Ethylene copolymer composition and use thereof

Abstract

To further advance the application of lamination with synthetic fibers, such as those in carcass layers of transport belts (conveyor belts), by improving the adhesiveness between ethylene α-olefin non-conjugated polyene copolymer rubber and synthetic fibers, and further improving heat resistance.SOLUTION: The present invention provides an ethylene copolymer composition comprising a component (A), which is an ethylene α-olefin non-conjugated polyene copolymer satisfying specific requirements, and a modified polyolefin wax (B), as well as uses thereof.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM generally have excellent weather resistance, heat resistance, and ozone resistance, and are used in industrial materials such as automotive industrial parts, industrial rubber products, electrical insulating materials, civil engineering and construction materials, and rubberized fabrics. Among these, use in the carcass layer of transport belts (conveyor belts) is desirable, and improvements are being sought to further improve productivity and lifespan. For this reason, studies have been conducted to improve the adhesion between ethylene-α-olefin-non-conjugated polyene copolymer rubber and synthetic fibers, and a proposal has been made to create a sulfur-vulcanized ethylene propylene rubber compound in which zinc oxide made by compounding ethylene-α-olefin-diene copolymer with trans-polyoctenylene rubber is compounded (Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 42-23632 [Patent Document 2] Patent No. 2528033 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to improve the adhesion between ethylene-α-olefin-non-conjugated polyene copolymer rubber and synthetic fibers, as well as the heat resistance, thereby further promoting the use of the rubber in lamination with synthetic fibers, such as the carcass layer of a transport belt (conveyor belt). [Means for solving the problem]

[0005] The present invention relates to the following items [1] to

[13] . [1] An ethylene-based copolymer composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer satisfying the following requirements (a1) to (a4), and a modified polyolefin wax (B). Requirement (a1): The copolymer contains a structural unit derived from ethylene [L], a structural unit derived from an α-olefin [M] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [N], and the molar ratio [L] / [M] of the structural unit derived from ethylene [L] to the structural unit derived from an α-olefin [M] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (a2): The content of structural units derived from the non-conjugated polyene [N] is 0.1 to 6.0 mol % (provided that the total of the structural units derived from [L], [M] and [N] is 100 mol %). Requirement (a3): Mooney viscosity (ML(1+4)125°C) is 5 to 100. Requirement (a4): The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) (wherein [E], [X] and [Y] respectively represent the molar fractions of structural units derived from ethylene [L], α-olefins [M] having 4 to 20 carbon atoms, and non-conjugated polyenes [N], and [EX] represents the dyad chain fraction of ethylene [L]-α-olefins [M] having 4 to 20 carbon atoms.)

[0006] [2] The ethylene copolymer composition according to the above item [1], wherein the α-olefin [M] having 4 to 20 carbon atoms constituting the ethylene-α-olefin-non-conjugated polyene copolymer (A) is 1-butene. [3] The ethylene copolymer composition according to the above [1] or [2], wherein the acid value of the modified polyolefin wax (B) is 30 to 90 mg-KOH / g. [4] The ethylene copolymer composition according to any one of the above [1] to [3], wherein the modified polyolefin wax (B) has a number average molecular weight (Mn) of 100 to 10,000. [5] The ethylene copolymer composition according to any one of the above [1] to [4], wherein the modified polyolefin wax (B) has a melt viscosity (140° C.) of 10 to 1000 mPa·s. [6] The ethylene copolymer composition according to any one of the above [1] to [5], wherein the modified polyolefin wax (B) is a maleic acid modified polyethylene wax.

[0007] [7] The ethylene copolymer composition according to any one of the above [1] to [6], comprising 0.5 to 100 parts by mass of a modified polyolefin wax (B) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). [8] The ethylene copolymer composition according to any one of the above [1] to [7], which contains a trans-polyoctenylene (C). [9] The ethylene copolymer composition according to the above item [8], comprising 0.5 to 50 parts by mass of trans-polyoctenylene (C) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0008]

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

[11] The laminate according to the above item

[10] , wherein the ethylene-based copolymer composition is crosslinked.

[12] The laminate according to

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

[13] An industrial belt comprising the laminate according to the above item

[10] . Effect of the Invention

[0009] According to the present invention, the adhesion between the ethylene-α-olefin-non-conjugated polyene copolymer rubber and the synthetic fiber is improved, and further the heat resistance of the laminate made thereof is improved, thereby enabling the productivity and life of the laminate to be improved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The ethylene-based copolymer composition of the present invention contains an ethylene-α-olefin-non-conjugated polyene copolymer (A) and a modified polyolefin wax (B). First, the ethylene-α-olefin-non-conjugated polyene copolymer (A) will be described below.

[0011] <Ethylene-α-olefin-non-conjugated polyene copolymer (A)> The ethylene-α-olefin-non-conjugated polyene copolymer (A) contains a structural unit derived from ethylene [L], a structural unit derived from an α-olefin [M] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [N], and satisfies the following requirements (a1) to (a4).

[0012] Regarding requirement (a1) The ethylene-α-olefin-non-conjugated polyene copolymer (A) contains structural units derived from ethylene [L], structural units derived from an α-olefin [M] having 4 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [N], and the molar ratio [[L] / [M]] of the structural units derived from ethylene [L] to the structural units derived from an α-olefin [M] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. The ethylene-α-olefin-non-conjugated polyene copolymer (A) having a molar ratio within the above range has an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature. The lower limit of [L] / [M] is preferably 45 / 55, more preferably 50 / 50, even more preferably 55 / 45, particularly preferably 60 / 40, and especially preferably 65 / 35. The upper limit of [L] / [M] is preferably 80 / 20, more preferably 75 / 25, and even more preferably 70 / 30.

[0013] Regarding requirement (a2) The ethylene-α-olefin-non-conjugated polyene copolymer (A) has a content of structural units derived from the non-conjugated polyene [N] of 0.1 to 6.0 mol %, where the total of the structural units derived from the [L], the structural units derived from the [M], and the structural units derived from the [N] is 100 mol %. The ethylene-α-olefin-non-conjugated polyene copolymer (A) having this content in the above range has sufficient crosslinkability and flexibility. The lower limit of the content of the structural unit derived from [N] is preferably 0.5 mol %. The upper limit of the content of the structural unit derived from [N] is preferably 4.0 mol %, more preferably 3.5 mol %, and even more preferably 3.0 mol %. When the content of the structural units derived from the non-conjugated polyene [N] is within the above range, an ethylene-α-olefin-non-conjugated polyene copolymer (A) having sufficient crosslinkability and flexibility can be obtained.

[0014] Regarding requirement (a3) The Mooney viscosity ML(1+4)125°C is in the range of 5-100, preferably 10-95, more preferably 10-60, further preferably 3-40, and particularly preferably 15-30. When the Mooney viscosity is within the above range, the ethylene-α-olefin-non-conjugated polyene copolymer (A) has good processability and flowability, and also exhibits good post-processing quality (ribbon handling properties), and can provide an ethylene-α-olefin-non-conjugated polyene copolymer (A) having excellent physical properties.

