Compositions, laminates, and industrial belts for industrial belts

Abstract

To provide an industrial belt composition that yields a crosslinked material with excellent elongation at break, heat resistance, and adhesion to fibrous materials. [Solution] An industrial belt composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A-1) that satisfies specific requirements, an ethylene-α-olefin copolymer (A-2) other than (A-1), a reinforcing agent, and a titanate coupling agent, wherein the reinforcing agent contains carbon black; a laminate comprising a layer made of the composition; and an industrial belt having the laminate.

Description

[Technical Field]

[0001] The present invention relates to industrial belt compositions, laminates, and industrial belts. [Background technology]

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

[0003] Disclosed are ethylene-α-olefin-non-conjugated polyene copolymers and modified polybutadiene (N) copolymers that can improve productivity by improving adhesion to layers containing fibrous materials, have excellent adhesion to layers containing fibrous materials, and maintain the mechanical properties of the resulting laminates, which can improve productivity by improving adhesion to layers containing fibrous materials, and also have excellent adhesion to layers containing fibrous materials and maintain the mechanical properties of the resulting laminates (see, for example, Patent Document 1). A rubber molded article is disclosed that has low elution and excellent mechanical properties, and is characterized by containing 100 parts by weight of rubber in which the proportion of low molecular weight components with a weight-average molecular weight of 10,000 or less is 1.5% by weight or less of the total amount of rubber, 50 to 100 parts by weight of carbon black, 0.5 to 3.0 parts by weight of a titanate-based coupling agent, and a crosslinking agent (see, for example, Patent Document 2). A rubber composition for tires that enhances the dispersibility of inorganic fillers and exhibits excellent air permeability prevention performance has been disclosed, characterized in that it contains 10 to 100 parts by mass of an inorganic filler and 0.1 to 20% by mass of a titanate-based coupling agent relative to the inorganic filler, with respect to 100 parts by mass of a rubber component containing 50 parts by mass or more of butyl rubber (see, for example, Patent Document 3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2024-070154 [Patent Document 2] Japanese Patent Publication No. 2005-298671 [Patent Document 3] Japanese Patent Publication No. 2021-38329 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Laminates in which a layer containing conventional fiber material and a layer made of an ethylene copolymer composition are in contact require high adhesion to the fiber material layer while maintaining mechanical properties.

[0006] The problem that one embodiment of the present invention aims to solve is to provide an industrial belt composition that yields a crosslinked material with an excellent balance of elongation at break, heat resistance, and adhesion to fibrous materials. Furthermore, one of the problems that this embodiment of the present invention aims to solve is to provide a laminate and an industrial belt that are excellent in terms of elongation at break, heat resistance, and adhesion to fibrous materials. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments. <1> An ethylene-α-olefin-non-conjugated polyene copolymer (A-1) that satisfies the following requirements (1) to (4) and contains structural units derived from ethylene [A], structural units derived from α-olefins [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyenes [C], Ethylene-α-olefin copolymer (A-2) other than (A-1) above, Reinforcement agent, Titanate coupling agent and Includes, A composition for industrial belts, wherein the reinforcing agent contains carbon black; (1) The molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefins [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) The content of structural units derived from non-conjugated polyenes [C] is 0.1 to 6.0 mol% relative to 100 mol% of the total structural units derived from ethylene [A], α-olefins having 4 to 20 carbon atoms [B], and non-conjugated polyenes [C]; (3) Mooney viscosity at 125°C ML (1+4) 125°C corresponds to 5-100°C; (4) The B value expressed by the following formula (i) is 1.20 or greater. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefins with 4 to 20 carbon atoms [B], and unconjugated polyenes [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A]-α-olefins with 4 to 20 carbon atoms [B].] <2> The structural unit derived from the α-olefin [B] having 4 to 20 carbon atoms is a structural unit derived from 1-butene. <1> The industrial belt composition described above. <3> The content of structural units derived from ethylene in the ethylene-α-olefin copolymer (A-2) is 50 to 80 mol% of the total number of moles of structural units constituting the copolymer (A-2). <1> or <2> The industrial belt composition described above. <4> The carbon black content is 5 to 100 parts by mass per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2). <1> ~ <3> A composition for industrial belts as described in any one of the following. <5> The titanate coupling agent is contained in an amount of 0.5 to 10 parts by mass per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2). <1> ~ <4> A composition for industrial belts as described in any one of the following. <6> The industrial belt composition according to any one of <1> to <5>, further comprising silica as the reinforcing agent. <7> The industrial belt composition according to any one of <1> to <6>, wherein the content of the titanate coupling agent is 1 to 50 parts by mass with respect to 100 parts by mass of the reinforcing agent. <8> The industrial belt composition according to any one of <1> to <7>, further comprising trans - polyoctenylene. <9> The industrial belt composition according to <8>, wherein the content of the trans - polyoctenylene is 0.5 to 50 parts by mass with respect to 100 parts by mass in total of the ethylene·α - olefin·non - conjugated polyene copolymer (A - 1) and the ethylene·α - olefin copolymer (A - 2). <10> The industrial belt composition according to any one of <1> to <9>, further comprising modified polybutadiene. <11> The industrial belt composition according to <10>, wherein the content of the modified polybutadiene is 0.1 to 50 parts by mass with respect to 100 parts by mass in total of the ethylene·α - olefin·non - conjugated polyene copolymer (A - 1) and the ethylene·α - olefin copolymer (A - 2). <12> The industrial belt composition according to any one of <1> to <11>, further comprising an organic peroxide as a cross - linking agent. <13> A layer [I] composed of the industrial belt composition according to any one of <1> to <12>, A layer [II] containing a fiber material, and comprising, A laminate in which the layer [I] and the layer [II] are in contact with each other. <14> The laminate according to <13>, wherein the layer [I] is a layer formed by cross - linking the industrial belt composition. <15> The laminate according to <13> or <l4>, wherein the fiber material comprises fibers treated with resorcinol·formaldehyde·latex (RFL). <16> The laminate according to any one of <13> to <15>, wherein the fiber material is canvas. <17> An industrial belt comprising the laminate according to any one of <13> to <16>.

