (L-1), copolymer (L-2), and components other than trans-polyoctenylene (M) and modified polybutadiene (N) (hereinafter also referred to as "other components"). Examples of other components include crosslinking agents, crosslinking aids, vulcanization accelerators, vulcanization aids, fillers, softeners, anti-aging agents, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. The other components may be used alone or in combination of two or more.

[0043] <<Organic peroxide>> The resin composition preferably further contains an organic peroxide as a crosslinking agent. 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-butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide. Among these, dicumyl perxide (DCP) and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane are preferred as the organic peroxide.

[0044] The content of the organic peroxide 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, and still more preferably 1 to 8 parts by mass with respect to a total of 100 parts by mass of the copolymer (L-1) and the copolymer (L-2). The organic peroxide may be contained in the resin composition alone or in combination of two or more. When the content of the organic peroxide is within the above range, blooming on the surface of the obtained molded article is suppressed, and the resin composition exhibits excellent crosslinking properties, which is preferable.

[0045] When the resin composition contains an organic peroxide as a crosslinking agent, it preferably further contains a crosslinking aid. Examples of the crosslinking aid include sulfur; quinone dioxime-based 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-based crosslinking aids; divinylbenzene; metal oxides such as zinc oxide (for example, two types of zinc oxide (JIS standard (K-1410)), zinc oxide manufactured by Hakusuitech Co., Ltd.), magnesium oxide, and activated zinc white (for example, "META-Z102" (trade name; manufactured by Inoue Sekkai Kogyo Co., Ltd.) and other zinc oxides).

[0046] When using a crosslinking aid, the content of the crosslinking aid is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 2 to 8 parts by mass with respect to a total of 100 parts by mass of the copolymer (L-1) and the copolymer (L-2). The crosslinking aid may be contained in the resin composition alone or in combination of two or more.

[0047] The resin composition may further contain a crosslinking agent other than the above organic peroxide. Examples of crosslinking agents other than organic peroxides include crosslinking agents generally used when crosslinking rubber, such as phenolic resins, sulfur-based compounds, hydrosilicone-based compounds, amino resins, quinones or their derivatives, amine-based compounds, azo-based compounds, epoxy-based compounds, isocyanate-based compounds, etc. Among these, as crosslinking agents other than organic peroxides, sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred.

[0048] Examples of sulfur-based compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0049] When the resin composition contains a sulfur-based compound as a crosslinking agent, the content of the sulfur-based compound 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 with respect to 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2). When the content of the sulfur-based compound is within the above range, blooming on the surface of the obtained molded body is suppressed, and the resin composition exhibits excellent crosslinking properties.

[0050] When the resin composition contains a sulfur-based compound as a crosslinking agent, it is preferable that the resin composition further contains a vulcanization accelerator. Examples of the vulcanization accelerator include thiazole-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (e.g., Sanseler M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio) benzothiazole (e.g., Nocceler MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl) mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio) benzothiazole, and dibenzothiazyl disulfide (e.g., Sanseler DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, and diorthotolylguanidine; aldehydeamine-based vulcanization accelerators such as acetaldehyde aniline condensate and butyraldehyde aniline condensate; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; thiuram-based vulcanization accelerators such as tetramethylthiuram monosulfide (e.g., Sanseler TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (e.g., Sanseler TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (e.g., Sanseler TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutylthiuram disulfide (e.g., Sanseler TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Sanseler TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (e.g., Sanseler PZ, Sanseler BZ, and Sanseler EZ (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators such as ethylene thiourea (e.g., Sanseler BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sanseler 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 dibutylxanthate.

[0051] When the resin composition contains a vulcanization accelerator, the content of the vulcanization accelerator 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 with respect to 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2). When the content of the vulcanization accelerator is within the above range, blooming on the surface of the obtained molded body is suppressed, and the resin composition exhibits excellent crosslinking properties.

[0052] When the resin composition contains a sulfur-based compound as a crosslinking agent, it may further contain a vulcanization aid.

