Ethylene-based copolymer composition, laminate and industrial belt

Abstract

To obtain an ethylene-based copolymer composition which can improve productivity by improving the tackiness to a layer comprising a fibrous material, has excellent adhesiveness to a layer comprising a fibrous material and can maintain mechanical properties such as abrasion resistance when formed into a laminate.SOLUTION: There is provided an ethylene-based copolymer composition which comprises (L) an ethylene-α-olefin-non-conjugated polyene copolymer which contains a structural unit derived from ethylene [A], a structural unit derived from an α-olefin having 3 to 20 carbon atoms [B] and a structural unit derived from a specific non-conjugated polyene [C] in a specific ratio, has a Mooney viscosity ML(1+4) at 125°C of 10 to 100 and has a B value, expressed by the following equation, of 1.10 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])](i) [Wherein, [E], [X] and [Y] represent the molar fractions of ethylene [A], α-olefin [B] having 3 to 20 carbon atoms and a non-conjugated polyene [C], respectively and [EX] represents the dyad fraction of ethylene [A]-α-olefin [B] having 3 to 20 carbon atoms.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a crosslinkable ethylene copolymer composition, a laminate using the composition together with a layer containing a fibrous material, and an industrial belt. [Background technology]

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

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

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

[0005] [Patent Document 1] Special Publication No. 42-23632 Summary of the Invention [Problem to be solved by the invention]

[0006] One application of ethylene-α-olefin-non-conjugated polyene copolymers is industrial belts, which are often used in the form of laminates containing a layer containing ethylene-α-olefin-non-conjugated polyene copolymer and a layer containing a fibrous material, with these layers in direct contact with each other, and these layers are required to be resistant to peeling and have excellent abrasion resistance.

[0007] Therefore, an object of the present invention is to provide an ethylene copolymer composition which can improve productivity by improving adhesion to a layer containing a fiber material, has excellent adhesion to a layer containing a fiber material, and can maintain mechanical properties such as abrasion resistance when formed into a laminate. [Means for solving the problem]

[0008] As a result of investigations aimed at solving the above-mentioned problems, the present inventors discovered that the above-mentioned problems can be solved by adding a resorcinol-based compound to an ethylene-α-olefin-non-conjugated polyene copolymer, and thus completed the present invention.

[0009] The present invention relates to the following [1] to

[13] . [1] An ethylene copolymer composition for industrial belts, comprising the following (L) and (M): (L) An ethylene-α-olefin-non-conjugated polyene copolymer comprising structural units derived from ethylene [A], structural units derived from an α-olefin [B] having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [C] containing a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II) in one molecule, and satisfying the following requirements (1) to (4): (M) Resorcinol compounds.

[0010] [ka]

[0011] (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from an α-olefin [B] having 3 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % relative to 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C is 10 to 100, (4) The B value represented by the following formula (i) is 1.10 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 3 to 20 carbon atoms, and non-conjugated polyene [C], respectively, and [EX] represents the dyad sequence fraction of ethylene [A] and α-olefin [B] having 3 to 20 carbon atoms.] [2] The ethylene copolymer composition for industrial belts according to [1], wherein the structural units derived from the non-conjugated polyene [C] include structural units derived from 5-vinyl-2-norbornene. [3] The ethylene copolymer composition for industrial belts according to [1] or [2], wherein the content of the structural units derived from the non-conjugated polyene [C] is 0.1 to 1.0 mol % relative to 100 mol % of the total of the structural units [A], [B] and [C]. [4] The ethylene copolymer composition for industrial belts according to any one of [1] to [3], wherein the α-olefin [B] having 3 to 20 carbon atoms constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) is propylene. [5] The ethylene copolymer composition for industrial belts according to any one of [1] to [4], further comprising (B) an organic peroxide as a crosslinking agent. [6] The ethylene copolymer composition for industrial belts according to any one of [1] to [5], comprising 0.1 to 20 parts by mass of a resorcinol compound (M) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L). [7] The ethylene copolymer composition for industrial belts according to any one of [1] to [6], further comprising the following (L'): (L') An ethylene-α-olefin-non-conjugated polyene copolymer comprising a structural unit derived from ethylene [A'], a structural unit derived from an α-olefin [B'] having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C'] containing a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II) in one molecule, and satisfying the requirements of (1'), (2'), (3') and (4') below.

[0012] [ka]

[0013] (1') the molar ratio [A'] / [B'] of the structural units derived from ethylene [A'] to the structural units derived from α-olefin [B'] is 40 / 60 to 90 / 10, (2') the content of the structural units derived from non-conjugated polyene [C'] is 0.1 to 6.0 mol % based on 100 mol % of the total of the structural units [A'], [B'] and [C'], (3') Mooney viscosity ML at 125°C (1+4) 125°C is 0.1 or more and less than 10, (4') The B value represented by the following formula (i') is 1.10 or more. B value=([EX']+2[Y']) / [2×[E']×([X']+[Y'])]···(i') Here, [E'], [X'], and [Y'] represent the mole fractions of ethylene [A'], α-olefin [B'] having 3 to 20 carbon atoms, and non-conjugated polyene [C'], respectively, and [EX'] represents the ethylene [A']-α-olefin [B'] having 3 to 20 carbon atoms dyad chain fraction. [8] The ethylene-based copolymer composition for industrial belts according to [7], containing 0.1 to 20 parts by mass of a resorcinol-based compound (M) per 100 parts by mass in total of the amount of the ethylene·α-olefin·non-conjugated polyene copolymer (L) and the amount of the ethylene·α-olefin·non-conjugated polyene copolymer (L’). [9] A laminate characterized in that a layer [I] composed of the ethylene-based copolymer composition for industrial belts according to any one of [1] to [8] is in contact with a layer [II] containing a fiber material.

[10] The laminate according to [9], wherein the ethylene-based copolymer composition for industrial belts is crosslinked.

[11] The laminate according to [9] or

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

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

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

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

[12] . [Advantages of the Invention]

[0014] When producing a laminate with a layer containing a fiber material, the ethylene-based copolymer composition of the present invention has improved adhesiveness with the layer, so that the production speed can be increased, and the laminate obtained by crosslinking has excellent adhesion strength and excellent abrasion resistance, and thus can be suitably used for industrial belts. [Embodiments for Carrying Out the Invention]

[0015] Hereinafter, the present invention will be described in more detail. Here, in this specification, "~" indicating a numerical range means a numerical range including the lower limit value and the upper limit value unless otherwise specified. For example, when expressed as "M~N" (M and N are numerical values satisfying M < N), it means "M or more and N or less" unless otherwise specified.

[0016] In this specification, the term "structural unit derived from ethylene" refers to a structural unit corresponding to ethylene, i.e., a structural unit represented by -CH-CH. The term "structural unit derived from an α-olefin" is similarly interpreted and refers to a structural unit corresponding to an α-olefin, i.e., a structural unit represented by -CH-CRR'- (R and R' are each independently a hydrogen atom or an alkyl group). The term "structural unit derived from a non-conjugated polyene" refers to a structural unit corresponding to a non-conjugated polyene, i.e., a structural unit having one or more pairs of bonds formed by cleavage of the π bond constituting one or more double bonds of the non-conjugated polyene.

[0017] [Ethylene copolymer composition for industrial belts] The ethylene copolymer composition for industrial belts according to the present invention (hereinafter, sometimes abbreviated as "ethylene copolymer composition" or "copolymer composition") comprises: Ethylene-α-olefin-non-conjugated polyene copolymer (L), Resorcinol compounds (M) Includes:

[0018] Ethylene-α-olefin-non-conjugated polyene copolymer (L) The ethylene-α-olefin-non-conjugated polyene copolymer (L), which is one of the components constituting the ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition that forms the layer [I] of the laminate of the present invention, is an ethylene-α-olefin-non-conjugated polyene copolymer that contains structural units derived from ethylene [A], structural units derived from an α-olefin [B] having 3 to 20 carbon atoms (hereinafter may be abbreviated as "α-olefin [B]"), and structural units derived from a non-conjugated polyene [C] containing, in one molecule, two or more partial structures selected from the group consisting of the following general formulae (I) and (II) (hereinafter may be abbreviated as "non-conjugated polyene [C]"), and satisfies the following requirements (1) to (4):

[0019] [ka]

[0020] (1) the molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefin [B] is 40 / 60 to 90 / 10; (2) the content of structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % relative to 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C is 10 to 100, (4) The B value represented by the following formula (i) is 1.10 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 3 to 20 carbon atoms, and non-conjugated polyene [C], respectively, and [EX] represents the ethylene [A]-α-olefin [B] having 3 to 20 carbon atoms dyad chain fraction. Such a specific ethylene-α-olefin-non-conjugated polyene copolymer is also called "ethylene-based copolymer (L)" and may be abbreviated as "ethylene-based copolymer (L)".