Advantages of the Invention

[0008] According to one embodiment of the present invention, there is provided a composition for an industrial belt capable of obtaining a crosslinked product excellent in elongation at break, heat resistance, and adhesion to a fiber material. Further, according to one embodiment of the present invention, there are provided a laminate and an industrial belt excellent in elongation at break, heat resistance, and adhesion to a fiber material.

Mode 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 made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the expression "polymer" is used in a meaning including a homopolymer and a copolymer unless otherwise specified. Also, in this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as a lower limit value and an upper limit value. Also, in this specification, when referring to the amount of each component in a 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 particularly limited, 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] <<Composition for Industrial Belt>> The industrial belt composition according to the present invention satisfies the following requirements (1) to (4) and comprises an ethylene-α-olefin-non-conjugated polyene copolymer (A-1) containing structural units derived from ethylene [A], structural units derived from α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyene [C], an ethylene-α-olefin copolymer (A-2) other than (A-1), a reinforcing agent, and a titanate coupling agent, wherein the reinforcing agent contains carbon black. The industrial belt composition, having the above structure, yields a crosslinked material with excellent elongation at break, heat resistance, and adhesion to fibrous materials. The reason for this is not clear, but the following mechanism is presumed. Ethylene-α-olefin copolymers other than (A-1), such as (A-2), have fewer double bonds than ethylene-α-olefin-non-conjugated polyene copolymers (A-1), which contain non-conjugated polyenes, resulting in better heat resistance. Furthermore, non-conjugated polyenes are highly reactive to peroxides. Therefore, when comparing copolymer (A-1) and copolymer (A-2), copolymer (A-2) has a slower reaction rate. In the industrial belt composition, the inclusion of copolymer (A-2), which has a slower reaction rate than copolymer (A-1), extends the lifespan of the cleaved peroxide radicals when crosslinked using peroxide. As a result, when the industrial belt composition and synthetic fibers are in contact in a laminate, the amount of radicals used in the reaction with the synthetic fibers increases, which increases the amount of chemical bonding between the industrial belt composition and the synthetic fibers, and is presumed to improve the adhesive strength between the industrial belt composition and synthetic fibers of the present invention. The titanate coupling agent in this invention reacts with reinforcing agents such as carbon black when the industrial belt composition is kneaded, thereby preventing aggregation of the reinforcing agents in the system and improving dispersibility. Therefore, it is presumed that it increases the elongation at break of the molded article obtained from the industrial belt composition while maintaining its heat resistance. Furthermore, it is presumed that the interaction between the surface hydroxyl groups of reinforcing agents such as carbon black and the fibrous material results in excellent adhesion to the fibrous material. The following describes each component of the industrial belt composition.

[0011] [Ethylene-α-olefin-non-conjugated polyene copolymer (A-1)] Ethylene-α-olefin-non-conjugated polyene copolymer (A-1) (hereinafter sometimes simply referred to as "copolymer (A-1)") satisfies the following requirements (1) to (4) and contains structural units derived from ethylene [A], structural units derived from α-olefins having 4 to 20 carbon atoms [B], and structural units derived from non-conjugated polyenes [C].

[0012] <<Structural units derived from α-olefins [B] with 4 to 20 carbon atoms>> There are no particular restrictions on the α-olefin [B] having 4 to 20 carbon atoms; for example, it may be a linear or branched α-olefin having 4 to 20 carbon atoms. Examples of α-olefins having 4 to 20 carbon atoms include linear α-olefins such as 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), 1-nonadecene (19 carbon atoms), and 1-eicosene (20 carbon atoms), or branched α-olefins such as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene.

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

[0014] <<Non-conjugated polyene [C]>> Examples of non-conjugated polyenes [C] include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, and 5-isopropylidene-2 Examples include cyclic non-conjugated dienes such as norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadien.

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

[0016] Specific examples of copolymers (A-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, and 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 (E NB) 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) Examples include 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, and ethylene·1-butene·1-octene·5-ethylidene-2-norbornene (ENB)·5-vinyl-2-norbornene copolymer. The copolymer (A-1) may be included in the industrial belt composition alone or in combination of two or more types.

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

[0018] <<Requirement (2)>> The content of structural units derived from non-conjugated polyene [C] is 0.1 to 6.0 mol% relative to 100 mol% of the total structural units derived from ethylene [A], the α-olefin [B] having 4 to 20 carbon atoms, and the non-conjugated polyene [C]. Copolymer (A-1) in which the content of structural units derived from non-conjugated polyene [C] is within the above range has sufficient crosslinkability and flexibility. The lower limit of the content of structural units derived from non-conjugated polyenes [C] is preferably 0.5 mol%, more preferably 1.0 mol%. The upper limit of the content of structural units derived from non-conjugated polyenes [C] is preferably 4.0 mol%, more preferably 3.5 mol%, and even more preferably 3.0 mol%. When the content of structural units derived from non-conjugated polyene [C] is within the above range, a copolymer (A-1) with sufficient crosslinkability and flexibility can be obtained.