[0053] Examples of the vulcanization aid include zinc oxide (for example, ZnO#1, two types of zinc oxide, manufactured by Hakusuitec Co., Ltd.), magnesium oxide, activated zinc white (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Sekkai Kogyo Co., Ltd.)), etc. mentioned above as the crosslinking aid. The content of the vulcanization aid is usually 1 to 20 parts by mass with respect to 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2).

[0054] <<Filler>> The resin composition may contain a filler. There is no particular limitation on the filler. For example, known rubber reinforcing agents compounded in rubber compositions can be mentioned. As the filler, inorganic fillers are preferably mentioned.

[0055] Examples of the inorganic filler include carbon blacks such as Asahi #55G, Asahi #60UG (above trade names, manufactured by Asahi Carbon Co., Ltd.), Seast V, Seast SO, v116, Seast 3, vSeast 6, Seast 9, Seast SP, Seast TA, etc. (above trade names, manufactured by Tokai Carbon Co., Ltd.), those obtained by surface-treating these carbon blacks with a silane coupling agent, etc., and silica, activated calcium carbonate, fine powder talc, fine powder silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, etc.

[0056] As the filler, it is preferably carbon black, silica, light calcium carbonate, heavy calcium carbonate, talc or clay, more preferably carbon black.

[0057] The content of the filler is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and still more preferably 20 to 50 parts by mass with respect to 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2). These fillers may be contained in the resin composition alone or in combination of two or more.

[0058] <<Antioxidant (Stabilizer)>> The resin composition may contain an antioxidant. When the resin composition contains an antioxidant (stabilizer), the lifespan of, for example, a seal packing formed from the resin composition can be prolonged. There is no particular limitation on the antioxidant, and conventionally known antioxidants can be used. Examples of the antioxidant include amine-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, etc.

[0059] Examples of the antioxidant include aromatic secondary amine-based antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenol-based antioxidants such as dibutylhydroxytoluene and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; thioether-based antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; sulfur-based antioxidants such as 2-mercaptobenzoyl imidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, and distearyl thiodipropionate. Among these, as the anti-aging agent, preferably a phenolic anti-aging agent and / or a sulfur-based anti-aging agent, more preferably a phenolic anti-aging agent and a sulfur-based anti-aging agent.

[0060] The content of the anti-aging agent (when two or more anti-aging agents are included, the total content) is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, based on 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2). When the content of the anti-aging agent is within the above range, blooming on the surface of the obtained molded article can be suppressed, and furthermore, vulcanization inhibition can be suppressed. The anti-aging agent may be contained in the resin composition alone or in combination of two or more.

[0061] <<Processing Aid>> The resin composition may contain a processing aid. There is no particular limitation on the processing aid, and generally those compounded with rubber as a processing aid can be mentioned. Specific examples of the processing aid include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. Among these, as the processing aid, stearic acid is preferred.

[0062] The content of the processing aid is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass, based on 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2). When the content of the processing aid is within the above range, it is suitable because it has excellent processability such as kneading processability, extrusion processability, and injection moldability. The processing aid may be contained in the resin composition alone or in combination of two or more.

[0063] <<Activator>> Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, and zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; zinc peroxide preparations; and cetyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0064] When the resin composition contains an activator, the content of the activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass in total of the copolymer (L-1) and the copolymer (L-2).

[0065] Since the resin composition includes the copolymer (L-1), the copolymer (L-2), and the transpolyooctenylene (M), the adhesiveness between the layer formed from the resin composition and the layer containing the fibrous material is improved. Therefore, when manufacturing the laminate, the manufacturing speed can be increased. The laminate provided with the layer obtained by crosslinking the resin composition is excellent in adhesive strength, and thus can be used for various purposes including hoses and belts.

[0066] [Laminate] The laminate according to the present invention includes a layer [I] containing the above resin composition and a layer [II] containing a fibrous material, and it is preferable that the layer [I] and the layer [II] are in contact with each other.

[0067] [[Layer [I]]] Layer [I] preferably contains the above resin composition, and more preferably is a layer formed by crosslinking the above resin composition.

[0068] [[Layer [II]]] Layer [II] contains a fibrous material. It is sufficient that at least a part of layer [II] contains the fibrous material.