[0021] The α-olefin [B] having 3 to 20 carbon atoms and the non-conjugated polyene [C] may each be used alone or in combination of two or more. That is, the ethylene-α-olefin-non-conjugated polyene copolymer (L) used in the present invention contains structural units derived from ethylene [A], structural units derived from at least one type of α-olefin [B] having 3 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [C].

[0022] Examples of the α-olefin [B] having 3 to 20 carbon atoms include propylene having 3 carbon atoms, which has a linear structure without side chains, through 1-nonene having 9 carbon atoms and 1-decene having 10 carbon atoms, 1-nonadecene having 19 carbon atoms, and 1-eicosene having 20 carbon atoms, as well as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and the like, which have side chains.

[0023] The α-olefin [B] may be one type alone or a combination of two or more types. Among these, α-olefins having 3 to 10 carbon atoms are preferred, and particularly propylene, 1-butene, 1-hexene, 1-octene, etc. are preferred, with propylene being particularly preferred.

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

[0025] Among these, linear non-conjugated dienes such as 1,4-hexadiene and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred, and cyclic non-conjugated dienes are more preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being particularly preferred. That is, in one preferred embodiment of the present invention, the ethylene copolymer (L) used in the present invention contains a structural unit derived from 5-vinyl-2-norbornene as a structural unit derived from the non-conjugated polyene [C]. The non-conjugated polyene [C] may be one type alone or a combination of two or more types.

[0026] In a further preferred embodiment of the present invention, the ethylene copolymer (L) used in the present invention consists solely of structural units derived from 5-vinyl-2-norbornene as structural units derived from the non-conjugated polyene [C]. The ethylene [A], the α-olefin [B] and the non-conjugated polyene [C] constituting the ethylene copolymer (L) may each be derived from biomass or from chemical recycling.

[0027] Examples of the ethylene copolymer (L) include ethylene-propylene-1,4-hexadiene copolymer, 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-propylene-1-octene-1,4-hexadiene copolymer, ethylene-1-butene-1-octene-1,4-Hexadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene copolymer, ethylene-1-octene-5-ethylidene-2-norbornene copolymer, Ethylene-1-nonene-5-ethylidene-2-norbornene copolymer, Ethylene-1-decene-5-ethylidene-2-norbornene copolymer, Ethylene-propylene-1-octene-5-ethylidene-2-norbornene copolymer, Ethylene-1-butene-1-octene-5-ethylidene-2-norbornene copolymer, Ethylene-propylene-5-ethylidene-2-norbornene copolymer, Ethylene-propylene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, Ethylene-1-butene-5-ethylidene-2- Norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer Ethylene copolymer, ethylene-1-nonene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-decene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-propylene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-butene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer.

[0028] One or more types of ethylene copolymers (L) are used as needed. The ethylene copolymer (L) used in the present invention satisfies the following requirements (1) to (4).

[0029] Requirement (1) The ethylene copolymer (L) has (1) a molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from an α-olefin [B] having 3 to 20 carbon atoms of 40 / 60 to 90 / 10. The ethylene copolymer (L) having a molar ratio [[A] / [B]] within the above range exhibits an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature. The lower limit of the molar ratio [A] / [B] is preferably 45 / 55, more preferably 50 / 50, even more preferably 55 / 45, particularly preferably 60 / 40, and even more 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. Such an ethylene copolymer (L) is preferred because the molded article obtained by crosslinking exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility.

[0030] The ethylene content (content of structural units derived from ethylene) and the propylene content (content of structural units derived from propylene) in the ethylene copolymer (L) are 13 It can be determined by C-NMR.

[0031] Requirement (2) The ethylene copolymer (L) has (2) a content ratio of structural units derived from the non-conjugated polyene [C] of 0.1 to 6.0 mol %, preferably 0.1 to 1.0 mol %, relative to 100 mol % of the total of the structural units derived from [A], the structural units derived from [B], and the structural units derived from [C]. The ethylene copolymer (L) having a content ratio of structural units derived from the non-conjugated polyene [C] within the above range has sufficient crosslinkability and flexibility.

[0032] The lower limit of the content of the structural units derived from [C] is preferably 0.2 mol%, more preferably 0.3 mol%, and the upper limit of the content of the structural units derived from [C] is preferably 4.0 mol%, more preferably 3.5 mol%, even more preferably 3.0 mol%, particularly preferably 1.0 mol%, and even more preferably 0.5 mol%.

[0033] When the content of the structural unit derived from the non-conjugated polyene [C] is within the above range, an ethylene copolymer (L) having sufficient crosslinkability and flexibility can be obtained. The amount of non-conjugated polyene [C] in the ethylene copolymer (L) (the content of structural units derived from non-conjugated polyene [C]) is 13 It can be determined by C-NMR.

[0034] Requirement (3) The ethylene copolymer (L) has a Mooney viscosity ML at 125°C. (1+4) The temperature at 125°C is in the range of 10 to 100, preferably 20 to 95, more preferably 50 to 90, further preferably 60 to 80, and particularly preferably 65 to 75. When the Mooney viscosity is within the above range, the ethylene copolymer (L) has good processability and flowability, and exhibits good post-treatment quality (ribbon handling property), and the ethylene copolymer (L) has excellent physical properties.

[0035] Requirement (4) The ethylene copolymer (L) has a (4) B value of 1.10 or more, preferably 1.10 to 1.80, more preferably 1.12 to 1.40, still more preferably 1.14 to 1.30, and particularly preferably in the range of 1.16 to 1.25. An ethylene copolymer having a B value of less than 1.10 has a large compression set at low temperatures, and there is a risk that an ethylene copolymer having an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature cannot be obtained.

[0036] Other requirements In addition to the above requirements (1) to (4), the ethylene copolymer (L) used in the present invention preferably satisfies one or more requirements selected from the group consisting of the following requirements (5) to (9), and more preferably satisfies all of the following requirements (5) to (9):

[0037] Requirement (5) The ethylene copolymer (L) preferably has a weight average molecular weight (Mw), a mass fraction of the structural unit derived from the non-conjugated polyene [C] in the copolymer (mass fraction of (C): mass %), and a molecular weight of the non-conjugated polyene [C] (molecular weight of [C]) that satisfy the following relational formula (1): 4.5≦Mw×[C] mass fraction / 100 / [C] molecular weight≦80 Equation (1)

[0038] When the ethylene-based copolymer (L) satisfies the requirement (5), the content of structural units derived from the non-conjugated polyene [C] such as VNB is appropriate, and sufficient crosslinking performance is exhibited. In addition, when an industrial belt is produced using an ethylene-based copolymer composition containing the ethylene-based copolymer (L), the crosslinking rate is excellent, and the crosslinked industrial belt exhibits excellent mechanical properties, which is preferable.

[0039] The ethylene copolymer (L), more preferably, satisfies the following relational formula (1A). 45≦Mw×[C] mass fraction / 100 / [C] molecular weight≦80 Equation (1A) The weight average molecular weight (Mw) of the ethylene copolymer (L) means a value measured by 3D-GPC.

[0040] When the "mass fraction of Mw × [C] / 100 / molecular weight of [C]" of the ethylene copolymer (L) satisfies the above formula (1) or (1A), the degree of crosslinking is appropriate, and by using this copolymer, molded articles with a good balance of mechanical properties and heat aging resistance can be produced. If the "mass fraction of Mw × [C] / 100 / molecular weight of [C]" is too low, the crosslinking rate may be slow due to insufficient crosslinking, while if it is too high, excessive crosslinking may occur, resulting in deterioration of mechanical properties.