[0015] Regarding requirement (a4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) (wherein [E], [X] and [Y] respectively represent the molar fractions of structural units derived from ethylene [L], α-olefins [M] having 4 to 20 carbon atoms, and non-conjugated polyenes [N], and [EX] represents the dyad chain fraction of ethylene [L]-α-olefins [M] having 4 to 20 carbon atoms.) The B value is 1.20 or more, preferably 1.20 to 1.80, and particularly preferably in the range of 1.22 to 1.40. An ethylene copolymer having a B value of less than 1.20 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.

[0016] Examples of the α-olefin [M] having 4 to 20 carbon atoms include 1-butene having 4 carbon atoms, which has a linear structure without side chains, through 1-nonene having 9 carbon atoms and 1-decene having 10 carbon atoms, 1-nonadecene having 19 carbon atoms, 1-eicosene having 20 carbon atoms, and 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and the like having side chains.

[0017] These α-olefins [M] can be used alone or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferred, and 1-butene, 1-hexene, 1-octene, etc. are particularly preferred, with 1-butene being particularly preferred.

[0018] Specific examples of the non-conjugated polyene [N] 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.

[0019] These non-conjugated polyenes [N] can be used alone or in combination of two or more kinds. Among these, linear non-conjugated dienes such as 1,4-hexadiene, and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferred, and among these, cyclic non-conjugated dienes are preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being particularly preferred.

[0020] Examples of the ethylene-α-olefin-non-conjugated polyene copolymer (A) include the following: Ethylene-1-butene-1,4-hexadiene copolymer, Ethylene-1-pentene-1,4-hexadiene copolymer, Ethylene-1-hexene-1,4-hexadiene copolymer, Ethylene-1-heptene-1,4-hexadiene copolymer, Ethylene-1-octene-1,4-hexadiene copolymer, Ethylene-1-nonene-1,4-hexadiene copolymer, Ethylene-1-decene-1,4-hexadiene copolymer, Ethylene-1-butene-1-octene-1,4-hexadiene copolymer , ethylene-1-butene-5-ethylidene-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene copolymer, ethylene-1-octene-5-ethylidene-2-norbornene copolymer, ethylene-1-nonene-5-ethylidene-2-norbornene copolymer, ethylene-1-decene-5-ethylidene-2-norbornene copolymer Norbornene copolymer, ethylene-1-butene-1-octene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer Ethylene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, Ethylene-1-nonene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, Ethylene-1-decene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, Ethylene-1-butene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer. The ethylene-α-olefin-non-conjugated polyene copolymer (A) may be used alone or in combination with two or more other types, as required. The copolymer (A) may contain at least one kind of biomass-derived monomer (biomass-derived ethylene [L], α-olefin [M] having 3 to 20 carbon atoms, and non-conjugated polyene [N]).

[0021] <Production method of ethylene-α-olefin-non-conjugated polyene copolymer (A)> The ethylene-α-olefin-non-conjugated polyene copolymer (A) according to the present invention can be obtained by various known production methods, for example, a conventionally known production method using a metallocene catalyst. As the metallocene catalyst and the production method using the catalyst, for example, the examples described in WO 2015 / 122415, particularly paragraphs

[0249] to

[0320] of the publication, can be adopted. Next, the modified polyolefin wax (B) will be described.

[0022] <Modified polyolefin wax (B)> The modified polyolefin wax (B) is a polymer different from the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymer (A), and includes the following: Acid-graft-modified polyolefin wax (acid-modified product) which is acid-graft-modified with an unsaturated carboxylic acid or its derivative, Oxidized polyolefin wax (oxidized product) in which polyolefin is oxidized with oxygen or oxygen-containing gas, Styrene-modified polyolefin waxes graft-modified with styrenes; modified polyolefin wax graft-modified with a mixture of these; Furthermore, Sulfonate-modified polyolefin wax (sulfonate-modified) modified with sulfonates.

[0023] These can be prepared by a conventionally known method, for example, (1) a method of oxidizing and modifying the raw material unmodified polyolefin wax with oxygen or an oxygen-containing gas, (2) a method of melt-kneading the raw material unmodified polyolefin wax with an unsaturated carboxylic acid or its derivative, and further with styrenes, sulfonates, etc., in the presence of a polymerization initiator such as an organic peroxide, or (3) a method of kneading the raw material unmodified polyolefin wax with an unsaturated carboxylic acid or its derivative, styrenes, or sulfonates in an organic solvent in the presence of a polymerization initiator such as an organic peroxide.

[0024] <Properties of modified polyolefin wax (B)> The modified polyolefin wax (B) preferably satisfies one or more of the following requirements (b1), (b2), and (b3), more preferably satisfies two or more of them, and even more preferably satisfies all of them. Requirement (b1) The acid value of the modified polyolefin wax (B) is 30 to 90 mg-KOH / g. Requirements (b2) The modified polyolefin wax (B) has a number average molecular weight (Mn) of 100 to 5,000. Requirement (b3) The melt viscosity (140°C) of the modified polyolefin wax (B) is 10 to 1000 mPa·s.

[0025] Regarding requirement (b1) When the modified polyolefin wax (B) is an oxidation modified product (air oxidation of unmodified polyolefin wax), an acid graft modified product (acid graft modified polyolefin wax), or a sulfonate modified product, the acid value (JIS K0070) of the modified polyolefin wax (B) is preferably 30 to 90 mgKOH / g, more preferably 35 to 85 mgKOH / g, even more preferably 40 to 80 mgKOH / g, particularly preferably 45 to 75 mgKOH / g, and even more preferably 50 to 70 mgKOH / g. Here, the acid value refers to the number of mg of potassium hydroxide required for neutralization per 1 g of sample. By setting it in this range, the affinity between the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the modified polyolefin wax (B) is appropriately increased, and the composition maintains relatively high heat resistance and mechanical strength.

[0026] Regarding requirement (b2) The number average molecular weight (Mn) of the modified polyolefin wax (B) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably in the range of 100 to 10,000. The upper limit of the number average molecular weight (Mn) is more preferably 8,000, even more preferably 5,000, particularly preferably 4,000, even more preferably 3,000, even more preferably 2,000, and even more preferably 1,800. The lower limit of the number average molecular weight (Mn) is more preferably 400, even more preferably 500, particularly preferably 600, even more preferably 1,000, even more preferably 1,300, and even more preferably 1,600.

[0027] Regarding requirement (b3) The melt viscosity (140°C) of the modified polyolefin wax (B) according to Brookfield is preferably 10 to 1000 mPa·s. The upper limit of the melt viscosity (140°C) is more preferably 800 mPa·s, even more preferably 600 mPa·s, particularly preferably 500 mPa·s, even more preferably 400 mPa·s, even more preferably 300 mPa·s, and even more preferably 200 mPa·s. The lower limit of the melt viscosity (140°C) is more preferably 30 mPa·s, even more preferably 40 mPa·s, particularly preferably 60 mPa·s, even more preferably 80 mPa·s, even more preferably 100 mPa·s, and even more preferably 120 mPa·s. The Brookfield viscosity at 140° C. was measured according to the method described in JIS K7117-1.