[0019] <<Requirement (3)>> Mooney viscosity at 125°C (ML) (1+4)125°C is in the range of 5 to 100, preferably 10 to 80, more preferably 12 to 60, even more preferably 15 to 40, and particularly preferably 20 to 25. Mooney viscosity ML of copolymer (A-1) at 125°C (1+4) When the temperature is within the above range of 125°C, copolymer (A-1) is obtained that exhibits good processability and fluidity, as well as good post-processing quality (ribbon handling properties) and excellent physical properties.

[0020] Copolymer (A-1) has a Mooney viscosity of ML at 100°C. (1+4) 100°C is preferably 10-200°C, more preferably 15-100°C, even more preferably 20-50°C, and particularly preferably 25-35°C.

[0021] <<Requirement (4)>> The B value, expressed by the following formula (i), is 1.20 or higher. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefins with 4 to 20 carbon atoms [B], and unconjugated polyenes [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A]-α-olefins with 4 to 20 carbon atoms [B].] The B value is preferably in the range of 1.20 to 1.80, and particularly preferably in the range of 1.22 to 1.40. When the B value is 1.20 or higher, the copolymer (A-1) exhibits suppressed compression set (CS) at low temperatures, making it easier to obtain a copolymer (A-1) with an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature.

[0022] The copolymer (A-1) may contain structural units derived from at least one monomer selected from the group consisting of ethylene [A], α-olefins having 4 to 20 carbon atoms [B], and non-conjugated polyenes [C], including units derived from biomass-derived monomers and / or chemically recycled monomers.

[0023] Copolymer (A-1) may contain at least one structural unit derived from biomass-derived monomers. The biomass-derived monomer used as a raw material for copolymer (A-1) may be biomass-derived ethylene, biomass-derived α-olefin, or biomass-derived non-conjugated polyene. Examples of biomass-derived α-olefins include biomass-derived propylene. Examples of biomass-derived non-conjugated polyenes include biomass-derived 5-ethylidene-2-norbornene (ENB) and biomass-derived 5-vinyl-2-norbornene. The monomers used as raw materials for copolymer (A-1) may contain only biomass-derived monomers, or they may contain both biomass-derived monomers and fossil fuel-derived monomers. 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 for copolymer (A-1) to contain structural units derived from biomass-derived monomers from the viewpoint of reducing environmental impact.

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

[0025] <<Method for producing ethylene-α-olefin-nonconjugated polyene copolymer (A-1)>> Copolymer (A-1) can be obtained by various known production methods, for example, by conventionally known production methods using metallocene catalysts. Examples of metallocene catalysts and production methods using such catalysts can be found in, for example, International Publication No. 2015 / 122415, particularly in paragraphs

[0249] to

[0320] of said publication.

[0026] The content of copolymer (A-1) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and even more preferably 45 to 55% by mass. However, the total content of copolymer (A-1) and copolymer (A-2), described later, shall be 100% by mass. The copolymer (A-1) may be included in the industrial belt composition alone or in combination of two or more types.

[0027] [Ethylene-α-olefin copolymer (A-2)] Ethylene-α-olefin copolymer (A-2) (hereinafter sometimes simply referred to as "polymer (A-2)") is an ethylene-α-olefin copolymer other than (A-1) mentioned above. The copolymer (A-2) contains structural units derived from ethylene and structural units derived from α-olefins. Examples of the above α-olefins include α-olefins having 3 to 20 carbon atoms. The α-olefins having 3 to 20 carbon atoms are not particularly limited and include, for example, 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, and 12-ethyl-1-tetradecene. Among these, the α-olefin is preferably an α-olefin having 3 to 12 carbon atoms, more preferably an α-olefin having 3 to 9 carbon atoms, even more preferably propylene, 1-butene, or 1-pentene, and particularly preferably propylene, from the viewpoint of obtaining a conveyor belt with excellent mechanical strength. These α-olefins may be used individually or in combination of two or more types.

[0028] The content of structural units derived from α-olefins in the ethylene-α-olefin copolymer (A-2) (the total content if there are two or more types of structural units derived from α-olefins) is preferably 20 to 50 mol%, more preferably 30 to 50 mol%, and even more preferably 40 to 50 mol%, relative to the total number of moles of structural units constituting the copolymer (A-2). The content of structural units derived from α-olefins is determined by the measurement method described in the examples below. The above α-olefins may be used individually or in combination of two or more.

[0029] The content of ethylene-derived structural units in the ethylene-α-olefin copolymer (A-2) is preferably 50 to 80 mol%, more preferably 50 to 75 mol%, and even more preferably 55 to 70 mol%, relative to the total number of moles of structural units constituting the copolymer (A-2). The content of structural units derived from ethylene is determined by the measurement method described in the examples below.

[0030] The copolymer (A-2) preferably satisfies at least one of the following requirements (i) and (ii). Requirement (i) Mooney viscosity Mooney viscosity ML of copolymer (A-2) at 100°C (1+4) At 100°C, the viscosity is preferably 10-100, more preferably 20-80, even more preferably 25-60, and particularly preferably 25-50. Mooney viscosity at 100°C is ML. (1+4)When 100°C is within the above range, an industrial belt composition with a small molding shrinkage rate and excellent processability can be obtained. Mooney viscosity ML at 100°C (1+4) 100°C can be measured and determined by the method described in JIS K6300.

[0031] Requirement (ii) Density The density of the copolymer (A-2) is preferably 840 - 920 kg / m 3 and more preferably 850 - 915 kg / m 3 and even more preferably 860 - 915 kg / m 3 When the density is within the above range, a conveyor belt with a small molding shrinkage rate and excellent strength characteristics and abrasion resistance can be obtained. The density can be measured and determined by the method described in ASTM D1505.

[0032] The copolymer (A-2) is preferably solid at room temperature to about 100°C, preferably at a temperature around 90°C.