[0041] Requirement (6) The ethylene copolymer (L) preferably satisfies the following formula (2): P / ([η] 2.9 ) ≦ [C] mass fraction × 6 Equation (2) In equation (2), P is the complex viscosity η at a frequency ω = 0.1 rad / s obtained by performing linear viscoelasticity measurement (190 ° C) on the ethylene copolymer (L) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / s * (ω=100) The mass fraction of [C] represents the mass fraction (% by mass) of the structural units derived from the non-conjugated polyene [C].

[0042] Here, the complex viscosity η at frequency ω=0.1 rad / s * ( ω =0.1) and the complex viscosity η at frequency ω=100rad / s * (ω=100) The ratio P(η * (ω=0.1) / η * (ω=100) ) represents the frequency dependence of viscosity, and is the left side of equation (2), P / ([η] 2.9 ) tends to show a high value when there is a lot of long-chain branching, although it is affected by factors such as short-chain branching and molecular weight. Generally, in an ethylene-α-olefin-non-conjugated polyene copolymer, the more structural units derived from non-conjugated polyenes it contains, the more long-chain branching it tends to contain. However, the ethylene copolymer (L) used in the present invention has less long-chain branching than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, and is therefore thought to be able to satisfy the above formula (2). In the present invention, the P value is determined by calculating the ratio (η) of the complex viscosity at 0.1 rad / s and the complex viscosity at 100 rad / s, which are measured using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) under conditions of 190°C, 1.0% strain, and various frequencies. * The ratio was calculated.

[0043] The ethylene copolymer (L) used in the present invention preferably satisfies the following formula (2A). P / ([η] 2.9 ) ≦ (C) mass fraction × 5.7 Equation (2A) The intrinsic viscosity [η] means the value measured in decalin at 135°C.

[0044] Requirement (7) The ethylene copolymer (L) used in the present invention preferably has an intrinsic viscosity [η] of 0.1 to 5.0 dL / g, more preferably 0.5 to 4.0 dL / g, even more preferably 1.0 to 3.8 dL / g, and particularly preferably 2.0 to 3.5 dL / g. Here, the intrinsic viscosity [η] is the same as that described above in the requirement (6).

[0045] Requirement (8) The ethylene copolymer (L) used in the present invention preferably has a weight average molecular weight (Mw) of 100,000 to 800,000, more preferably 200,000 to 700,000, still more preferably 250,000 to 650,000, particularly preferably 300,000 to 600,000, and most preferably 400,000 to 500,000. The ethylene copolymer (L) used in the present invention preferably satisfies both the above requirements (7) and (8).

[0046] Requirement (9) The ethylene copolymer (L) used in the present invention has a complex viscosity η at a frequency ω=0.01 rad / s obtained by linear viscoelasticity measurement (190°C) using a rheometer. * (ω=0.01) (Pa·sec) and the complex viscosity η at frequency ω=10 rad / s * (ω=10) It is preferable that the iodine value (Pa·sec) and the iodine value derived from the non-conjugated polyene [C] satisfy the following formula (5): Log{η * (ω=0.01)} / Log{η * (ω=10)}≦0.0753 × {iodine value derived from non-conjugated polyene [C]} + 1.42 Equation (5) Here, the complex viscosity η * (ω=0.01) and complex viscosity η * (ω=10) is the complex viscosity η in requirement (6) except for the measurement frequency. * (ω=0.1) and complex viscosity η * (ω=100) can be obtained in the same way.

[0047] The iodine value derived from the non-conjugated polyene [C] can be calculated by the following formula: Iodine value derived from [C] = mass fraction of [C] × 253.81 / molecular weight of [C] In the above formula (5), the left side represents the shear rate dependency, which is an index of the amount of long chain branches, and the right side represents an index of the content of non-conjugated polyene [C] that is not consumed as long chain branches during polymerization. When the ethylene copolymer (L) satisfies the above formula (5), the degree of long chain branching is not too high, which is preferable. On the other hand, when the ethylene copolymer (L) does not satisfy the above formula (5), it is found that a large proportion of the copolymerized non-conjugated polyene (C) is consumed in the formation of long chain branches.

[0048] <Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (L)> The ethylene-α-olefin-non-conjugated polyene copolymer (L) used in the present invention can be obtained by various known production methods, for example, a conventionally known production method using a metallocene catalyst. Examples of metallocene catalysts and production methods using such catalysts include those described in WO 2015 / 122415, particularly paragraphs

[0249] to

[0320] of that publication.

[0049] Ethylene-α-olefin-non-conjugated polyene copolymer (L') The ethylene-based copolymer composition of the present invention may contain only the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymer (L) as the ethylene-α-olefin-non-conjugated polyene copolymer, but may also contain the following ethylene-α-olefin-non-conjugated polyene copolymer (L') [hereinafter sometimes abbreviated as "ethylene-based copolymer (L')"] as a second ethylene-α-olefin-non-conjugated polyene copolymer, in addition to the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymer (L), depending on the application, usage conditions and desired physical properties of the industrial belt:

[0050] (L') An ethylene-α-olefin-non-conjugated polyene copolymer comprising structural units derived from ethylene [A'], structural units derived from an α-olefin [B'] having 3 to 20 carbon atoms (hereinafter may be abbreviated as "α-olefin (B')"), and structural units derived from a non-conjugated polyene [C'] (hereinafter may be abbreviated as "non-conjugated polyene [C']") containing a total of two or more partial structures selected from the group consisting of the following general formulae (I) and (II) in one molecule, and satisfying the following requirements (1'), (2'), (3'), and (4'):

[0051] [ka]

[0052] (1') the molar ratio [[A'] / [B']] of the structural units derived from ethylene [A'] to the structural units derived from α-olefin [B'] 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 % of the total of the structural units [A'], [B'] and [C']; (3') Mooney viscosity ML at 125°C (1+4) 125°C is 0.1 or more and less than 10, (4') The B value represented by the following formula (i') is 1.10 or more. B value=([EX']+2[Y']) / [2×[E']×([X']+[Y'])]···(i') Here, [E'], [X'], and [Y'] represent the mole fractions of ethylene [A'], α-olefin [B'] having 3 to 20 carbon atoms, and non-conjugated polyene [C'], respectively, and [EX'] represents the ethylene [A']-α-olefin [B'] having 3 to 20 carbon atoms dyad chain fraction.

[0053] When the ethylene copolymer composition of the present invention contains such an ethylene-α-olefin-non-conjugated polyene copolymer (L'), it becomes possible to reduce the Mooney viscosity while maintaining the mechanical properties, and further improvement in moldability and processability can be expected, which is preferable.

[0054] Examples of the ethylene [A'], α-olefin [B'], and non-conjugated polyene [C'] constituting the ethylene copolymer (L') include the same as the ethylene [A], α-olefin [B], and non-conjugated polyene [C] described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," and they may be the same as or different from the ethylene [A], α-olefin [B], and non-conjugated polyene [C], respectively. In one preferred exemplary embodiment of the present invention, the ethylene [A'], α-olefin [B'], and non-conjugated polyene [C'] are the same as the ethylene [A], α-olefin [B], and non-conjugated polyene [C] described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," respectively.

[0055] The above requirement (1') corresponds to the requirement (1) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," and the range of the molar ratio [[A'] / [B']] is also the same as the molar ratio [[A] / [B]] specified in requirement (1). The above requirement (2') corresponds to the requirement (2) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," and the range of the content of structural units derived from the non-conjugated polyene [C'] is also the same as the content of structural units derived from the non-conjugated polyene [C] specified in requirement (2).

[0056] The above requirement (4') corresponds to the requirement (4) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," and the range of the B value possessed by the ethylene copolymer (L') is also the same as the range of the B value specified in requirement (4). On the other hand, the ethylene copolymer (L') has some differences from the ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0057] Requirement (3) The ethylene copolymer (L') has a Mooney viscosity ML at 125°C (3') (1+4) The Mooney viscosity ML at 125°C is in the range of 0.1 or more and less than 10, preferably 1 to 9, more preferably 3 to 8, and even more preferably 5 to 7. That is, the ethylene copolymer (L') has a lower Mooney viscosity ML compared to the ethylene-α-olefin-non-conjugated polyene copolymer (L). (1+4) It has a temperature of 125°C. When the Mooney viscosity is within the above range, the ethylene copolymer (L') has good processability and flowability.