[0028] Other physical properties of the modified polyolefin wax (B), such as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn) and the softening point, are preferably in the following ranges.

[0029] Ratio of weight average molecular weight to number average molecular weight (Mw / Mn) [-] The ratio of weight average molecular weight to number average molecular weight (Mw / Mn) of the modified polyolefin wax (B) measured by gel permeation chromatography (GPC) is preferably 7.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less.

[0030] Softening point [℃] The softening point of the modified polyolefin wax (B) measured according to JIS K2207 is preferably in the range of 70 to 170° C. The upper limit of the softening point is more preferably 160° C., even more preferably 150° C., particularly preferably 135° C., even more preferably 120° C., and even more preferably 115° C. The lower limit is more preferably 80° C., even more preferably 90° C., particularly preferably 100° C., and most preferably 105° C.

[0031] <Structure of modified polyolefin wax (B)> The modified polyolefin wax (B) is an air-oxidized product, an unsaturated carboxylic acid graft-modified product (e.g., a maleic anhydride graft-modified product), or a styrene graft-modified product of at least one homopolymer or copolymer selected from ethylene and an α-olefin having 3 to 12 carbon atoms. More preferably, it is an air-oxidized product, an unsaturated carboxylic acid graft-modified product (e.g., a maleic anhydride graft-modified product), or a styrene graft-modified product of a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms.

[0032] Examples of the α-olefins having 3 to 12 carbon atoms include propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, 1-pentene having 5 carbon atoms, 1-hexene and 4-methyl-1-pentene having 6 carbon atoms, and 1-octene having 8 carbon atoms, and more preferably propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene.

[0033] As described above, the modified polyolefin wax (B) is obtained by air-oxidizing an unmodified propylene wax such as at least one homopolymer or copolymer selected from ethylene and an α-olefin having 3 to 12 carbon atoms, or modifying it with an unsaturated carboxylic acid or a derivative thereof, or a styrene. Hereinafter, the unmodified polyolefin wax and the production method thereof will be described first, and then the modified polyolefin wax obtained by modifying them will be described.

[0034] <Unmodified polyolefin wax> Specific examples of the unmodified polyolefin wax include polyethylene wax, polypropylene wax, and 4-methyl-1-pentene wax, but the unmodified polyolefin wax is not limited to these.

[0035] Polyethylene wax When the unmodified polyolefin wax is a polyethylene wax, examples of preferred polyethylene waxes are described in, for example, JP-A-2009-144146, but will be briefly described below.

[0036] When the unmodified polyolefin wax is a polyethylene wax, it is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Specific examples of the ethylene homopolymer include high-density polyethylene wax, medium-density polyethylene wax, low-density polyethylene wax, and linear low-density polyethylene wax.

[0037] On the other hand, when the polyethylene wax is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, the amount of the ethylene-derived structural unit (a) is preferably 87.0 to 99.9 mass%, more preferably 90.0 to 99.9 mass%, even more preferably 93.0 to 99.9 mass%, and particularly preferably 93.0 to 98.5 mass%. On the other hand, the amount of the structural unit (b) derived from an α-olefin having 3 or more carbon atoms is preferably 0.1 to 13.0 mass%, preferably 0.1 to 10.0 mass%, even more preferably 0.1 to 7.0 mass%, and particularly preferably 1.5 to 7.0 mass%, where (a) + (b) = 100 mass%. The content ratio of the structural unit of the olefin polymer is, 13 It can be determined by analysis of the C-NMR spectrum.

[0038] Examples of the α-olefin having 3 to 12 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. Preferred are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene, more preferred are α-olefins having 3 to 8 carbon atoms, particularly preferred are propylene and 1-butene, and most preferred is 1-butene. When ethylene is copolymerized with propylene or 1-butene, the modified polyolefin wax (B) tends to become hard and less sticky, so that the surface properties of the molded article are good. It is also preferred in terms of increasing mechanical strength and heat resistance. The reason why the modified polyolefin wax (B) becomes harder and less sticky is not clear, but compared to other α-olefins, propylene and 1-butene efficiently lower the melting point with a small amount of copolymerization, and therefore tend to have a higher degree of crystallinity than other waxes with the same melting point, and this is presumably the reason. The α-olefins may be used alone or in combination of two or more.

[0039] Polypropylene wax The unmodified polyolefin wax may be a polypropylene wax. The polypropylene wax may be a homopolymer of propylene obtained by copolymerizing propylene and other monomers as necessary in the presence of a stereospecific catalyst, or a copolymer mainly composed of propylene, or may be obtained by pyrolyzing a high molecular weight polypropylene. The polypropylene wax may be purified using a method such as solvent fractionation for fractionation based on the difference in solubility in a solvent, or molecular distillation for fractionation based on the difference in boiling point. The polypropylene wax may be a propylene homopolymer, a copolymer of propylene and ethylene, or a copolymer of propylene and an α-olefin having 4 to 12 carbon atoms.

[0040] When ethylene is copolymerized with a propylene polymer, the amount of the propylene-derived structural unit may be 60 to 99.5 mol %. The amount of the propylene-derived structural unit is preferably 80 to 99 mol %, more preferably 90 to 98.5 mol %, and even more preferably 95 to 98 mol %. By using the above propylene (co)polymer, a composition having an excellent balance of appearance, mechanical strength, and heat resistance can be obtained.

[0041] When an α-olefin having 4 to 12 carbon atoms is copolymerized to produce a propylene (co)polymer, examples of the α-olefin having 4 to 12 carbon atoms include linear or branched α-olefins such as 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. Among these, 1-butene is particularly preferred.

[0042] When the propylene (co)polymer is a propylene-α-olefin copolymer, the amount of the structural unit (a') derived from propylene is preferably 53 to 87 mass%, more preferably 58 to 85 mass%, even more preferably 64 to 81 mass%, and particularly preferably 69 to 77 mass%. On the other hand, the amount of the structural unit (b') derived from an α-olefin having 4 or more carbon atoms is preferably 13 to 47 mass%, more preferably 15 to 42 mass%, even more preferably 19 to 36 mass%, and particularly preferably 23 to 31 mass%, with the proviso that (a') + (b') = 100 mass%.

[0043] When the composition of the propylene-α-olefin copolymer is within the above range, an ethylene copolymer composition having excellent appearance can be obtained. In addition, the heat resistance and mechanical strength also tend to be excellent.

[0044] 4-Methyl-1-pentene wax The unmodified polyolefin wax may be one obtained by pyrolysis of a 4-methyl-1-pentene-α-olefin copolymer as disclosed in WO 2011 / 055803 or a 4-methyl-1-pentene polymer as disclosed in JP 2015-028187 A.