[0033] The copolymer (A-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 (A-2) that satisfies the above physical properties, etc., the copolymer (A-2) is preferably synthesized by a method using a metallocene catalyst. Specifically, it is more preferably synthesized by using a catalyst containing a metallocene compound and an aluminum-containing compound, etc. 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.

[0034] The content of the copolymer (A-2) is preferably 30 - 70% by mass, more preferably 40 - 60% by mass, and even more preferably 45 - 55% by mass. However, the total content of the above copolymers (A-1) and (A-2) is 100% by mass. The copolymer (A-2) may be included in the industrial belt composition alone or in combination of two or more types.

[0035] The copolymer (A-2) may include structural units derived from at least one monomer selected from the group consisting of ethylene and α-olefins as described above, including structural units derived from biomass-derived monomers and / or chemically recycled monomers. The biomass-derived monomers in copolymer (A-2) are the same as the biomass-derived monomers in copolymer (A-1) described above. Similarly, the chemically recycled monomers in copolymer (A-2) are the same as the chemically recycled monomers in copolymer (A-1) described above.

[0036] <<Titanate coupling agent>> Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, and isopropyl tri(N-aminoethyl-aminoethyl) titanate. Among these, isopropyl triisostearoyl titanate and tetraoctylbis[ditridecylphosphite] titanate (46B) are preferred as titanate coupling agents, and isopropyl triisostearoyl titanate is more preferred. The titanate coupling agent content is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, based on 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2), from the viewpoint of increasing the heat resistance and elongation at break of the resulting molded article. Furthermore, from the viewpoint of increasing the heat resistance and elongation at break of the resulting molded article, the content of the titanate coupling agent is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by weight, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the reinforcing agent. When the titanate coupling agent content is within the above range, the industrial belt composition exhibits excellent elongation at break and heat resistance of the crosslinked sheet (crosslinked body), and, when formed into a laminate, excellent adhesive strength with the layer containing fibrous material. The titanate coupling agent may be included in the composition alone or in combination of two or more types.

[0037] <<Reinforcement agent>> The industrial belt composition contains carbon black as a reinforcing agent. Examples of carbon black include Asahi #55G, Asahi #60UG (product names, manufactured by Asahi Carbon Co., Ltd.), Seast V, Seast SO, v116, Seast 3, vSeast 6, Seast 9, Seast SP, Seast TA, etc. (product names, manufactured by Tokai Carbon Co., Ltd.). Furthermore, carbon black may be carbon black that has been surface-treated with a silane coupling agent or the like.

[0038] The carbon black content is preferably 5 to 100 parts by mass, more preferably 5 to 60 parts by mass, even more preferably 10 to 40 parts by mass, and particularly preferably 10 to 30 parts by mass, based on 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2).

[0039] The reinforcing agent preferably further contains silica. Examples of silica include, specifically, wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, and aluminum silicate. Among these, wet silica (hydrated silica) is preferred as the silica.

[0040] The silica content is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 3 to 15 parts by mass, based on 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). Silica may be used individually or in combination of two or more types.

[0041] <<Transpolyoctenylene>> The industrial belt composition preferably further contains trans-polyoctenylene. Trans-polyoctenylene is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond. A metathesis polymer refers to a polymer obtained by metathesis polymerization of trans-double bonded cyclooctene using a metal atom as a polymerization catalyst. When transpolyoctenylene is included, the industrial belt composition exhibits good adhesion to layers containing other materials, such as fibrous materials like industrial belts, and the resulting crosslinked laminate has excellent adhesive strength to layers containing fibrous materials.

[0042] Transpolyoctenylene may be obtained by synthesis or as a commercially available product. An example of a commercially available product is VESTENAMER (trade name) from Evonik Industries.

[0043] The transpolyoctenylene content is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the copolymer (A-2).

[0044] <<Modified polybutadiene>> The industrial belt composition may further contain modified polybutadiene. When modified polybutadiene (N) is included, the adhesive properties are excellent, and the adhesive strength to synthetic fibers is further improved. Suitable examples of modified polybutadiene include polybutadiene modified with an unsaturated carboxylic acid or its derivative. Examples of unsaturated carboxylic acids or their derivatives 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 endocis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (Nadic acid (trademark)), as well as derivatives thereof such as acid halides, amides, imides, acid anhydrides, and esters. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred as modified polybutadienes, maleic acid, nadic acid and their acid anhydrides are more preferred, and maleic anhydride is particularly preferred.

[0045] Commercially available modified polybutadiene may be used. For example, commercially available maleic anhydride modified polybutadienes include Ricon130MA8, Ricon130MA13, Ricon130MA20, Ricon131MA5, Ricon131MA10, Ricon131MA17, Ricon131MA20, and Ricon184MA6 (all trade names, manufactured by Cray Valley).

[0046] The content of modified polybutadiene is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 10 parts by mass, even more preferably 0.4 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). Modified polybutadiene may be included in the composition alone or in combination of two or more types.

[0047] The industrial belt composition may contain components other than the copolymer (A-1), copolymer (A-2), titanate coupling agent, carbon black and silica, trans-polyoctenylene, and modified polybutadiene as reinforcing agents (hereinafter also referred to as "other components") to the extent that they do not impair the effects of the present invention. Other components include, for example, crosslinking agents, crosslinking aids, vulcanization accelerators, vulcanization aids, reinforcing agents other than carbon black and silica, softeners, antioxidants, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. These other components may be used individually or in combination of two or more.

[0048] <<Organic peroxide>> The industrial belt 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)hexine-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, and tert-butylcumyl peroxide. Among these, dicumyl peroxide (DCP) and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane are preferred as organic peroxides.