[0058] Furthermore, the ethylene-based copolymer (L') is usually an ethylene-α-olefin-non-conjugated polyene copolymer different from the ethylene-α-olefin-non-conjugated polyene copolymer (L). In a typical embodiment of the present invention, the ethylene-based copolymer (L') tends to have a smaller intrinsic viscosity [η] and a smaller weight-average molecular weight (Mw) than the ethylene-α-olefin-non-conjugated polyene copolymer (L). Such an ethylene-α-olefin-non-conjugated polyene copolymer (L') preferably satisfies the following requirements (7') and (8'), which correspond to the requirements (7) and (8) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," respectively.

[0059] Requirements (7) The ethylene copolymer (L') preferably has an intrinsic viscosity [η] of 0.1 to 5.0 dL / g, more preferably 0.5 to 4.0 dL / g, even more preferably 1.0 to 3.8 dL / g, and particularly preferably 1.0 dL / g or more and less than 2.0 dL / g. Here, the intrinsic viscosity [η] is the same as that described above in the requirement (6').

[0060] Requirements (8) The ethylene copolymer (L') preferably has a weight average molecular weight (Mw) of less than 100,000, more preferably 50,000 or more and less than 100,000, even more preferably 70,000 or more and 95,000 or less, and particularly preferably 80,000 or more and 90,000 or less. On the other hand, among the requirements (5) to (9) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," the requirements other than the requirements (7) and (8) can basically be satisfied in the ethylene copolymer (L') in the same way. For example, the ethylene copolymer (L') may satisfy the same requirement as requirement (5) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," i.e., the following requirement (5'):

[0061] Requirements (5') The ethylene copolymer (L') preferably has a weight average molecular weight (Mw), a mass fraction of the structural unit derived from the non-conjugated polyene [C'] in the copolymer (mass fraction of (C'): mass %), and a molecular weight of the non-conjugated polyene [C'] (molecular weight of [C']) that satisfy the following relational formula (1'): 4.5≦Mw×[C'] mass fraction / 100 / [C'] molecular weight≦80 Equation (1') Here, when the Mw of the ethylene copolymer (L') is small, the value of the above "Mw × mass fraction of [C'] / 100 / molecular weight of [C']" for the ethylene copolymer (L') may be less than 45. Furthermore, the ethylene copolymer (L') preferably satisfies the same requirement as requirement (6) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," i.e., requirement (6') below.

[0062] Requirements (6') The ethylene copolymer (L') preferably satisfies the following formula (2'): P' / ([η] 2.9 ) ≦ [C'] mass fraction × 6 Equation (2') In equation (2'), P' is the complex viscosity η at a frequency ω = 0.1 rad / s obtained by performing linear viscoelasticity measurement (190 ° C) on the ethylene copolymer (L') using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / s * (ω=100) The mass fraction of [C'] represents the mass fraction (% by mass) of the structural units derived from the non-conjugated polyene [C]. Furthermore, the ethylene copolymer (L') preferably satisfies the same requirement as requirement (9) described above in the section "Ethylene-α-olefin-non-conjugated polyene copolymer (L)," i.e., requirement (9') below.

[0063] Requirements (9') The ethylene copolymer (L') was measured by linear viscoelasticity measurement (190°C) using a rheometer, and the complex viscosity η at a frequency of ω = 0.01 rad / s was * (ω=0.01) (Pa·sec) and the complex viscosity η at frequency ω=10 rad / s * (ω=10) It is preferable that the iodine value (Pa·sec) and the iodine value derived from the non-conjugated polyene [C] satisfy the following formula (5′). Log{η * (ω=0.01)} / Log{η * (ω=10)}≦0.0753 × {iodine value derived from non-conjugated polyene [C']} + 1.42 Equation (5')

[0064] <Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (L')> The ethylene-α-olefin-non-conjugated polyene copolymer (L') that can be used in combination with the ethylene-α-olefin-non-conjugated polyene copolymer (L) in the present invention can basically be obtained by the same production method as described above in the "Production method of ethylene-α-olefin-non-conjugated polyene copolymer (L)." For example, when the ethylene-α-olefin-non-conjugated polyene copolymer (L') is obtained by a production method using a metallocene catalyst, the same conditions as those for the corresponding ethylene-α-olefin-non-conjugated polyene copolymer (L) can basically be employed, and the intrinsic viscosity [η] and the limiting viscosity [η] can be adjusted by appropriately adjusting the amount of hydrogen supplied during the polymerization reaction.

[0065] When the ethylene-based copolymer composition of the present invention contains the ethylene-α-olefin-non-conjugated polyene copolymer (L') in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L), the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L') is, for example, within a range of more than 0 part by mass and not more than 80 parts by mass, preferably 10 to 75 parts by mass, more preferably 20 to 70 parts by mass, even more preferably 30 to 65 parts by mass, and particularly preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin-non-conjugated polyene copolymer (L') in the ethylene-based copolymer composition.

[0066] Resorcinol compounds (M) The resorcinol compound (M), which is one of the components constituting the ethylene copolymer composition of the present invention, is not particularly limited as long as it acts primarily as an adhesive, and examples thereof include modified resorcinol-formaldehyde resin, resorcin, resorcinol-formaldehyde (RF) resin, etc. These may be used alone or in combination of two or more. Among these, modified resorcinol-formaldehyde resin is preferably used in terms of transpiration, moisture absorption, and compatibility with rubber.

[0067] The ethylene copolymer composition of the present invention contains the resorcinol compound (M), which improves compatibility with fibrous materials, thereby improving tackiness and adhesion to fibrous materials, and also improves abrasion resistance.

[0068] The modified resorcinol-formaldehyde resin may be, for example, one represented by the following general formula (1) or (3). Among these, the one represented by the following general formula (1) is particularly preferred.

[0069] [ka]

[0070] [ka]

[0071] An example of the resorcinol compound (M) is Sumikanol 620 (modified resorcinol-formaldehyde resin), manufactured and sold by Taoka Chemical Co., Ltd.

[0072] <Ethylene-based copolymer composition> The ethylene copolymer composition used in the present invention is a composition containing the ethylene-α-olefin-non-conjugated polyene copolymer (L), the resorcinol compound (M), and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'), and preferably contains 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1.0 to 7 parts by mass, and particularly preferably 2.0 to 4.0 parts by mass of the resorcinol compound (M) per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L').

[0073] The ethylene-based copolymer composition of the present invention contains a resorcinol-based compound (M) in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'). Therefore, the ethylene-based copolymer composition of the present invention has good adhesion to other materials, such as layers containing fibrous materials, and the crosslinked laminate exhibits excellent adhesive strength with layers containing fibrous materials. Furthermore, the inclusion of the resorcinol-based compound (M) also contributes to improved abrasion resistance. For these reasons, the ethylene-based copolymer composition of the present invention is suitable for use as an industrial belt. Industrial belts often have a layer made of a polymer-containing composition and a layer containing a fibrous material, with these layers in direct contact with each other. When the ethylene-based copolymer composition of the present invention is used for an industrial belt, the industrial belt often has a layer [I] made of the ethylene-based copolymer composition and a layer [II] containing a fibrous material, with the layers [I] and [II] being in contact with each other.

[0074] In addition to the ethylene copolymer (L), the resorcinol compound (M), and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'), the ethylene copolymer composition of the present invention may contain other components depending on the desired purpose, provided that the effects of the present invention are not impaired. Examples of such other components include a melamine resin (N) and a crosslinking agent (B). The ethylene copolymer composition of the present invention may also contain at least one component selected from the group consisting of a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a filler, a softener, an antioxidant, a processing aid, an activator, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener. Each of these additives may be used alone or in combination.

[0075] <Melamine resin (N)> The ethylene copolymer composition according to the present invention may further contain a melamine resin (N) in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L), the resorcinol compound (M), and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'). The melamine resin (N) is not particularly limited as long as it functions primarily as an adhesion promoter, and examples thereof include methylated formaldehyde-melamine polymers. The melamine resin (N) may be a single type or a combination of two or more types. Among these, methylated formaldehyde-melamine polymers are preferred in terms of transpiration, moisture absorption, and compatibility with rubber.