[0045] <Method of manufacturing unmodified polyolefin wax> The unmodified polyolefin wax such as the polyethylene wax or polypropylene wax may be obtained by directly polymerizing ethylene or α-olefin, or may be obtained by thermally decomposing a high molecular weight copolymer. When thermally decomposing, it is preferable to thermally decompose at 300 to 450°C for 5 minutes to 10 hours. In this case, the unmodified polyolefin wax has an unsaturated end. Specifically, it is particularly preferable that the number of vinylidene groups per 1000 carbon atoms measured by 1H-NMR is 0.5 to 5, since this enhances the compatibilizing effect with the carbon material (B). In addition, the unmodified polyolefin wax may be purified by a method such as solvent fractionation, which fractionates based on the difference in solubility in a solvent, or distillation. In addition, it may be made of one kind of single polymer, or may be made of a mixture of two or more kinds of polymers.

[0046] When ethylene or an α-olefin is directly polymerized to obtain a polyolefin wax, the polyolefin wax can be produced by various known production methods, for example, a production method in which ethylene or an α-olefin is polymerized using a Ziegler / Natta catalyst or a metallocene catalyst.

[0047] <Production method of modified polyolefin wax (B)> The number average molecular weight (Mn) and Brookfield melt viscosity (mPa·s) of the modified polyolefin wax (B) tend to decrease when the polymerization temperature during polymerization of the unmodified polyolefin wax is increased or when the hydrogen concentration is increased, and can be controlled within the above range. Alternatively, they can be adjusted by the amount of organoaluminum oxy-compound and / or ionizing ionic compound used as a cocatalyst. Furthermore, they can also be adjusted by purification after polymerization.

[0048] The content of the structural units selected from ethylene and each α-olefin in the modified polyolefin wax (B) can be controlled by adjusting the blending amount during polymerization, as well as the type of catalyst and polymerization temperature.

[0049] The Mw / Mn of the modified polyolefin wax (B) can be controlled by the type of catalyst and the polymerization temperature during polymerization of the unmodified polyolefin wax. Generally, Ziegler-Natta catalysts and metallocene catalysts are used for polymerization, but it is preferable to use metallocene catalysts to achieve a suitable range of Mw / Mn. It can also be achieved by refining the wax by solvent fractionation, which separates the wax based on the difference in solubility in the solvent, or by distillation or other methods.

[0050] The softening point of the modified polyolefin wax (B) can be adjusted by the composition of ethylene or α-olefin during polymerization of the unmodified polyolefin wax. For example, in the case of a copolymer of ethylene and α-olefin, the softening point tends to be lowered by increasing the content of α-olefin. It can also be controlled by the type of catalyst and polymerization temperature. It can also be adjusted by purification after polymerization.

[0051] Air oxidation of unmodified polyolefin wax (oxidized product) The air oxidation of unmodified polyolefin wax is obtained by contacting the raw material unmodified polyolefin wax with oxygen or an oxygen-containing gas while stirring in a molten state, thereby oxidizing and modifying the unmodified polyolefin wax. The unmodified polyolefin wax is usually brought into a molten state at a temperature of 130 to 200°C, preferably 140 to 170°C.

[0052] In the oxidative modification, the raw material unmodified polyolefin wax is brought into contact with oxygen or an oxygen-containing gas in a molten state while being stirred to carry out the oxidation reaction. The term "oxygen or oxygen-containing gas" is used to include pure oxygen (oxygen obtained by ordinary liquid air fractional distillation or water electrolysis, which may contain other components at the impurity level), mixed gas of pure oxygen with other gases, such as air, and ozone.

[0053] As a method for contacting the raw material unmodified polyolefin wax with oxygen, etc., specifically, a method of continuously supplying an oxygen-containing gas from the bottom of a reactor to contact the unmodified polyolefin wax is preferred. In this case, the oxygen-containing gas is preferably supplied so that the amount of oxygen per minute is 1.0 to 8.0 NL per 1 kg of the raw material mixture.

[0054] An example of an air-oxidized unmodified polyolefin wax includes oxidized paraffin (manufactured by Nippon Seiro Co., Ltd.).

[0055] Acid-grafted modified polyolefin wax The graft modified product of the unmodified polyolefin wax may be, for example, a modified polyolefin wax obtained by acid graft-modifying an unmodified polyolefin wax with an unsaturated carboxylic acid or its derivative (hereinafter also referred to as acid graft modified polyolefin wax (B')), a styrene graft modified polyolefin wax obtained by graft-modifying the unmodified polyolefin wax with a styrene, a modified polyolefin wax obtained by graft-modifying the unmodified polyolefin wax with a mixture of these, or a sulfonate graft modified polyolefin wax obtained by modifying the unmodified polyolefin wax with a sulfonate. These may be prepared by a conventionally known method. For example, the unmodified polyolefin wax may be melt-kneaded with (1) the raw material unmodified polyolefin wax and (2) an unsaturated carboxylic acid or its derivative, a styrene, or a sulfonate in the presence of (3) a polymerization initiator such as an organic peroxide, or may be kneaded in a solution in which (1) the raw material unmodified polyolefin wax and (2) an unsaturated carboxylic acid or its derivative, a styrene, or a sulfonate are dissolved in an organic solvent in the presence of (3) a polymerization initiator such as an organic peroxide.

[0056] For melt kneading, for example, an autoclave, a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, a single screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc. are used. Among these, the use of a device with excellent batch-type melt kneading performance, such as an autoclave, makes it possible to obtain a polyolefin wax in which each component is more uniformly dispersed and reacted. Compared with the continuous type, the batch type makes it easier to adjust the residence time, and since the residence time can be made longer, it is relatively easy to increase the modification rate and modification efficiency, and is the most preferred embodiment in the present invention.

[0057] When the modified polyolefin wax (B) is an acid-grafted modified polyolefin wax (B') grafted with an unsaturated carboxylic acid or a derivative thereof and a styrene, the graft ratio "(unsaturated carboxylic acid or a derivative thereof) / (styrene)" (unit: mass ratio) is preferably 0.01 to 1, more preferably 0.03 to 0.8, and particularly preferably 0.05 to 0.6. When the graft ratio is 0.01 or more, the interaction of the unsaturated carboxylic acid or a derivative thereof with the surface of the carbon material (B) is easily obtained sufficiently, and thus the impact resistance is easily improved. In addition, when the graft ratio is 1 or less, the melt viscosity of the acid-modified polyolefin wax (B') does not become too high, and thus the processability is not easily impaired.

[0058] Examples of the unsaturated carboxylic acid or a derivative thereof that can be used for the acid graft modification include unsaturated carboxylic acids, their anhydrides, esters, acid halides, amides, and imides. Examples of such acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, sec-butyl acrylate, isobutyl acrylate, propyl acrylate, isopropyl acrylate, 2-octyl acrylate, dodecyl acrylate, stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate, 2-chlorophenyl acrylate, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxylate acrylate, and 2,2,2-trifluoroethyl acrylate;

[0059] Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, isopropyl methacrylate, 2-octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, 2-chlorohexyl methacrylate, diethylaminoethyl methacrylate, 2-hexylethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate; Other esters similar to those mentioned above, such as crotonic acid, isocrotonic acid, etc.