[0069] [[Fibrous Material]] As the above fiber material, there is no particular limitation, and various known fiber materials can be used. Examples of the fiber material include natural fibers such as cotton and wood cellulose fiber; organic fiber materials of fibers made of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyetheretherketone, 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.

[0070] These fiber materials may be long fibers (filaments) or short fibers (staples). Further, the fiber material may be cord yarn, spun yarn, woven fabric, knitted fabric, canvas, non-woven fabric, or the like.

[0071] Examples of the above 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), or copolymer polyamides containing these units; and wholly aromatic polyamides such as polybenzamide, poly-p-phenylene terephthalamide, and poly-m-phenylene isophthalamide.

[0072] <<RFL treatment>> In addition, these fiber materials may be surface-treated by a known method in order to improve the adhesiveness between the fiber materials or with the above layer [I]. Examples of the surface treatment method of the fiber material include a method such as resorcinol-formalin-latex (RFL) treatment.

[0073] The RFL treatment is an adhesion treatment of a fiber material using a treatment liquid (RFL liquid) containing resorcinol-formalin-latex. The RFL liquid is a mixed liquid of an initial condensate of resorcinol and formalin and a rubber latex. Examples of the rubber latex include 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. The rubber latex may be used alone or in a blend of two or more kinds. The fiber material preferably includes fibers treated with resorcinol-formalin-latex (RFL).

[0074] <Method for manufacturing a laminate> The method for manufacturing a laminate is not particularly limited, and a known method for manufacturing a laminate may be adopted. Examples of the method for manufacturing a laminate include, for example, a method of laminating a layer [I] containing an uncrosslinked resin composition manufactured (formed) by a known method in advance and a layer [II] containing a fiber material, and then crosslinking the layer [I] made of the resin composition; a method of laminating a layer [I] made of a crosslinked resin composition and a layer [II] containing a fiber material; or a method of extruding and coating a layer [I] made of a resin composition on a layer [II] containing a fiber material and then crosslinking the layer [I] made of the resin composition.

[0075] The method for preparing the resin composition is not particularly limited, and various known kneading and mixing apparatuses, such as internal mixers (sealed mixers) like Banbury mixers, kneaders, and intermixers, and rolls, etc., are used to knead the ethylene-α-olefin-non-conjugated polyene copolymer (L-1), copolymer (L-2), the above-mentioned transpolyoctenylene (M), and, if necessary, the above-mentioned modified polybutadiene (N), crosslinking agents, fillers, softeners, anti-aging agents, processing aids, and other additives.

[0076] The uncrosslinked resin composition obtained by kneading can be formed into a desired shape by various molding methods such as an extrusion molding machine, calender rolls, a press, an injection molding machine, a transfer molding machine, etc. After that, the resin composition can be further crosslinked to form layer [I] and laminated (bonded) with layer [II], or the uncrosslinked resin composition can be formed into a desired shape by the above method and then laminated (bonded) with layer [II] and crosslinked.

[0077] There is no particular limitation on the method for crosslinking layer [I]. For example, methods such as heating using a crosslinking agent or methods by irradiation with light, γ-rays or electron beams can be mentioned.

[0078] Also, when crosslinking, a mold may be used, or crosslinking may be carried out without using a mold. When crosslinking without using a mold, the molding and crosslinking steps are usually carried out continuously. As the heating method in the crosslinking tank, heating tanks such as hot air, glass bead fluidized bed, UHF (extremely high frequency electromagnetic wave), and steam can be used.

[0079] <<Applications of the laminate>> The laminate is suitably used for, for example, automotive hoses, water supply hoses, gas hoses; industrial belts such as transmission belts and conveyor belts; and escalator handrails.

[0080] Examples of the above automotive hoses include brake hoses, radiator hoses, heater hoses, air cleaner hoses, etc. Examples of the above transmission belts include V-belts, flat belts, toothed belts, etc. Examples of the above conveyor belts include light conveyor belts, cylindrical belts, raft top belts, conveyor belts with flanges, conveyor belts with U-shaped guides, conveyor belts with V-shaped guides, etc.

Examples

[0081] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples in any way. In the examples and comparative examples, the following copolymers were used.