[0076] As the methylated formaldehyde-melamine polymer, for example, one represented by the following general formula (4) is preferably used.

[0077] [ka]

[0078] Among the melamine resins (N) according to the present invention, a mixture of compounds represented by the above general formula (4) is preferred, and a mixture containing 43 to 44 mass% of a compound where n=1, 27 to 30 mass% of a compound where n=2, and 26 to 30 mass% of a compound where n=3 is particularly preferred.

[0079] An example of the melamine resin (N) is Sumikanol 507AP (a methylated formaldehyde-melamine polymer) manufactured and sold by Taoka Chemical Co., Ltd.

[0080] When the ethylene-based copolymer composition according to the present invention further contains the melamine resin (N), the ethylene-based copolymer composition contains the melamine resin (N) in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L').

[0081] <Crosslinking agent (B)> The ethylene-based copolymer composition of the present invention may further contain a crosslinking agent (B) in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (L), the resorcinol-based compound (M), the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'), and the optional melamine resin (N). The ethylene-based copolymer composition of the present invention does not necessarily need to contain the crosslinking agent (B) as long as the object of the present invention can be achieved. However, the ethylene-based copolymer composition of the present invention is often used in the form of a crosslinked product for industrial belts. Therefore, the ethylene-based copolymer composition of the present invention usually contains the crosslinking agent (B).

[0082] Examples of the crosslinking agent (B) include crosslinking agents commonly used in crosslinking rubber, such as organic peroxides, phenolic resins, sulfur-based compounds, hydrosilicone-based compounds, amino resins, quinone or its derivatives, amine-based compounds, azo-based compounds, epoxy-based compounds, and isocyanate-based compounds. Among these, organic peroxides and sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred. In one exemplary and preferred embodiment of the present invention, the ethylene copolymer composition according to the present invention contains an organic peroxide as the crosslinking agent (B).

[0083] Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0084] When an organic peroxide is used as the crosslinking agent (B), the amount of the organic peroxide in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1.0 to 7 parts by mass, and particularly preferably 2.0 to 4.0 parts by mass, per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'). When the amount of the organic peroxide is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the resulting molded article, which is advantageous.

[0085] <Crosslinking aids, vulcanization accelerators and vulcanization aids> When the ethylene copolymer composition according to the present invention further contains the crosslinking agent (B), the ethylene copolymer composition may further contain a crosslinking aid, a vulcanization accelerator and / or a vulcanization aid.

[0086] When an organic peroxide is used as the crosslinking agent (B), it is preferable to use a crosslinking aid in combination. Examples of the crosslinking aid include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate (for example, Sunester EG (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; and divinylbenzene.

[0087] When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 1.0 to 10 mol, preferably 0.2 to 7.0 mol, more preferably 0.5 to 5.0 mol, and even more preferably 1.0 to 3.0 mol, per mol of the organic peroxide.

[0088] Examples of sulfur-based compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0089] When a sulfur-based compound is used as the crosslinking agent (B), the blending amount thereof in the ethylene-based copolymer composition is usually 0.1 to 10 parts by mass, preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass, per 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L'). When the blending amount of the sulfur-based compound is within the above range, there is no blooming on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties.

[0090] When a sulfur-based compound is used as the crosslinking agent (B), it is preferable to use a vulcanization accelerator in combination. Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N'-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (e.g., Suncerer M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noccelaer MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-dinitrophenyl)mercaptobenzothiazole, Thiazole-based vulcanization accelerators such as ethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (e.g., Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, and diorthotolylguanidine; aldehyde-amine-based vulcanization accelerators such as acetaldehyde-aniline condensation product and butyraldehyde-aniline condensation product; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; tetramethylthiuram monosulfide (e.g., Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); thiuram-based vulcanization accelerators such as Sancerer TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (e.g., Sancerer TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (e.g., Sancerer TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutylthiuram disulfide (e.g., Sancerer TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Sancerer TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, diethyldithio Examples of such vulcanization accelerators include dithioacid salt vulcanization accelerators such as zinc carbamate, zinc dibutyldithiocarbamate (for example, Sancerar PZ, Sancerar BZ, and Sancerar EZ (trade names; manufactured by Sanshin Chemical Industry Co., Ltd.)) and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators such as ethylenethiourea (for example, Sancerar BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sancerar 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea; and xanthate-based vulcanization accelerators such as zinc dibutylxatogenate.

[0091] When a vulcanization accelerator is used, the amount of the vulcanization accelerator in the ethylene copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L'). When the amount of the vulcanization accelerator is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the resulting molded article. When a sulfur-based compound is used as the crosslinking agent (B), a vulcanization aid can be used in combination.

[0092] When a vulcanization aid is used, the amount of the vulcanization aid in the ethylene copolymer composition is usually 1 to 20 parts by mass per 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L').

[0093] Filler The ethylene copolymer composition of the present invention may further contain a filler. The filler is a known rubber reinforcing agent blended into a rubber composition, and is usually an inorganic substance called carbon black or an inorganic reinforcing agent.

[0094] Specific examples of fillers that can be used in the present invention include Asahi #55G, Asahi #60UG, and Asahi #70 (all manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, and other carbon blacks) (manufactured by Tokai Carbon Co., Ltd.), carbon blacks surface-treated with a silane coupling agent or the like, silica, activated calcium carbonate, finely divided talc, finely divided silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, zinc oxide (e.g., ZnO#1 / zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0095] These fillers may be used alone or in combination of two or more. Preferred fillers used in the present invention include carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. Zinc oxide is also one of the fillers that can be suitably used in the present invention.

[0096] When the ethylene copolymer composition of the present invention contains a filler, the filler may be blended in an amount of usually 10 to 300 parts by mass, preferably 15 to 150 parts by mass, more preferably 20 to 100 parts by mass, even more preferably 30 to 80 parts by mass, and particularly preferably 40 to 65 parts by mass, relative to 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L').

[0097] <Softener> The ethylene copolymer composition of the present invention may further contain a softener. Examples of the softener include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or derivatives thereof; synthetic polymers such as terpene resin, petroleum resin, and coumarone-indene resin; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factice). Among these, petroleum-based softeners are preferred, and process oil is particularly preferred.

[0098] When the ethylene copolymer composition contains a softener, the amount of the softener is generally 2 to 100 parts by mass, preferably 4 to 80 parts by mass, more preferably 6 to 50 parts by mass, even more preferably 8 to 30 parts by mass, and particularly preferably 10 to 20 parts by mass, relative to 100 parts by mass of the total amount of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L').

[0099] <Anti-aging agent (stabilizer)> The life of a seal packing formed from the ethylene copolymer composition of the present invention can be extended by blending an antioxidant (stabilizer). Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0100] Examples of antioxidants include aromatic secondary amine antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate antioxidants such as nickel dibutyldithiocarbamate; and sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0101] When the ethylene copolymer composition contains an antioxidant, the amount of the antioxidant is usually 0.3 to 10 parts by mass, preferably 0.5 to 8.0 parts by mass, more preferably 1.0 to 7.0 parts by mass, even more preferably 1.5 to 5.0 parts by mass, and particularly preferably 2.0 to 4.0 parts by mass, per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'). When the amount of the antioxidant is within the above range, there is no bloom on the surface of the obtained molded article, and furthermore, vulcanization inhibition can be suppressed.

[0102] <Processing aids> As the processing aid, a wide variety of processing aids that are generally compounded in rubber can be used. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters thereof. Of these, stearic acid is preferred.

[0103] When the ethylene copolymer composition contains a processing aid, it can be appropriately blended in an amount of usually 0.1 to 10 parts by mass, preferably 0.2 to 5.0 parts by mass, more preferably 0.4 to 3.0 parts by mass, even more preferably 0.6 to 2.0 parts by mass, and particularly preferably 0.8 to 1.5 parts by mass, per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'). When the blending amount of the processing aid is within the above range, excellent processability such as kneading processability, extrusion processability, and injection moldability is obtained, which is preferable. The processing aid may be used alone or in combination of two or more kinds.

[0104] <Activator> Examples of the surfactant include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0105] When the ethylene copolymer composition contains an activator, the amount of the activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the total of the ethylene copolymer (L) and the optional ethylene-α-olefin-non-conjugated polyene copolymer (L').