[0060] Maleate esters such as ethyl maleate, propyl maleate, butyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate; Fumarate esters such as ethyl fumarate, butyl fumarate, and dibutyl fumarate; Furthermore, as the above esters, hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and hydroxyethoxy methacrylate, and glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and glycidyl maleate can also be used.

[0061] Maleic acid, fumaric acid, itaconic acid, crotonic acid, norbornene dicarboxylic acid, Dicarboxylic acids such as nadic acid and methylhexahydrophthalic acid; Anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, allylsuccinic anhydride, glutaconic anhydride, and nadic anhydride; As for the halide, malenyl chloride, dichloromaleic anhydride (C 4 C 12 O 3 Examples of amides include sulfamide, phthalamide, and maleamide, and examples of imides include maleimide, phthalimide, and sulfimide. These unsaturated carboxylic acids and derivatives thereof may be used alone or in combination of two or more.

[0062] Among these, maleic anhydride is preferred. Maleic anhydride has a relatively high reactivity with the raw material unmodified polyolefin wax, and is itself less likely to undergo large structural changes due to polymerization or the like, and tends to be stable as a basic structure. Therefore, when the modified polyolefin wax (B) is a polyolefin wax grafted with maleic anhydride, the maleic anhydride grafted polyolefin wax added to the composition remains stable even in a high-temperature environment during molding, and as a result, the resin composition is considered to have a good balance of appearance, heat resistance, processability, and mechanical strength.

[0063] The acid-grafted polyolefin wax (B') may be a commercially available product. Examples of commercially available acid-modified polyolefin waxes include Diacarna-PA30 (manufactured by Mitsubishi Chemical Corporation) and high wax acid-treated NP0555A, 2203A, and 1105A (manufactured by Mitsui Chemicals, Inc.).

[0064] Styrene modified Examples of styrenes used for styrene modification include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, and N-vinylpyrrolidone.

[0065] Sulfonate Modified The unmodified polyolefin wax or the graft-modified polyolefin wax may be further modified with a sulfonate. In this case, the amount of modification with sulfonic acid is preferably 0.1 to 100 mmol, more preferably 5 to 50 mmol, per 1 g of the polymer (unmodified polyolefin wax or the graft-modified polyolefin wax). When the amount of modification with sulfonate is within the above range, the mechanical strength of the molded article obtained from the composition is improved.

[0066] The acid value of the modified polyolefin wax (B) can be adjusted by one or more of the amount of air oxidation, the amount of acid graft modification, and the amount of sulfonate modification.

[0067] When the modified polyolefin wax (B) is a styrene modified product (styrene modified polyolefin wax), the content of styrenes (styrene content) is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and particularly preferably 20 to 50 parts by mass, based on 100 parts by mass of the modified polyolefin wax (B). When the content of styrenes in the modified polyolefin wax (B) is within the above range, the balance between heat resistance and mechanical strength is excellent. The content of styrenes can be calculated from the amount of styrenes added during modification.

[0068] The styrene content of the modified polyolefin wax (B) can be adjusted by the amount of styrene modification.

[0069] As described above in the acid graft modified product of unmodified polyolefin wax, the graft modified product of unmodified polyolefin wax can be obtained, for example, by kneading (1) the raw material unmodified polyolefin wax and (2) an unsaturated carboxylic acid or a derivative thereof, a styrene or a sulfonate in a solution dissolved in an organic solvent in the presence of (3) a polymerization initiator such as an organic peroxide. The radical initiator used here may be an organic peroxide, an organic perester, an azo compound, or the like. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(peroxidebenzoate)-3-hexyne, 1,4-bis(t-butylperoxyisopropyl)benzene, lauroyl peroxide, t-butyl peracetate, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl perpivalate, cumyl perpivalate, t-butyl perdiethyl acetate; azobisisobutyronitrile, and dimethyl azoisobutyrate. Of these, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 1,4-bis(t-butylperoxyisopropyl)benzene are preferably used. The radical initiator is preferably used in a proportion of 0.001 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the unmodified polyolefin wax. The reaction temperature for the above-mentioned graft reaction using a radical initiator or for the graft reaction carried out without using a radical initiator is usually set within the range of 120°C to 350°C.

[0070] <Trans polyoctenylene (C)> The ethylene copolymer composition of the present invention preferably contains trans polyoctenylene (C). By containing trans polyoctenylene (C), the composition has good adhesion to other materials, for example, layers containing fibrous materials such as industrial belts, and a laminate obtained from the composition has excellent adhesive strength between a layer formed by crosslinking the composition and a layer containing a fibrous material. Trans polyoctenylene (C) is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond. The ethylene copolymer composition of the present invention contains the trans-polyoctenylene (C), and thus the compatibility with fibrous materials can be improved, leading to improved tackiness and improved adhesion to fibrous materials. Incidentally, trans-polyoctenylene (C) is manufactured and sold by Evonik Industries under the trade name VESTENAMER.

[0071] <Ethylene-Based Copolymer Composition> The ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition forming the layer [I] of the laminate of the present invention are compositions containing the ethylene-α-olefin-non-conjugated polyene copolymer (A) and a modified polyolefin wax (B), and preferably contain the modified polyolefin wax (B) in an amount of 0.5 to 100 parts by mass, more preferably 1 to 70 parts by mass, even more preferably 2 to 50 parts by mass, particularly preferably 4 to 30 parts by mass, and particularly preferably 6 to 15 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0072] The ethylene-based copolymer composition of the present invention contains the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the modified polyolefin wax (B), and therefore has excellent adhesion to other materials, for example layers containing fibrous materials such as industrial belts, and molded articles and laminates obtained from the composition also have good mechanical properties.

[0073] The ethylene copolymer composition of the present invention desirably further contains a trans-polyoctenylene (C). When the ethylene copolymer composition of the present invention contains a trans-polyoctenylene (C), the amount thereof is in the range of 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, further preferably 1 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, and particularly preferably 1 to 6 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). The ethylene copolymer composition containing the trans-polyoctenylene (C) has good adhesion to other materials, for example, layers containing fibrous materials such as industrial belts, and a laminate obtained by crosslinking the composition has excellent adhesive strength to layers containing fibrous materials.

[0074] In addition to the ethylene-α-olefin-non-conjugated polyene copolymer (A), modified polyolefin wax (B), and trans-polyoctenylene (C), the ethylene copolymer composition of the present invention may contain other components according to the desired purpose within the range that does not impair the effects of the present invention. The other components may contain at least one selected from, for example, a crosslinking agent, a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a filler, a softener, an antiaging agent, a processing aid, an activator, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener. Each additive may be used alone or in combination of two or more.

[0075] <Crosslinking agents, crosslinking assistants, vulcanization accelerators and vulcanization assistants> Examples of the crosslinking agent include crosslinking agents generally used when crosslinking rubber, such as organic peroxides, phenolic resins, sulfur-based compounds, hydrosilicone-based compounds, amino resins, quinones or their derivatives, amine-based compounds, azo-based compounds, epoxy-based compounds, isocyanate-based compounds, etc. Among these, organic peroxides and sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred.