[0082] <Ethylene·α-olefin·non-conjugated polyene copolymer (L-1)> According to the description of [Synthesis Example C1] in International Publication No. 2015 / 122415, an ethylene·1-butene·5-ethylidene-2-norbornene (ENB) copolymer having the following physical properties was synthesized. Hereinafter, this will be referred to as "ethylene-based copolymer (L-1)". The composition and physical properties of the ethylene-based copolymer (L-1) are as follows.

[0083] <<Composition and physical properties of ethylene-based copolymer (L-1)>> Structural unit derived from ethylene: 67.7 mol% Structural unit derived from 1-butene: 30.0 mol% Structural unit derived from 5-ethylidene-2-norbornene (ENB): 2.3 mol% Mooney viscosity ML (1+4) 100 °C: 30 Mooney viscosity ML (1+4) 125 °C: 22 B value: 1.3

[0084] [Table 1]

[0085] The above content (mol%) was 1 determined by intensity measurement using an H-NMR spectrometer. The details of the measurement conditions are as described in International Publication No. 2015 / 122415.

[0086] <Ethylene·α-olefin copolymer (L-2)> ·Ethylene·propylene copolymer As the ethylene·α-olefin copolymer (L-2), the following ethylene·propylene copolymer was used. Trade name: Mitsui EPT 0045, Mooney viscosity ML(1+4) 100 °C = 40, ethylene content = 51 mass%.

[0087] <Modified polybutadiene (N)> As the modified polybutadiene (N), maleic anhydride modified polybutadiene (N-1) of Ricon131MA17 [trade name, Cray Valley] was used.

[0088] <Trans - polyoctenylene (M)> As the trans - polyoctenylene (M), the product name: VESTENAMER 8012 of Evonik Industries was used.

[0089] <<Mooney viscosity>> Mooney viscosity ML (1+4) 100 °C and Mooney viscosity ML (1+4) For 125 °C, it was measured in accordance with JIS K6300 (1994) using a Mooney viscometer (manufactured by Shimadzu Corporation, model number: SMV202 type).

[0090] <> Using o - dichlorobenzene - d4 / benzene - d6 (4 / 1 [v / v]) as the measurement solvent, at a measurement temperature of 120 °C, 13 The C - NMR spectrum (100 MHz, manufactured by JEOL Ltd., model number: ECX400P) was measured and calculated based on the following formula (i). B value = ([EX] + 2[Y]) / 〔2×[E]×([X] + [Y])〕···(i) [Here, [E], [X], and [Y] respectively represent the mole fractions of the structural units derived from ethylene [A1], α - olefins with 4 to 20 carbon atoms [A2], and non - conjugated polyenes [A3], and [EX] represents the ethylene [A1] - α - olefin with 4 to 20 carbon atoms [A2] dyad chain fraction.]

[0091] <<Durometer A hardness>> The hardness (Type A durometer, HA) of the crosslinked sheet produced below was measured in accordance with JIS K 6253. First, six 2-mm crosslinked sheets with smooth surfaces were used, and the flat parts were stacked to produce a test piece with a thickness of approximately 12 mm. The hardness was measured using this test piece. However, in the test piece, those with foreign matter mixed in, those with air bubbles, and those with scratches were not used for hardness measurement. Also, the dimensions of the measurement surface of the test piece were set to a size such that the tip of the pressing needle could be measured at a position more than 12 mm away from the edge of the test piece.

[0092] [Tensile breaking point stress and tensile breaking point elongation] The tensile breaking point stress and tensile breaking point elongation of the crosslinked sheet produced below were measured by the following method. The crosslinked sheet was punched out to produce a No. 3 dumbbell test piece described in JIS K 6251 (1993). Using this test piece, a tensile test was conducted under the conditions of a measurement temperature of 25°C and a tensile speed of 500 mm / min in accordance with the method specified in Paragraph 3 of JIS K 6251 (1993), and the tensile breaking point stress (TB) and tensile breaking point elongation (EB) were measured.

[0093] -Evaluation- [Adhesion to synthetic fibers] The adhesion to synthetic fibers was evaluated by measuring the peel strength (adhesion strength) between layer [I] containing the crosslinked resin composition and layer [II] containing the fiber material.