[0106] <Method for producing ethylene copolymer composition> The ethylene copolymer composition of the present invention can be obtained by a production method including a step of kneading the ethylene-α-olefin-non-conjugated polyene copolymer (L), the resorcinol compound (M), the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'), the optional melamine resin (N), and, as necessary, a processing aid, a crosslinking aid, and the like, using an internal mixer (internal mixer) such as a Banbury mixer, a kneader, or an intermix, at 80 to 160°C for 1 to 5 minutes. Here, the ethylene copolymer composition containing the crosslinking agent (B) can be prepared by mixing additives such as the crosslinking agent (B), the crosslinking aid, and the vulcanization accelerator into the blend (compound) obtained by the kneading step using rolls such as open rolls or a kneader, and optionally adding the vulcanization accelerator and the crosslinking aid; kneading the mixture at a roll surface temperature of 40 to 80°C for 5 to 30 minutes, preferably 40 to 70°C for 6 to 25 minutes, more preferably 45 to 65°C for 7 to 20 minutes, and even more preferably 45 to 60°C for 8 to 15 minutes; and then further performing a separating step.

[0107] In addition, when the kneading temperature in an internal mixer is low, the crosslinking agent (B) may be kneaded simultaneously with components other than the crosslinking agent (B), such as the ethylene-α-olefin-non-conjugated polyene copolymer (L), the resorcinol compound (M), the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'), and the optional melamine resin (N).

[0108] <Physical Properties of Uncrosslinked Ethylene Copolymer Composition> Mooney viscosity ML of the uncrosslinked ethylene copolymer composition of the present invention (1+4) The temperature at 100°C is preferably 20 to 80, more preferably 30 to 70, even more preferably 40 to 60, and particularly preferably 50 to 55. Mooney viscosity ML (1+4) When 100°C is within the above range, the ethylene copolymer composition has good processability and flowability. Mooney viscosity ML (1+4) 100°C can be measured in accordance with JIS K 6300 (1994).

[0109] <Laminate> The laminate of the present invention is a laminate in which a layer [I] made of the ethylene copolymer composition and a layer [II] containing a fibrous material are in contact with each other. That is, the laminate of the present invention includes a layer [I] made of the ethylene copolymer composition and a layer [II] containing a fibrous material, and the layer [I] and the layer [II] are in contact with each other.

[0110] <<Layer [I] Made of Ethylene-Based Copolymer Composition>> The layer [I] constituting the laminate of the present invention is a layer made of the above ethylene copolymer composition, and is preferably a layer made by crosslinking the above ethylene copolymer composition.

[0111] <Layer containing fibrous material [II]> The layer [II] constituting the laminate of the present invention contains a fibrous material. This layer [II] contains a fibrous material in at least a part of the layer.

[0112] <Textile materials> Examples of the fiber material forming the layer [II] used in the present invention include various known fiber materials, such as natural fibers such as cotton, hemp, flax (linen), and wood cellulose fibers; organic fiber materials such as fibers made of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymers; and inorganic fiber materials such as glass fiber, PAN-based carbon fiber, pitch-based carbon fiber, alumina fiber, silicon carbide fiber, aluminum borate fiber, and potassium titanate whisker.

[0113] These fiber materials may be long fibers (filaments) or short fibers (staples), and may be cord yarns, spun yarns, woven fabrics, knitted fabrics, nonwoven fabrics, etc.

[0114] Examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 6,6, and nylon 6,10; semi-aromatic polyamides such as polymetaxylylene adipamide (MXD6), polyhexamethylene terephthalamide (6T), and copolymer polyamides containing these units; and wholly aromatic polyamides such as polybenzamide, poly-p-phenylene terephthalamide, and poly-m-phenylene isophthalamide.

[0115] In one preferred and exemplary embodiment of the present invention, the fiber material forming the layer [II] is canvas. Canvas is a thick cloth woven in a plain weave, and is often made from cotton, hemp, or flax (linen). In another preferred and exemplary embodiment of the present invention, the fiber material forming the layer [II] is a woven fabric of nylon fibers.

[0116] Furthermore, these fiber materials may be surface-treated by a known method such as resorcinol-formaldehyde latex treatment (RFL treatment) in order to improve adhesion between the fiber materials themselves or between the fiber materials and the layer [I] made of the ethylene copolymer composition.

[0117] <RFL treatment> The fiber material forming the layer [II] used in the present invention may contain fibers that have been treated with resorcinol formaldehyde latex (RFL treatment). RFL treatment involves the adhesive treatment of textile materials using a treatment liquid (RFL liquid) containing resorcinol, formalin, and latex. This RFL liquid is a mixture of the initial condensation product of resorcinol and formalin and rubber latex. Rubber latex can be styrene-butadiene-vinylpyridine terpolymer (VP), styrene-butadiene copolymer (SBR), chloroprene (CR), acrylonitrile-butadiene copolymer (NBR), hydrogenated NBR (H-NBR), chlorosulfonated ethylene (CSM), natural rubber, etc. These can be used alone or in a blend of two or more.

[0118] <Method of manufacturing laminate> The laminate of the present invention can be produced by various known methods for producing laminates. For example, a method of laminating a layer [I] made of an uncrosslinked ethylene copolymer composition produced (molded) in advance by a known method with a layer [II] containing a fibrous material, and then crosslinking the layer [I] made of the ethylene copolymer composition, a method of laminating a layer [I] made of a crosslinked ethylene copolymer composition with a layer [II] containing a fibrous material, or a method of extrusion coating a layer [I] made of an ethylene copolymer composition onto a layer [II] containing a fibrous material, and then crosslinking the layer [I] made of the ethylene copolymer composition, The layer [I] made of the ethylene copolymer composition can be produced by various known methods.

[0119] The ethylene copolymer composition can be obtained by kneading the ethylene-α-olefin-non-conjugated polyene copolymer (L), the resorcinol compound (M), the optional ethylene-α-olefin-non-conjugated polyene copolymer (L'), the optional melamine resin (N), and further a crosslinking agent, and, if necessary, additives such as a filler, a softener, an antioxidant, and a processing aid, using any of various known kneading and mixing devices, for example, a Banbury mixer, a kneader, an internal mixer (internal mixer) such as an Intermix, or a roll.

[0120] The uncrosslinked ethylene copolymer composition obtained by kneading may be molded into an intended shape by various molding methods such as an extruder, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then crosslinked to form a layer [I] made of the ethylene copolymer composition, which may then be laminated (bonded) with a layer [II] containing a fibrous material; alternatively, the uncrosslinked ethylene copolymer composition may be molded into an intended shape by the above-mentioned method, and then laminated (bonded) with a layer [II] containing a fibrous material, followed by crosslinking.

[0121] The layer [I] made of the ethylene copolymer composition may be crosslinked by heating using a crosslinking agent or by irradiating with light, gamma rays or electron beams. Furthermore, crosslinking may be performed using a mold or without a mold. When a mold is not used, the molding and crosslinking steps are usually performed continuously. Heating methods that can be used in the crosslinking tank include hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, and other heating tanks.

[0122] <<Uses of laminates>> A laminate in which a layer [I] made of the ethylene copolymer composition of the present invention and a layer [II] containing a fibrous material are in contact with each other is suitably used for an industrial belt, that is, it can be said that the industrial belt of the present invention has the laminate. The laminate is also suitable for use in automobile hoses, water hoses, gas hoses, power transmission belts, conveyor belts, and escalator handrails.

[0123] Examples of the automotive hose include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the transmission belt include a V-belt, a flat belt, a toothed belt, etc. Examples of the conveyor belt include a light conveyor belt, a cylindrical belt, a rough-top belt, a flanged conveyor belt, a U-shaped guide conveyor belt, a V-guide conveyor belt, etc. [Example]

[0124] The present invention will now be described in more detail with reference to examples. It is not limited to:

[0125] [Measurement and evaluation method] In the following examples and comparative examples, the methods for measuring and evaluating the various physical properties and characteristics are as follows.