[0076] 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, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0077] When an organic peroxide is used as a crosslinking agent, 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, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). When the amount of the organic peroxide is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article, which is preferable.

[0078] When an organic peroxide is used as a crosslinking agent, it is preferable to use a crosslinking assistant in combination. Examples of the crosslinking assistant include sulfur; quinone dioxime crosslinking assistant such as p-quinone dioxime; acrylic crosslinking assistant such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking assistant such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking assistant; divinylbenzene; and metal oxides such as 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 Seki Kogyo Co., Ltd.)).

[0079] When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, more preferably 1 to 6 mol, per mol of the organic peroxide.

[0080] Examples of sulfur-based compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0081] When a sulfur-based compound is used as a crosslinking agent, the blending amount thereof in the copolymer composition is usually 0.1 to 10 parts by mass, preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass, based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). When the blending amount of the sulfur-based compound is within the above range, there is no bloom on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties.

[0082] When a sulfur-based compound is used as the crosslinking agent, 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 (for example, Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenyl guanidine, triphenyl guanidine, and diorthotolyl guanidine; 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 (for example, Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (e.g., 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 (e.g., Sancerar PZ, Sancerar BZ, and Sancerar EZ (trade names; manufactured by Sanshin Chemical Industry Co., Ltd.)) and tellurium diethyldithiocarbamate; thiourea vulcanization accelerators such as ethylenethiourea (e.g., 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 vulcanization accelerators such as zinc dibutylxatogenate.

[0083] When a vulcanization accelerator is used, the blending amount of the vulcanization accelerator in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). When the blending 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 obtained molded article. When a sulfur-based compound is used as a crosslinking agent, a vulcanization assistant can be used in combination.

[0084] Examples of the vulcanization aid include zinc oxide (e.g., ZnO#1 and zinc oxide type 2, 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 Seki Kogyo Co., Ltd.)). When a vulcanization aid is used, the amount of the vulcanization aid in the ethylene copolymer composition is usually 1 to 20 parts by mass based on 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A).

[0085] <Filler> The filler constituting the ethylene copolymer composition of the present invention is a known rubber reinforcing agent blended into a rubber composition, and is usually an inorganic substance called carbon black or an inorganic reinforcing agent.

[0086] Specific examples of the filler used in the present invention include Asahi #55G, Asahi #60UG, Asahi #70 (all manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, etc.) carbon black (manufactured by Tokai Carbon Co., Ltd.), these carbon blacks which have been surface-treated with a silane coupling agent or the like, as well as silica, activated calcium carbonate, finely divided talc, finely divided silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like.

[0087] These fillers may be used alone or in combination of two or more. As the filler in the present invention, preferably used are carbon black, silica, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like.

[0088] When the 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 20 to 100 parts by mass, and more preferably 30 to 50 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0089] <Softener> Examples of softeners 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 polymeric substances such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others, such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub(factice). Of these, petroleum-based softeners are preferred, and process oil is particularly preferred.

[0090] When the ethylene-based copolymer composition contains a softener, the amount of the softener is generally 2 to 100 parts by mass, preferably 3 to 100 parts by mass, more preferably 4 to 40 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0091] <Anti-aging agent (stabilizer)> By blending an antioxidant (stabilizer) with the ethylene copolymer composition of the present invention, the life of the seal packing formed therefrom can be extended. Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0092] Examples of the antioxidant include aromatic secondary amine antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; and thioether antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide. Antiaging agents: dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0093] When the ethylene copolymer composition contains an antioxidant, the amount of the antioxidant is usually 0.3 to 25 parts by mass, preferably 3 to 20 parts by mass, more preferably 8.0 to 15 parts by mass, and particularly preferably 10 to 14 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). 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, the occurrence of vulcanization inhibition can be suppressed.

[0094] <Processing aids> As the processing aid, a wide variety of processing aids that are generally compounded with 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.Of these, stearic acid is preferred.

[0095] When the copolymer composition contains a processing aid, it can be appropriately blended in an amount of usually 0.1 to 3 parts by mass, preferably 0.5 to 1.5 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). When the blending amount of the processing aid is within the above range, it is preferable since the processability, such as kneading processability, extrusion processability, and injection moldability, is excellent. The processing aid may be used alone or in combination with two or more kinds.

[0096] <Activator> Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triaryl methylate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0097] When the copolymer composition contains an activator, the amount of the activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A).

[0098] <Laminate> The laminate of the present invention is a laminate in which a layer [I] made of the ethylene copolymer composition of the present invention is in contact with a layer [II] containing a fibrous material.

[0099] <Layer [I] made of ethylene-based copolymer composition> The layer [I] made of an ethylene-based copolymer composition constituting the laminate of the present invention is preferably a layer obtained by crosslinking the above-mentioned ethylene-based copolymer composition.

[0100] <Layer containing fiber material [II]> The layer [II] containing a fiber material that constitutes the laminate of the present invention contains a fiber material in at least a part of the layer.

[0101] Textile materials The fibrous material for forming layer [II] according to the present invention includes various known fibrous materials, such as natural fibers such as cotton and wood cellulose fibers; organic fibrous materials of 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; inorganic fibrous 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, etc. are exemplified.

[0102] These fibrous materials may be long fibers (filaments) or short fibers (staples). Also, the fibrous material may be cord yarn, spun yarn, woven fabric, knitted fabric, canvas, non-woven fabric, etc.

[0103] 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.

[0104] Also, these fibrous materials may be surface-treated by known methods such as resorcinol formalin latex treatment (RFL treatment) in order to improve the adhesiveness between the fibrous materials or with layer [I] composed of the above ethylene-based copolymer composition.

[0105] <RFL treatment> RFL treatment is a process in which textile materials are treated with a treatment liquid (RFL liquid) containing resorcinol, formalin, and latex, and this RFL liquid is a mixture of the initial condensation product of resorcinol and formalin and rubber latex. Examples of rubber latex that can be used 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. These can be used alone or in a blend of two or more types.

[0106] <Method of manufacturing laminate> In order to manufacture the laminate of the present invention, various known methods for manufacturing laminates can be adopted. For example, a method of laminating a layer [I] made of an uncrosslinked ethylene-based copolymer composition previously manufactured (molded) by a known method with a layer [II] containing a fiber material, and then crosslinking the layer [I] made of the ethylene-based copolymer composition, a method of laminating a layer [I] made of a crosslinked ethylene-based copolymer composition with a layer [II] containing a fiber material, or a method of extrusion coating a layer [I] made of an ethylene-based copolymer composition on a layer [II] containing a fiber material, and then crosslinking the layer [I] made of the ethylene-based copolymer composition, The layer [I] made of the ethylene copolymer composition can be produced by various known methods.