[0094] The uncrosslinked sheet with a thickness of 3 mm prepared below was placed on a woven fabric of nylon fibers (manufactured by Ayaba Kogyo Co., Ltd.) treated with resorcinol-formaldehyde-latex (RFL), and pressed at 170 °C for 15 minutes using a 200-ton press molding machine to crosslink the uncrosslinked sheet, thereby producing a laminate comprising a layer [I] containing the crosslinked resin composition and a layer [II] containing the fiber material. A test piece with a width of 25 mm was punched out from the laminate, and a T-peel test was conducted at a tensile speed of 50 mm / min. to determine the peel strength (adhesive strength) (N / cm) between the above layer [I] and layer [II]. The peel test was performed three times, and the arithmetic mean value was taken as the peel strength. If the adhesive strength is 130 N / cm or more, it can be said that the adhesiveness to synthetic fibers is excellent.

[0095] [Heat Aging Resistance] According to JIS K 6257, a heat aging test was conducted on the crosslinked sheet prepared below by heating it at 165 °C for 168 hours and holding it at each time. The hardness, tensile breaking point stress (MPa), and tensile breaking point elongation (%) of the crosslinked sheet after the heat aging test were measured by the methods described for the above-mentioned durometer A hardness, tensile breaking point stress, and tensile breaking point elongation, and the difference in hardness before and after the heat aging test: ΔH (Duro-A) was determined. Also, the difference in the tensile breaking point elongation (EB) before and after the heat aging test was divided by the value of the tensile breaking point elongation (EB) before the heat aging test to obtain the change rate [Ac(EB)] of the tensile breaking point elongation (EB) before and after the heat aging test. Change rate [Ac(EB)] of the tensile breaking point elongation (EB) before and after the heat aging test =(EB after heat aging test - EB before heat aging test) / EB before aging test × 100

[0096] -Evaluation Criteria- Also, for heat aging resistance, if the difference in hardness: ΔH (Duro-A) is +13 or less and the change rate Ac(EB) is -32 or more, it can be said that the heat aging resistance is excellent.

[0097] [Example 1] 50 parts by mass of the above ethylene-based copolymer (L-1) and 50 parts by mass of the ethylene-based copolymer (L-2) were each kneaded for 30 seconds. To the kneaded ethylene-based copolymer, 5 parts by mass of activated zinc white (trade name: META-Z L40, manufactured by Inoue Lime Industry Co., Ltd.) as a crosslinking aid, 0.5 parts by mass of stearic acid as a processing aid, 2 parts by mass of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1010, manufactured by BASF Japan Ltd.) as antioxidant 1, 4 parts by mass of 2-mercaptobenzimidazole (trade name: Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.) as antioxidant 2, 30 parts by mass of carbon black (manufactured by Asahi Carbon Co., Ltd., trade name Asahi #60UG), and 5 parts by mass of trans-polyoctenylene (M) (Evonik Industries, trade name: VESTENAMER 8012) were kneaded for 2 minutes in a 1.7-liter Banbury mixer (manufactured by Kobe Steel, Ltd.). Then, the ram was raised for cleaning, and further kneaded for 1 minute and discharged at about 150°C to obtain an uncrosslinked resin composition (formulation-1). This kneading was carried out at a filling rate of 70%.

[0098] Next, 146.5 parts by mass of this resin composition was wound around an 8-inch roll (the surface temperature of the front roll is 50°C, the surface temperature of the rear roll is 50°C, the rotational speed of the front roll is 16 rpm, and the rotational speed of the rear roll is 18 rpm). As a crosslinking agent, 5.1 parts by mass of a 40% by mass product of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name: Mitsui DCP-40C) was added and kneaded for 10 minutes to obtain a resin composition (formulation-2). Then, according to the test pieces used in the above-described measurement or evaluation method of physical properties, formulation-2 was separated into a sheet shape, and an uncrosslinked sheet with a thickness of 2 mm and an uncrosslinked sheet with a thickness of 3 mm were each prepared. The obtained uncrosslinked sheet with 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. Each physical property of the obtained crosslinked sheet was measured by the method described above. The results are shown in Table 2.