[0126] (1) Physical properties of ethylene-α-olefin-non-conjugated polyene copolymer (L) and ethylene-α-olefin-non-conjugated polyene copolymer (L')

[0127] <Composition of Ethylene-α-olefin-non-conjugated polyene copolymer (L) and Ethylene-α-olefin-non-conjugated polyene copolymer (L')> The molar ratio and mass fraction (mass%) of each structural unit of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin-non-conjugated polyene copolymer (L') are as follows: 13 The measured values ​​were obtained by C-NMR using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.), with a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an accumulation number of 8000. 13The C-NMR spectrum was obtained.

[0128] <Intrinsic viscosity> The intrinsic viscosity [η] was measured using a fully automatic intrinsic viscometer manufactured by Rigo Co., Ltd. at a temperature of 135° C. and in decalin as a measurement solvent.

[0129] <Complex viscosity η * and P value The rheometer used was a viscoelasticity measuring device, Ares (manufactured by Rheometric Scientific), and the complex viscosity η was measured at a frequency of ω = 0.01 rad / s under the conditions of 190°C and 1.0% strain. * (ω=0.01) , complex viscosity η at frequency ω=0.1rad / s * (ω=0.1) , complex viscosity η at frequency ω=10 rad / s * (ω=10) and the complex viscosity η at frequency ω = 100 rad / s * (ω=100) (All units are Pa·sec) were measured. * (ω=0.1) and η * (ω=100) The ratio of the complex viscosity to * P-value (η * (ω=0.1) / η * (ω=100) ) was calculated.

[0130] <Weight average molecular weight (Mw)> Mw was determined by structural analysis using 3D-GPC. Specifically, it was determined as follows.

[0131] The absolute molecular weight distribution was determined using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was simultaneously determined using a viscometer. The main measurement conditions were as follows: Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Bridge-type viscometer PL-BV400 (Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT x 2 + TSKgel GMH HR -M(S)×1 piece (Each piece has an inner diameter of 7.8mm and a length of 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: ca 1.5mg / mL Sample filtration: Filtration through a sintered filter with a pore size of 1.0 μm The dn / dc value (differential value of refractive index n with respect to concentration c) required to determine the absolute molecular weight was determined for each sample from the dn / dc value of standard polystyrene (molecular weight 190,000) of 0.053 and the response intensity of the differential refractometer per unit injected mass.

[0132] The long chain branching parameter g'i for each eluted component was calculated from the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer using equation (v-1).

[0133]

number

[0134] where [η]=KM v The relational equation of v = 0.725 was applied, where M is the absolute molecular weight value determined by 3D-GPC, and K is the viscosity coefficient. Further, the average values ​​of g' were calculated from the following formulas (v-2), (v-3), and (v-4): A trendline assuming only short chain branches was determined for each sample.

[0135]

number

[0136] Furthermore, using g'w, the number of branch points per molecular chain, BrNo, and the number of long chain branches per 1000 carbon atoms, LCB, are calculated. 1000C The branching degree λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer formula (v-5). 1000C Equations (v-6) and (v-7) were used to calculate λ. g is the long-chain branching parameter calculated from the radius of gyration Rg, and the following simple correlation is established between g' calculated from the intrinsic viscosity. Various values ​​have been proposed for ε in the equation depending on the shape of the molecule. Here, calculations were performed assuming ε = 1 (i.e., g' = g).

[0137]

number

[0138] λ=BrNo / M (v-6) LCB 1000C =λ×14000 (v-7) *In formula (v-7), 14,000 represents the molecular weight of 1,000 methylene (CH2) units.

[0139] <Mooney viscosity> Mooney viscosity (ML (1+4) 100℃ and ML (1+4) The viscosity (ML 125°C) was measured using a Mooney viscometer (Model SMV-301 manufactured by Shimadzu Corporation) in accordance with JIS K6300 (1994). (1+4) At 100°C, ML (1+4) At 125°C, the temperature was set to 125°C.

[0140] The measurement solvent was o-dichlorobenzene-d4 / benzene-d6 (4 / 1 [v / v]) at a measurement temperature of 120°C. 13 A C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured, and the value was calculated based on the following formula (i). B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) Here, [E], [X], and [Y] represent the molar fractions of structural units derived from ethylene [A], α-olefin [B] having 3 to 20 carbon atoms, and non-conjugated polyene [C], respectively, and [EX] represents the ethylene [A]-α-olefin [B] having 3 to 20 carbon atoms dyad chain fraction.

[0141] (2) Physical Properties of Uncrosslinked Ethylene Copolymer Composition <Mooney viscosity> Mooney viscosity ML of uncrosslinked ethylene copolymer composition (1+4) The viscosity was measured at 100°C using a Mooney viscometer (Model SMV-301 manufactured by Shimadzu Corporation) in accordance with JIS K 6300 (1994).

[0142] <Adhesion (probe tack integral value)> Using a tack tester (TAC-II) manufactured by Rhesca Co., Ltd., a 200 gf load was applied to a 5 mm diameter stainless steel probe, which was pressed for 5 seconds against each of the resins in Example 1 and Comparative Examples 1 and 2. The peak value (gf) and stress integral value (gf·sec) were measured when the probe was peeled off at a speed of 120 mm / min. This measurement was carried out 10 times at 50°C, and the average integral value (probe tack integral value) was calculated and used as an index of adhesiveness.

[0143] (3) Physical Properties of Ethylene-Based Copolymer Composition (Crosslinked Product) <Hardness test (Durometer-A)> The flat portions of the 2 mm thick crosslinked sheets produced in the examples were stacked to form a 12 mm thick sheet, and the hardness (JIS-A) was measured in accordance with JIS K 6253 (2012).

[0144] <Tensile test: modulus, tensile stress at break, tensile elongation at break> The crosslinked sheets prepared in the examples and the like were punched out to prepare No. 3 dumbbell test pieces described in JIS K 6251 (1993). Using these test pieces, tensile tests were carried out according to the method specified in JIS K 6251, paragraph 3, at a measurement temperature of 170°C and a tensile speed of 500 mm / min, and the tensile stress (25% modulus (M25) to 200% modulus (M200)), tensile stress at break (TB), and tensile elongation at break (EB) were measured.

[0145] (DIN friction test (amount of wear loss)) In accordance with JIS-K6264-2:2005, three 2 mm thick crosslinked sheets were stacked to prepare a disk-shaped test piece with a diameter of 16.0±0.2 mm and a thickness of 6 mm. Using a DIN abrasion tester, the test piece was rotated on a drum with a diameter of 150.0±0.2 mm and a length of 500 mm at 40 revolutions per minute under a load of 1 kgf over an abrasion distance of 40.0±0.2 m, and the abrasion amount (DIN abrasion amount: unit: mg) was measured.

[0146] (Peel test (peel strength)) The peel strength (adhesion strength) between the layer [I] made of the crosslinked ethylene copolymer composition and the layer [II] containing a fibrous material was measured by the following method.

[0147] A 3 mm thick uncrosslinked sheet was placed on top of an RFL-treated nylon fiber woven fabric (manufactured by Ayaha Kogyo Co., Ltd.) and pressed at 170°C for 15 minutes using a 200-ton press molding machine to crosslink the uncrosslinked sheet and obtain a laminate. A 25 mm wide test piece was punched out of the laminate and subjected to a T-peel test at a tensile speed of 50 mm / min. The peel test was performed three times, and the average value was taken as the peel strength.

[0148] The ethylene-α-olefin-non-conjugated polyene copolymer (L) used in the examples of the present invention is shown below.

[0149] [Ethylene-α-olefin-non-conjugated polyene copolymer (L)] As the ethylene-α-olefin-non-conjugated polyene copolymer (L), the ethylene-propylene-VNB copolymer [copolymer (L-1)] obtained in Production Example 1 was used.

[0150] [Manufacturing Example 1] A 300-liter polymerization reactor was continuously fed with 58.3 L / hr of dehydrated and purified hexane solvent through line 1, and 4.5 mmol / hr of triisobutylaluminum (TiBA), 0.150 mmol / hr of (C6H5)3CB(C6F5)4, and 0.030 mmol / hr of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride through line 2. Simultaneously, 6.6 kg / hr of ethylene, 9.3 kg / hr of propylene, 18 L / hr of hydrogen, and 340 g / hr of VNB were continuously fed into the polymerization reactor through separate lines, and copolymerization was carried out under the conditions of a polymerization temperature of 87°C, a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

[0151] The ethylene-propylene-VNB copolymer solution produced in the polymerization reactor was continuously discharged at a flow rate of 88.0 L / hr, heated to 170°C (pressure increased to 4.1 MPaG), and fed to a phase separator. At this time, ethanol, a polymerization inhibitor, was continuously introduced into the discharge line in an amount of 0.1 mol times the TiBA in the liquid component extracted from the polymerization reactor.