[0049] The content of 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 even more preferably 1 to 8 parts by mass, based on 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). Organic peroxides may be included in the industrial belt composition individually or in combination of two or more types. When the content of organic peroxides is within the above range, blooming on the surface of the resulting molded article is suppressed, and the industrial belt composition exhibits excellent crosslinking properties, making it preferable.

[0050] When an organic peroxide is included as a crosslinking agent, it is preferable that the industrial belt composition further includes 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; zinc oxide (e.g., ZnO#1, zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.); magnesium oxide; and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0051] When a crosslinking aid is used, the content of the crosslinking aid is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, based on 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). The crosslinking agent may be included in the industrial belt composition alone or in combination of two or more types.

[0052] The industrial belt composition may further contain crosslinking agents other than the organic peroxides mentioned above. Examples of crosslinking agents other than organic peroxides include phenolic resins, sulfur compounds, hydrosilicone compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, epoxy compounds, and isocyanate compounds, which are commonly used when crosslinking rubber. Of these, sulfur compounds (hereinafter also referred to as "vulcanizing agents") are preferred as crosslinking agents other than organic peroxides.

[0053] Examples of sulfur compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0054] When the industrial belt 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, per 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). When the sulfur compound content is within the above range, blooming on the surface of the resulting molded article is suppressed, and the industrial belt composition exhibits excellent crosslinking properties.

[0055] If the industrial belt composition contains a sulfur-based compound as a crosslinking agent, it is preferable that the industrial belt composition further contains a vulcanization accelerator. Examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N'-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (e.g., Sunceller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noxellar MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, and 2-(2,6-diethyl Thiazole-based vulcanization accelerators such as ru-4-morpholinothio)benzothiazole and dibenzothiadyl disulfide (e.g., Suncellar DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorthotrylguanidine; aldehydeamine-based vulcanization accelerators such as acetaldehyde-aniline condensate and butyraldehyde-aniline condensate; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; tetramethylthiuram monosulfide (e.g., Suncellar TS ( Thiuram-based vulcanization accelerators such as (product name; manufactured by Sanshin Chemical Industry Co., Ltd.), tetramethyl thiuram disulfide (e.g., Suncellar TT (product name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethyl thiuram disulfide (e.g., Suncellar TET (product name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutyl thiuram disulfide (e.g., Suncellar TBT (product name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Suncellar TRA (product name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, diethyldithio Examples of dithioate-based vulcanization accelerators include zinc carbamate, zinc dibutyldithiocarbamate (e.g., Suncellar PZ, Suncellar BZ, and Suncellar EZ (product names; manufactured by Sanshin Chemical Industry Co., Ltd.)), and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators include ethylenethiourea (e.g., Suncellar BUR (product name; manufactured by Sanshin Chemical Industry Co., Ltd.), Suncellar 22-C (product name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea); and xantate-based vulcanization accelerators such as zinc dibutylxatonate.

[0056] When the industrial belt composition contains a vulcanization accelerator, the amount 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, based on 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). When the content of the vulcanization accelerator is within the above range, blooming on the surface of the resulting molded article is suppressed, and the industrial belt composition exhibits excellent crosslinking properties.

[0057] If the industrial belt composition contains a sulfur-based compound as a crosslinking agent, it may further contain a vulcanization aid.

[0058] Examples of vulcanization aids include the aforementioned crosslinking aids such as zinc oxide (e.g., ZnO#1 and two types of zinc oxide, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)). The amount of vulcanization aid is typically 1 to 20 parts by mass per 100 parts by mass of the total copolymer (A-1) and copolymer (A-2).

[0059] <<Anti-aging agent (stabilizer)>> The industrial belt composition may contain an anti-aging agent. When an industrial belt composition contains an anti-aging agent (stabilizer), the lifespan of components formed from the industrial belt composition, such as seal packings, can be extended. There are no particular restrictions on the anti-aging agent, and conventionally known anti-aging agents can be used. Examples of anti-aging agents include amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

[0060] Examples of anti-aging agents include aromatic 2-amine anti-aging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic anti-aging agents such as dibutylhydroxytoluene and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; thioether anti-aging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl] sulfide; dithiocarbamate anti-aging agents such as dibutyldithiocarbamate nickel; and sulfur-based anti-aging agents such as 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, and distearylthiodipropionate. Among these, the preferred anti-aging agent is a phenolic anti-aging agent and / or a sulfuric anti-aging agent, and more preferably a phenolic anti-aging agent and a sulfuric anti-aging agent.

[0061] The amount of antioxidant (total amount if two or more types of antioxidants are included) is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, per 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2). When the content of the antioxidant is within the above range, blooming on the surface of the resulting molded article is suppressed, and vulcanization inhibition can be further suppressed. Anti-aging agents may be included in the industrial belt composition either individually or in combination of two or more.

[0062] <<Processing aids>> The industrial belt composition may contain processing aids. There are no particular restrictions on processing aids, and generally, those that are added to rubber as processing aids are included. Specifically, examples of processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. Among these, stearic acid is preferred as a processing aid.

[0063] 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 even more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total amount of copolymer (A-1) and copolymer (A-2). When the content of the processing aid is within the above range, it is preferable because it exhibits excellent processability such as kneadability, extrusionability, and injection moldability. Processing aids may be included in the industrial belt composition either individually or in combination of two or more.

[0064] <<Activating agent>> Examples of activators include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triaryl merilate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide moduloides; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0065] If the industrial belt composition contains an activator, the activator content is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2).

[0066] Examples of reinforcing agents other than carbon black and silica include inorganic fillers, which are known rubber reinforcing agents that are incorporated into rubber compositions. Examples of inorganic fillers other than carbon black and silica include activated calcium carbonate, fine talc, fine silicic acid, light calcium carbonate, heavy calcium carbonate, talc, and clay. The content of reinforcing agents other than carbon black and silica is preferably 5 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the total of copolymer (A-1) and copolymer (A-2).