[0107] The ethylene copolymer composition can be obtained by kneading the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the modified polyolefin wax (B), if necessary, trans-polyoctenylene (C), and further additives such as a filler, an antioxidant, and a processing aid, using various known kneading and mixing devices, for example, a Banbury mixer, a kneader, an internal mixer (internal mixer) such as an Intermix, and a roll.

[0108] The uncrosslinked ethylene-based copolymer composition obtained by kneading may be molded into an intended shape by various molding methods such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then crosslinked to form a layer [I] consisting of the ethylene-based copolymer composition, which may then be laminated (bonded) with a layer [II] containing a fiber material; alternatively, the uncrosslinked ethylene-based copolymer composition may be molded into an intended shape by the above-mentioned method, and then laminated (bonded) with a layer [II] containing a fiber material, thereby crosslinking the composition.

[0109] 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.

[0110] In addition, when crosslinking, a mold may be used, or crosslinking may be performed without using a mold. When a mold is not used, the molding and crosslinking steps are usually performed continuously. As a heating method in the crosslinking tank, a heating tank using hot air, a glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, etc. may be used.

[0111] <Applications of laminates> A laminate in which a layer [I] made of the ethylene-based copolymer composition of the present invention is in contact with a layer [II] containing a fiber material is suitably used for automobile hoses, water hoses, and gas hoses; industrial belts such as transmission belts and conveyor belts; and escalator handrails.

[0112] Examples of the automobile 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. EXAMPLES

[0113] The present invention will now be described in more detail with reference to examples. Not limited to this. The ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the examples and comparative examples was The copolymers are the following copolymer (A-1) and copolymer (A-2). Copolymer (A-1) According to the description of [Synthesis Example C1] in WO 2015 / 122415, the following physical properties were obtained. Ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer Hereinafter, this is referred to as "copolymer (A-1)". Copolymer (A-2) Ethylene-propylene-5-ethylidene-2-norbornene (ENB) copolymer (ENB-EPT). Trade name: Mitsui EPT 4045M manufactured by Mitsui Chemicals, Inc.

[0114] Item Copolymer (A-1) Copolymer (A-2) Structural units derived from ethylene: 69.1 mol% 57.4 mol% Structural units derived from 1-butene: 27.8 mol% - Structural units derived from propylene: - 40.3 mol% Structural units derived from ENB: 2.2 mol% 2.3 mol% Molar ratio: 70 / 30 58.7 / 41.3 (Structure derived from ethylene Units / α-olefin (Structural unit from which it is derived) Mooney Viscosity ML(1+4)125℃: 22 - B value: 1.3 -

[0115] The method for preparing the maleic anhydride modified polyethylene wax (B-1), which is the modified polyolefin wax (B) used in the Examples and Comparative Examples, is described below.

[0116] [Production Example 1] (1) Preparation of catalyst In a glass autoclave with an internal volume of 1.5 liters, 25 g of commercially available anhydrous magnesium chloride was suspended in 500 ml of hexane. This was kept at 30°C and stirred while 92 ml of ethanol was added dropwise over 1 hour, and the reaction was continued for another 1 hour. After the reaction was completed, 93 ml of diethylaluminum monochloride was added dropwise over 1 hour, and the reaction was continued for another 1 hour. After the reaction was completed, 90 ml of titanium tetrachloride was added dropwise, and the reaction vessel was heated to 80°C and reacted for 1 hour. After the reaction was completed, the solid portion was washed with hexane by decantation until no free titanium was detected. This was suspended in hexane and the titanium concentration was quantified by titration, and the suspension was used in the following experiment. (2) Manufacture of ethylene-propylene copolymer (unmodified polyolefin wax) A 2-liter stainless steel autoclave was thoroughly purged with nitrogen and charged with 930 ml of hexane and 70 ml of propylene. Hydrogen was then pumped in at 20.0 kg / cm. 2 (gauge pressure). Next, the temperature inside the system was raised to 170° C., and then 0.1 mmol of triethylaluminum, 0.4 mmol of ethylaluminum sesquichloride, and a hexane suspension of the solid obtained above were injected with ethylene so that the amount of titanium component was 0.008 mmol in atomic terms, to initiate polymerization. Then, the total pressure was increased to 40 kg / cm by continuously feeding only ethylene. 2 (gauge pressure), and polymerization was carried out at 170° C. for 40 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, the unreacted ethylene and propylene were purged. The resulting polymer solution was dried overnight under reduced pressure at 100°C to obtain an ethylene-propylene copolymer. (3) Manufacturing of modified polyolefin wax 500 g of the unmodified polyolefin wax prepared above was charged into a glass reactor and melted at 160° C. under a nitrogen atmosphere. Next, 30 g of maleic anhydride and 3 g of di-t-butyl peroxide (hereinafter abbreviated as DTBPO) were continuously fed into the reaction system (temperature 160° C.) over 5 hours. After that, the mixture was heated and reacted for another hour, and then degassed in a molten state under a vacuum of 10 mmHg for 0.5 hours to remove volatile matter, and then cooled to obtain a modified polyolefin wax (B-1).

[0117] Item (B-1) Ethylene content: 96% by mass Propylene content: 4% by mass Acid value (JIS K 0070): 60mg-KOH / g Mn by GPC: 1,700 Mw / Mn: 2.4 BF viscosity (140℃): 150mPa·s Density (JIS K 7112): 920kg / m 3 Softening point (JIS K 2207): 110℃

[0118] The physical properties of the copolymer (A-1) and the copolymer (A-2) were determined by the following methods. Molar amounts of structural units derived from ethylene, structural units derived from α-olefins, and structural units derived from non-conjugated polyenes These molar amounts are 1 The intensity was measured using a H-NMR spectrometer. Details of the measurement conditions are described in WO 2015 / 122415.

[0119] Mooney Viscosity The Mooney viscosity (ML(1+4) 125° C.) was measured using a Mooney viscometer (Shimadzu Corporation, SMV202 type) in accordance with JIS K6300 (1994).

[0120] B value o-Dichlorobenzene-d 4 / benzene-d6 (4 / 1 [v / v]) was used as the measurement solvent, and the measurement temperature was 120°C. 13 A C-NMR spectrum (100 MHz, JEOL ECX400P) was measured, and calculation was performed based on the following formula (i). B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X] and [Y] respectively represent the molar fractions of structural units derived from ethylene [A1], α-olefins [A2] having 4 to 20 carbon atoms, and non-conjugated polyenes [A3], and [EX] represents the ethylene [A1]-α-olefins [A2] having 4 to 20 carbon atoms dyad chain fraction.]

[0121] The physical properties of the ethylene-α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid were measured by the following methods.

[0122] Brookfield Viscosity (140℃) The Brookfield (BF) viscosity (mPa·s) at 140°C was measured according to the method described in JIS K7117-1.

[0123] Weight average molecular weight (Mw) The number average molecular weight Mn of the modified polyolefin wax (B) was determined by GPC measurement. The measurement was performed under the following conditions. The number average molecular weight (Mn) and weight average molecular weight (Mw) were determined from a calibration curve using a commercially available monodisperse standard polystyrene, and Mw / Mn was calculated. Equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Solvent: o-dichlorobenzene Columns: 2 TSKgel GMH6-HT and 2 TSKgel GMH6-HTL columns (both manufactured by Tosoh Corporation) Flow rate: 1.0ml / min Sample: 0.15mg / mL o-dichlorobenzene solution

[0124] softening point Measurements were performed in accordance with JIS K2207.