[0152] In the phase separator, the ethylene-propylene-VNB copolymer solution separated into a dense phase (lower phase) containing the majority of the ethylene-propylene-VNB copolymer and a dilute phase (upper phase) containing a small amount of the polymer.

[0153] The separated thick phase was introduced into a heat exchanger at a rate of 85.4 L / hr and then into a hopper where the solvent was evaporated and separated, yielding an ethylene-propylene-VNB copolymer at a rate of 7.8 kg / hr.

[0154] The physical properties of the resulting ethylene-propylene-VNB copolymer (L-1) were evaluated by the following methods. The results are shown in Table 1. The molecular weight distribution of the obtained copolymer (L-1) was bimodal, and the chart obtained by GPC measurement showed two or more peaks, and the area of ​​the peak appearing on the side with the smallest molecular weight was 5% of the total peak area.

[0155] [Ethylene-α-olefin-non-conjugated polyene copolymer (L')] The ethylene-propylene-VNB copolymer (copolymer (L'-1)) obtained in Production Example R1 was used as the ethylene-α-olefin-non-conjugated polyene copolymer (L') that does not satisfy the requirement (3) specified in the present invention.

[0156] [Manufacturing example R1] Ethylene-propylene-VNB copolymer (L'-1) was produced in the same manner as in Production Example 1, except that the molecular weight of the resulting copolymer was controlled by the amount of hydrogen fed. The results are shown in Table 1. [Table 1]

[0157] Example 1 Fifty parts by mass of the ethylene-propylene-VNB copolymer [copolymer (L-1)] obtained in Production Example 1 and 50 parts by mass of the ethylene-propylene-VNB copolymer [copolymer (L'-1)] obtained in Production Example A1 were masticated for 30 seconds, and 100 parts by mass of the resulting mixture was mixed with 1 part by mass of stearic acid as a lubricant, 1 part by mass of tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane (trade name Irganox 1010, manufactured by BASFF Japan Co., Ltd.) as an antioxidant, 2 parts by mass of 2-mercaptobenzimidazole (trade name Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.) as a filler, 5 parts by mass of zinc oxide (ZnO#1) and 50 parts by mass of carbon black [trade name Asahi #70, manufactured by Asahi Carbon Co., Ltd.] as a filler, and a softener [trade name Diana Process Oil PW-380 15 parts by mass of a modified resorcinol-formaldehyde resin (manufactured by Idemitsu Kosan Co., Ltd.) as a resorcinol compound (M) (trade name: Sumikanol 620, manufactured by Taoka Chemical Co., Ltd.) was added and mixed for 2 minutes at 150°C in a 1.7-liter Banbury mixer (manufactured by Kobe Steel, Ltd.). The ram was then raised and cleaned, and the mixture was mixed for another 1 minute and then discharged at approximately 150°C to obtain a compound. This mixing was performed at a filling rate of 70%.

[0158] Next, 177 parts by mass of this blend was wound around an 8-inch roll (front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and 2.7 parts by mass of dicumyl peroxide (Percumyl D (NOF Corporation; purity 98% or higher (industrially pure product)) as a crosslinking agent and 4 parts by mass of ethylene glycol dimethacrylate (trade name Sunester EG, Sanshin Chemical Industry Co., Ltd.) as a crosslinking aid were added and kneaded for 10 minutes, and the resulting composition was cut into sheets to prepare uncrosslinked sheets with thicknesses of 2 mm and 3 mm.

[0159] The adhesive strength (gf) of the resulting 2 mm thick uncrosslinked sheet was measured by the method described above. The results are shown in Table 2. Next, the resulting 2 mm-thick uncrosslinked sheet was pressed at 170°C for 15 minutes using a 100-ton press molding machine to produce a crosslinked sheet. The physical properties of the resulting crosslinked sheet were measured using the methods described above. The results are shown in Table 2.

[0160] Comparative Example 1 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, except that the resorcinol compound (M) was not added, and the physical properties thereof were evaluated by the methods described above. The results are shown in Table 2.

[0161] Comparative Example 2 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the same method as in Example 1, except that neither the resorcinol compound (M) nor the vulcanization accelerator (ethylene glycol dimethacrylate) was added, and the physical properties thereof were evaluated by the same methods as described above. The results are shown in Table 2.

[0162] [Table 2]

Claims

1. An ethylene copolymer composition for industrial belts, comprising the following (L) and (M): (L) An ethylene-α-olefin-non-conjugated polyene copolymer comprising a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C] containing, in one molecule, two or more partial structures selected from the group consisting of the following general formulae (I) and (II), and satisfying the following requirements (1) to (4): (M) Resorcinol compounds. 【Chemical 1】 (1) the molar ratio [[A] / [B]] of the structural units derived from ethylene [A] to the structural units derived from an α-olefin [B] having 3 to 20 carbon atoms is 40 / 60 to 90 / 10; (2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol %, based on 100 mol % of the total of the structural units [A], [B], and [C]; (3) Mooney viscosity ML at 125°C (1+4) 125°C is 10 to 100, (4) The B value represented by the following formula (i) is 1.10 or more. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], the α-olefin [B] having 3 to 20 carbon atoms, and the non-conjugated polyene [C], respectively, and [EX] represents the dyad sequence fraction of ethylene [A]-α-olefin [B] having 3 to 20 carbon atoms.]

2. 2. The ethylene copolymer composition for industrial belts according to claim 1, wherein the structural units derived from the non-conjugated polyene [C] include structural units derived from 5-vinyl-2-norbornene.

3. 2. The ethylene copolymer composition for industrial belts according to claim 1, wherein the content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 1.0 mol %, relative to 100 mol % of the total of the structural units [A], [B], and [C].

4. The ethylene copolymer composition for industrial belts according to claim 1, wherein the α-olefin [B] having 3 to 20 carbon atoms constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) is propylene.

5. The ethylene copolymer composition for industrial belts according to claim 1, further comprising (B) an organic peroxide as a crosslinking agent.

6. 2. The ethylene copolymer composition for industrial belts according to claim 1, comprising 0.1 to 20 parts by mass of a resorcinol compound (M) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

7. The ethylene copolymer composition for industrial belts according to claim 1, further comprising the following (L'): (L') An ethylene-α-olefin-non-conjugated polyene copolymer comprising a structural unit derived from ethylene [A'], a structural unit derived from an α-olefin [B'] having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C'] containing, in one molecule, two or more partial structures selected from the group consisting of the following general formulae (I) and (II), and satisfying the following requirements (1'), (2'), (3'), and (4'): 【Chemistry 2】 (1') the molar ratio [[A'] / [B']] of the structural units derived from ethylene [A'] to the structural units derived from α-olefin [B'] 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 % of the total of the structural units [A'], [B'] and [C']; (3') Mooney viscosity ML at 125°C (1+4) 125°C is 0.1 or more and less than 10, (4') The B value represented by the following formula (i') is 1.10 or more. B value = ([EX']+2[Y']) / [2×[E']×([X']+[Y'])]...(i') Here, [E'], [X'] and [Y'] represent the molar fractions of ethylene [A'], C3-C20 α-olefin [B'] and non-conjugated polyene [C'], respectively, and [EX'] represents the ethylene [A']-C3-C20 α-olefin [B'] dyad chain fraction.

8. 8. The ethylene copolymer composition for industrial belts according to claim 7, comprising 0.1 to 20 parts by mass of the resorcinol compound (M) per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (L) and the ethylene-α-olefin-non-conjugated polyene copolymer (L').

9. A laminate comprising a layer [I] made of the ethylene copolymer composition for industrial belts according to any one of claims 1 to 8 and a layer [II] containing a fiber material in contact with each other.

10. The laminate according to claim 9, wherein the ethylene copolymer composition for industrial belts is crosslinked.

11. The laminate according to claim 9, wherein the fiber material of the layer [II] comprises a fiber treated with resorcinol formaldehyde latex (RFL treatment).

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

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

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