[0099] [Example 2] 146.5 parts by mass of the resin composition (Formulation - 1) obtained in Example 1 was wound around an 8 - inch roll (the surface temperature of the front roll was 50°C, the surface temperature of the rear roll was 50°C, the rotational speed of the front roll was 16 rpm, and the rotational speed of the rear roll was 18 rpm). As a cross - linking agent, 5.1 parts by mass of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP - 40C), and 1 part by mass of maleic anhydride - modified polybutadiene (N) (maleic anhydride - modified polybutadiene, trade name: Ricon131MA17, manufactured by Cray Valley) were added and kneaded for 10 minutes to obtain a resin composition (Formulation - 2). Then, according to the test pieces used for the measurement or evaluation method of the above - mentioned physical property values, Formulation - 2 was separated into a sheet form, and an uncrosslinked sheet with a thickness of 2 mm and an uncrosslinked sheet with a thickness of 3 mm were respectively prepared.

[0100] The obtained uncrosslinked sheet with a thickness of 2 mm was pressed at 170°C for 15 minutes using a 100 - ton press - molding machine to produce a cross - linked sheet. The physical properties of the obtained cross - linked sheet were measured by the method described above. The results are shown in Table 2.

[0101] [Comparative Example 1] An uncrosslinked resin composition was prepared in the same manner as in Example 2, except that the blending amount of the ethylene - based copolymer (L - 1) used in Example 2 was changed to 30 parts by mass and the blending amount of the ethylene - based copolymer (L - 2) was changed to 70 parts by mass. Using this, an uncrosslinked sheet was produced. Further, using the obtained uncrosslinked sheet, a cross - linked sheet and a laminate were produced in the same manner as in Example 2. The physical properties of the obtained cross - linked sheet were measured by the method described above. The results are shown in Table 2.

[0102] [Table 2]

[0103] As shown in Table 2, it can be seen that the sheets of Examples 1 and 2 are superior in heat - aging resistance and adhesion to synthetic fibers compared to the sheet of Comparative Example 1.

Claims

1. An ethylene / α-olefin / non-conjugated polyene copolymer (L-1) which satisfies the following requirements (1) to (4) and 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]; An ethylene / α-olefin copolymer (L-2) other than the (L-1), trans polyoctenylene (M); A resin composition comprising: (1) the molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] to the structural unit 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 % relative to 100 mol % in total of the structural units derived from [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] respectively represent the molar fractions of ethylene [A], the α-olefin [B] having 4 to 20 carbon atoms, and the non-conjugated polyene [C], and [EX] represents the dyad chain fraction of ethylene [A]-α-olefin [B] having 4 to 20 carbon atoms.]

2. The resin composition according to claim 1, wherein the structural unit derived from the α-olefin [B] having 4 to 20 carbon atoms is a structural unit derived from 1-butene.

3. The content of structural units derived from ethylene in the ethylene-α-olefin copolymer (L-2) is more than 50 mol% and not more than 80 mol% based on the total number of moles of structural units constituting the copolymer (L-2). The resin composition according to claim 1.

4. The resin composition according to claim 1 , further comprising a modified polybutadiene (N).

5. The content of the modified polybutadiene (N) is 0.1 to 50 parts by mass relative to a total of 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L-1) and the ethylene-α-olefin copolymer (L-2). The resin composition according to claim 4.

6. The resin composition according to claim 1, wherein the content of the trans polyoctenylene (M) is 0.5 to 50 parts by mass relative to a total of 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L-1) and the ethylene-α-olefin copolymer (L-2).

7. The resin composition according to claim 1 , further comprising an organic peroxide as a crosslinking agent.

8. A laminate comprising a layer [I] containing the resin composition according to any one of claims 1 to 7 and a layer [II] containing a fiber material, A laminate, in which the layer [I] and the layer [II] are in contact with each other.

9. The laminate according to claim 8 , wherein the layer [I] is a layer formed by crosslinking the resin composition.

10. 9. The laminate of claim 8, wherein the fibrous material comprises resorcinol-formaldehyde-latex treated (RFL treated) fibers.

11. The laminate of claim 8 , wherein the textile material is canvas.

12. An industrial belt comprising the laminate of claim 8.

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