[0067] The industrial belt composition contains copolymer (A-1), copolymer (A-2), titanate coupling agent, and carbon black as a reinforcing agent. Therefore, the adhesion between the layer formed from this industrial belt composition and the layer containing fibrous material is improved, allowing for faster manufacturing of laminates. Furthermore, laminates comprising a layer obtained by crosslinking this industrial belt composition exhibit excellent adhesive strength and can be used in a wide range of applications, including hoses and belts.

[0068] Mooney viscosity ML at 100°C for uncrosslinked industrial belt compositions (1+4) The temperature at 100°C is preferably 25-60, more preferably 30-50. Mooney viscosity at 100°C is ML. (1+4) When the temperature is within the aforementioned range of 100°C, an industrial belt composition with excellent processability can be obtained. Mooney viscosity ML of uncrosslinked industrial belt composition (1+4) 100℃ is measured and determined by the method described in the examples below. Furthermore, the uncrosslinked industrial belt composition does not contain the aforementioned crosslinking agent.

[0069] [Laminate] The laminate according to the present invention comprises a layer [I] containing the above-mentioned industrial belt composition and a layer [II] containing a fibrous material, wherein it is preferable that layer [I] and layer [II] are in contact with each other.

[0070] <<Layer [I]>> Layer [I] preferably contains the above-mentioned industrial belt composition, and more preferably is a layer formed by crosslinking the above-mentioned industrial belt composition.

[0071] <<Layer[II]>> Layer [II] contains fibrous material. It is sufficient that at least a portion of layer [II] contains fibrous material.

[0072] <<Textile Materials>> There are no particular restrictions on the above fiber materials, and various publicly known fiber materials can be used. Examples of fiber materials include natural fibers such as cotton and wood cellulose fibers; organic fiber materials made of fibers composed of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymers; and inorganic fiber materials such as glass fibers, PAN-based carbon fibers, pitch-based carbon fibers, alumina fibers, silicon carbide fibers, aluminum borate fibers, and potassium titanate whiskers.

[0073] These fiber materials may be long fibers (filaments) or short fibers (staples). Also, the fiber materials may be cord yarns, spun yarns, woven fabrics, knitted fabrics, canvas, non-woven fabrics, etc. Among these, as the fiber material, canvas is preferred.

[0074] Examples of the above polyamides 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.

[0075] <<RFL treatment>> In addition, these fiber materials may be surface-treated by known methods in order to improve the adhesiveness between the fiber materials or with the above layer [I]. Examples of the surface treatment method for fiber materials include methods such as resorcinol formaldehyde latex (RFL) treatment.

[0076] RFL treatment is an adhesive treatment for fibrous materials using a treatment solution (RFL solution) containing resorcinol, formalin, and latex. The RFL solution is a mixture of the initial condensate of resorcinol and formalin and rubber latex. Examples of the above-mentioned 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), and natural rubber. The rubber latex may be used individually or as a blend of two or more types. The fibrous material preferably contains fibers treated with resorcinol-formaldehyde latex (RFL).

[0077] <Method for manufacturing laminates> There are no particular restrictions on the method for manufacturing the laminate, and known methods for manufacturing laminates can be used. Examples of methods for manufacturing the laminate include a method in which a layer [I] containing an uncrosslinked industrial belt composition manufactured (molded) in advance by a known method is bonded to a layer [II] containing a fiber material, and then the layer [I] made of the industrial belt composition is crosslinked; a method in which a layer [I] made of a crosslinked industrial belt composition is bonded to a layer [II] containing a fiber material; or a method in which a layer [I] made of an industrial belt composition is extruded onto a layer [II] containing a fiber material, and then the layer [I] made of the industrial belt composition is crosslinked.

[0078] There are no particular limitations on the method for preparing the above industrial belt composition. It can be obtained by kneading the above ethylene-α-olefin-non-conjugated polyene copolymer (A-1), copolymer (A-2), a reinforcing agent containing the above carbon black, a titanate coupling agent, and, if necessary, other components such as the above silica, trans polyoctenylene, modified polybutadiene, a crosslinking agent, an antioxidant, and a processing aid, using various known kneading and mixing equipment, such as a Banbury mixer, a kneader, an internal mixer (closed mixer) like an Intermix, and rolls.

[0079] The uncrosslinked industrial belt composition obtained by kneading may be molded into a desired shape by various molding methods such as an extrusion molding machine, calender roll, press, injection molding machine, or transfer molding machine, and then the composition may be further crosslinked to form layer [I] and laminated (bonded) with layer [II], or the uncrosslinked industrial belt composition may be molded into a desired shape by the above method and then laminated (bonded) with layer [II] and crosslinked.

[0080] There are no particular limitations on the method of crosslinking layer [I], and examples include heating with a crosslinking agent, or irradiation with light, gamma rays, or electron beams.

[0081] Furthermore, when crosslinking, a mold may be used, or the crosslinking may be performed without a mold. When crosslinking is performed without a mold, the molding and crosslinking processes are usually carried out continuously. As for heating methods in the crosslinking tank, heating tanks such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), and steam can be used.

[0082] <<Applications of Laminates>> From the viewpoint of excellent elongation at break, heat resistance, and adhesion to fibrous materials, the above laminate can be suitably used as an industrial belt. The laminate can be suitably used, for example, in automobile hoses, water supply hoses, gas hoses; industrial belts such as power transmission belts and conveyor belts; and escalator handrails.