[0125] density Measurements were performed in accordance with JIS K7112.

[0126] Acid value The measurement was performed in accordance with JIS K 0070. An acid value of 11 mg KOH / g is converted to a polar group content of 1 mass %.

[0127] [Trans-polyoctenylene] As the trans-polyoctenylene, Vestenamer 8012 (trade name, manufactured by Evonik Industries) was used.

[0128] The physical properties of the ethylene copolymer composition (non-crosslinked product) are determined as follows. Measurement of adhesion The tackiness (Peak Value (gf)) was evaluated using a probe tack tester under the following conditions. Measurements were performed under the following conditions using an uncrosslinked sheet with a thickness of 1 mm. 5mm diameter stainless steel probe Approach speed: 120mm / min. Pressure: 100g Pressurization time: 20 sec. Peeling speed: 120mm / min. Temperature at which the probe and test piece (uncrosslinked sheet) are placed: 50°C.

[0129] The physical properties of the crosslinked ethylene copolymer composition are determined as follows.

[0130] Peel strength The peel strength (adhesion strength) between the layer [I] made of the crosslinked ethylene copolymer composition and the layer [II] containing a fiber material was measured by the following method.

[0131] A 3 mm thick uncrosslinked sheet was placed on top of a 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 from the laminate and subjected to a T-peel test at a tensile speed of 50 mm / min. to determine the peel strength (adhesive strength) (N / cm). The peel test was carried out three times, and the average value was regarded as the peel strength.

[0132] Example 1 The copolymer (A-1) was masticated for 30 seconds, and then 100 parts by weight of the masticated copolymer (A-1) was added to 5 parts by weight of zinc oxide (Hakusui Tech Co., Ltd. zinc oxide type 2) as a crosslinking assistant, Stearic acid as a lubricant: 1 part by weight Anti-aging agent: Tetrakis[methylene(3,5- Di-t-butyl-4-hydroxy)hydrocinnamate Methane (product name Irganox 1010 BASFF Japan Co., Ltd.] 4 parts by weight, 2-Mercaptobenzimidazole (Product name: Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.) 8 parts by weight, Carbon black (manufactured by Asahi Carbon Co., Ltd., product name Asahi #70) 40 parts by weight, Silica (manufactured by Evonik, trade name ULTRASIL VN2) 10 parts by weight, Softener [Product name: Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.] 10 parts by mass, and Trans-polyoctenylene (M) from Evonik (Evonik Industries AG) Product name: VESTENAMER 8012 5 parts by mass The mixture was mixed for 2 minutes in a 1.7-liter Banbury mixer (manufactured by Kobe Steel, Ltd.). After that, the ram was raised and cleaned, and the mixture was mixed for another minute and discharged at about 150°C to obtain a mixture (mixture 1). This mixing was performed at a filling rate of 70%.

[0133] Next, 172 parts by weight of this compound (Compound-1) 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 8 parts by weight of copolymer (B-1) and 6.8 parts by weight of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP-40C) as a crosslinking agent were added and kneaded for 10 minutes to obtain a compound (Compound-2), which was then cut into sheets according to the test pieces to prepare uncrosslinked sheets with thicknesses of 1 mm, 2 mm, and 3 mm.

[0134] The adhesiveness (gf) of the obtained uncrosslinked sheet having a thickness of 1 mm was measured by the method described above. The results are shown in Table 1. The obtained uncrosslinked sheet having a thickness of 2 mm was then subjected to a 170 The crosslinked sheet was then pressed at 0.degree. C. for 15 minutes to prepare a crosslinked sheet. The physical properties of the crosslinked sheet thus obtained were measured by the methods described above. The results are shown in Table 1.

[0135] [Comparative Example 1 and Comparative Example 2] In the case where the copolymer (B-1) was not used, except that the compositions shown in Table 2 were used, an uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, and the physical properties and the like were evaluated by the same method. However, in Comparative Example 1, instead of dicumyl peroxide, the compounds shown in Table 3 were added, and vulcanization was carried out with sulfur and a vulcanization accelerator. The evaluation results are shown in Table 2. The compounds used in the examples and comparative examples are shown in Table 1.

[0136] [Table 1]

[0137]

Table 2

[0138]

Table 3

Claims

1. An ethylene-based copolymer composition comprising an ethylene / α-olefin / non-conjugated polyene copolymer (A) that satisfies the following requirements (a1) to (a4), and a modified polyolefin wax (B). Requirement (a1): The polymer contains a structural unit derived from ethylene [L], a structural unit derived from an α-olefin [M] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [N], and the molar ratio [[L] / [M]] of the structural unit derived from ethylene [L] to the structural unit derived from the α-olefin [M] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (a2): The content of structural units derived from the non-conjugated polyene [N] is 0.1 to 6.0 mol % (where the total of the structural units derived from [L], [M] and [N] is 100 mol %). Requirement (a3): Mooney viscosity (ML(1+4) 125°C) is 5 to 100. Requirement (a4): The B value represented by the following formula (i) is 1.20 or more. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) (wherein [E], [X] and [Y] respectively represent the molar fractions of structural units derived from ethylene [L], an α-olefin [M] having 4 to 20 carbon atoms, and a non-conjugated polyene [N], and [EX] represents the dyad chain fraction of ethylene [L]-α-olefin [M] having 4 to 20 carbon atoms.)

2. The ethylene-based copolymer composition according to claim 1, wherein the α-olefin [M] having 4 to 20 carbon atoms constituting the ethylene / α-olefin / non-conjugated polyene copolymer (A) is 1-butene.

3. 2. The ethylene copolymer composition according to claim 1, wherein the acid value of the modified polyolefin wax (B) is 30 to 90 mg-KOH / g.

4. The ethylene copolymer composition according to claim 1, wherein the modified polyolefin wax (B) has a number average molecular weight (Mn) of 100 to 10,000.

5. The ethylene copolymer composition according to claim 1, wherein the modified polyolefin wax (B) has a melt viscosity (140° C.) of 10 to 1,000 mPa·s.

6. 2. The ethylene copolymer composition according to claim 1, wherein the modified polyolefin wax (B) is a maleic acid modified polyethylene wax.

7. The ethylene-based copolymer composition according to claim 1, comprising 0.5 to 100 parts by mass of the modified polyolefin wax (B) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

8. The ethylene copolymer composition according to claim 1, which contains a trans-polyoctenylene (C).

9. The ethylene-based copolymer composition according to claim 8, comprising 0.5 to 50 parts by mass of trans-polyoctenylene (C) per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A).

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

11. The laminate according to claim 10, wherein the ethylene-based copolymer composition is crosslinked.

12. The laminate according to claim 10, wherein the textile material of the layer [II] is canvas.

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

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