[0083] Examples of automotive hoses include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the above-mentioned power transmission belts include V-belts, flat belts, and toothed belts. Examples of the above-mentioned conveying belts include light conveying belts, cylindrical belts, rough-top belts, flanged conveying belts, U-shaped guided conveying belts, and V-guided conveying belts. [Examples]

[0084] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples. The following copolymers were used in the examples and comparative examples.

[0085] <Ethylene-α-olefin-nonconjugated polyene copolymer (A-1)> Following the description in [Synthesis Example C1] of International Publication No. 2015 / 122415, an ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer having the following properties was synthesized. Hereinafter, this will be referred to as "ethylene copolymer (A-1)". The composition and properties of ethylene copolymer (A-1) are as follows.

[0086] <<Composition and physical properties of ethylene-1-butene-ENB copolymer>> Ethylene-derived structural units: 67.7 mol% Structural units derived from 1-butene: 30.0 mol% Structural units derived from 5-ethylidene-2-norbornene (ENB): 2.3 mol% Mooney Viscosity ML (1+4) 100℃:30 Mooney Viscosity ML (1+4) 125℃:22 B value: 1.3

[0087] The aforementioned content (mol%) is 1 The intensity was determined by measuring it using an H-NMR spectrometer. Details of the measurement conditions are as described in International Publication No. 2015 / 122415.

[0088] <Ethylene-α-olefin copolymer (A-2)> The following ethylene-propylene copolymer was used as the ethylene-α-olefin copolymer (A-2). Product name: Mitsui EPT 0045, Mooney viscosity ML (1+4) 100℃ = 40, Ethylene content = 61 mol%.

[0089] [Example 1] As the first stage, using a batch-type mixer (Kobe Steel, Ltd.: BB-1800 Mixtron mixer, volume 1.63L), 50 parts by mass of ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer as ethylene copolymer (A-1), 50 parts by mass of ethylene-propylene copolymer as ethylene-α-olefin copolymer (A-2), 20 parts by mass of carbon black (Asahi #60UG (FEF): Asahi Carbon Co., Ltd.) and 10 parts by mass of silica (Nipsil LP: Tosoh Silica Co., Ltd.) as reinforcing agents, and activated zinc oxide (META-Z) as an activator. 5 parts by mass of 40L (manufactured by Inoue Lime Industry Co., Ltd.), 0.5 parts by mass of stearic acid (Tsubaki series stearic acid: manufactured by NOF Corporation) as a processing aid, 2 parts by mass of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010: manufactured by BASF Japan Ltd.) as an antioxidant, 4 parts by mass of 2-mercaptobenzimidazole (Sandant MB: manufactured by Sanshin Chemical Industry Co., Ltd.), 5 parts by mass of transpolyoctenylene (VESTENAMER 8012: manufactured by Evonik Industries), and 3 parts by mass of isopropyltriisostearoyl titanate (Plenact TTS: manufactured by Ajinomoto Fine Techno Co., Ltd.) as a titanate coupling agent were kneaded to obtain an uncrosslinked rubber composition (composition-1). The above mixing was performed with a rotor speed of 36 rpm and a mixing time of 5 minutes.

[0090] After confirming that the temperature of the uncrosslinked rubber composition (compound-1) obtained in the first stage was 40°C or lower, 6.8 parts by mass of dicumyl peroxide (Mitsui DCP-40C: manufactured by Kayaku Akzo Co., Ltd.) and 1 part by mass of maleic anhydride-modified polybutadiene (Ricon 131MA17: manufactured by Cray Valley) were added as crosslinking agents using a 6-inch roll (manufactured by Nippon Roll Co., Ltd.) and kneaded to obtain an uncrosslinked rubber composition (compound-2). The above mixing was performed with roll temperatures of 50°C / 50°C for the front roll and 15 rpm / 18 rpm for the front roll and rear roll. Furthermore, as a test specimen to be used in the method for evaluating adhesion to fibrous materials described later, the rubber composition (compound-2) was separated into a sheet, and an uncrosslinked sheet with a thickness of 3 mm was prepared.

[0091] Next, this rubber composition (compound-2) was crosslinked by pressurizing it at 170°C for 15 minutes using a 100-ton press molding machine to produce a 2 mm thick crosslinked sheet (crosslinked body). The physical properties and evaluation of the obtained crosslinked sheet were performed using the following measurement methods. The results are shown in Table 1.

[0092] <Moony Viscosity ML> (1+4) 100℃> Mooney viscosity ML at 100°C for uncrosslinked rubber composition (compound-1) (1+4) The temperature at 100°C was measured using a Mooney viscometer (Shimadzu Corporation, model number: SMV-301RT) in accordance with JIS K6300-1 (2013).

[0093] [Physical properties of crosslinked sheets] (1) Durometer A hardness The hardness (Duro-A) of the 2 mm thick crosslinked sheet prepared as described above was measured in accordance with the description of test type A of the "Durometer hardness test" in section 6 of JIS K6253 (2012) "Vulcanized rubber and thermoplastic rubber - Method for determining hardness".

[0094] (2) Tensile test: Tensile stress at fracture, Tensile elongation at fracture The tensile stress at the breaking point and the tensile elongation at the breaking point of the 2 mm thick crosslinked sheet prepared as described above were measured using the following method. The cross-linked sheet prepared as described above was punched out to create a Type 3 dumbbell test specimen as described in JIS K6251 (2017). Using this specimen, a tensile test was performed under the conditions of a measurement temperature of 23°C and a tensile speed of 500 mm / min, according to the method specified in Section 3 of JIS K6251, and the tensile stress at fracture (TB) and tensile elongation at fracture (EB) were measured. A crosslinked sheet (crosslinked body) can be said to have excellent elongation at break if its tensile stress at break (TB) is 10 MPa or higher and its tensile elongation at break (EB) is 440% or higher.

[0095] (3) Compression set (CS) A rubber composition (compound-2) was crosslinked at 170°C for 20 minutes using a 100-ton press molding machine to produce a straight cylindrical specimen (crosslinked body) with a thickness of 12.5 mm and a diameter of 29 mm for measuring compression set (CS). The compression set of the obtained specimen was measured after treatment at 120°C for 72 hours according to JIS K6262 (1997). If the compression set is 40% or less, the cross-linked sheet (cross-linked material) can be said to have excellent heat resistance.

[0096] (4) Peel strength (adhesion to fibrous materials) Adhesion to fibrous materials was measured by the peel strength (adhesion strength) between the layer containing the crosslinked rubber composition [I] and the layer containing the fibrous material [II]. The 3mm thick uncrosslinked sheet prepared as described above was placed on a nylon fiber woven fabric (manufactured by Ayaha 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, creating a laminate comprising a layer [I] containing the crosslinked rubber composition and a layer [II] containing the fiber material. A 25mm wide test piece was punched out from the laminate, and a T peel test was performed at a tensile speed of 50mm / min. to determine the peel strength (adhesion strength) (N / cm) between layer [I] and layer [II]. The peel test was performed three times, and the arithmetic mean was taken as the peel strength. A peel strength value of 115 N / cm or higher indicates excellent adhesion to fibrous materials.

[0097] [Example 2] Except for changing the amount of titanate coupling agent used in Example 1 to 5 parts by mass, a rubber composition and a crosslinked sheet (crosslinked body) were manufactured in the same manner as in Example 1. The physical properties and the above evaluation were performed on the obtained rubber composition and crosslinked sheet in the same manner as in Example 1. The results are shown in Table 1.

[0098] [Comparative Example 1] A rubber composition and a crosslinked sheet (crosslinked body) were manufactured in the same manner as in Example 1, except that the titanate coupling agent used in Example 1 was not included. The physical properties and the above evaluation were performed on the obtained rubber composition and crosslinked sheet in the same manner as in Example 1. The results are shown in Table 1.

[0099] [Comparative Example 2] A rubber composition and a crosslinked sheet (crosslinked material) were prepared in the same manner as in Example 1, except that 3 parts by mass of 7-octenyltrimethoxysilane (product name: KBM-1083, manufactured by Shin-Etsu Chemical Co., Ltd.) were added as a silane coupling agent instead of the titanate coupling agent. The physical properties and the above evaluations were performed on the obtained rubber composition and crosslinked sheet in the same manner as in Example 1. The results are shown in Table 1.

[0100] [Table 1]

[0101] As shown in Table 1, the crosslinked sheets (crosslinked bodies) obtained from the rubber compositions of Examples 1 and 2 exhibit superior elongation at break, heat resistance, and adhesion to fibrous materials compared to the crosslinked sheets (crosslinked bodies) obtained from the rubber compositions of Comparative Examples 1 and 2.

Claims

1. An ethylene-α-olefin-non-conjugated polyene copolymer (A-1) that satisfies the following requirements (1) to (4) and contains structural units derived from ethylene [A], structural units derived from α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyene [C], Ethylene-α-olefin copolymer (A-2) other than (A-1) above, Reinforcement agent, Titanate coupling agent and Includes, A composition for industrial belts, wherein the reinforcing agent contains carbon black; (1) The molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefins [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) The content of structural units derived from non-conjugated polyene [C] is 0.1 to 6.0 mol% relative to 100 mol% of the total structural units derived from ethylene [A], α-olefins having 4 to 20 carbon atoms [B], and non-conjugated polyene [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C corresponds to 5-100; (4) The B value expressed by the following formula (i) is 1.20 or higher. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefins with 4 to 20 carbon atoms [B], and unconjugated polyenes [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A]-α-olefins with 4 to 20 carbon atoms [B].]

2. The industrial belt 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 industrial belt composition according to claim 1, wherein the content of structural units derived from ethylene in the ethylene-α-olefin copolymer (A-2) is 50 to 80 mol% of the total number of moles of structural units constituting the copolymer (A-2).

4. The industrial belt composition according to claim 1, wherein the carbon black content is 5 to 100 parts by mass per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2).

5. The industrial belt composition according to claim 1, wherein the content of the titanate coupling agent is 0.5 to 10 parts by mass per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2).

6. The industrial belt composition according to claim 1, wherein the reinforcing agent further comprises silica.

7. The industrial belt composition according to claim 1, wherein the content of the titanate coupling agent is 1 to 50 parts by mass per 100 parts by mass of the reinforcing agent.

8. The industrial belt composition according to claim 1, further comprising transpolyoctenylene.

9. The industrial belt composition according to claim 8, wherein the content of transpolyoctenylene is 0.5 to 50 parts by mass per 100 parts by mass of the total of the ethylene-α-olefin-nonconjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2).

10. The industrial belt composition according to claim 1, further comprising modified polybutadiene.

11. The industrial belt composition according to claim 10, wherein the content of the modified polybutadiene is 0.1 to 50 parts by mass per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) and the ethylene-α-olefin copolymer (A-2).

12. The industrial belt composition according to claim 1, further comprising an organic peroxide as a crosslinking agent.

13. A layer [I] made of the industrial belt composition according to any one of claims 1 to 12, A layer containing fibrous material [II], Equipped with, A laminate in which layer [I] and layer [II] are in contact.

14. The laminate according to claim 13, wherein the layer [I] is a layer formed by crosslinking the industrial belt composition.

15. The laminate according to claim 13, wherein the fibrous material includes fibers treated with resorcinol-formaldehyde latex (RFL).

16. The laminate according to claim 13, wherein the fibrous material is canvas.

17. An industrial belt having the laminate described in claim 13.

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