Ethylene copolymer composition and use thereof

Abstract

To improve the adhesion between an ethylene / α-olefin / nonconjugated polyene rubber and synthetic fibers and the heat resistance of rubber and to further develop the use of the rubber for lamination of the rubber with synthetic fibers such as a carcass layer of a conveyer belt.SOLUTION: The present invention provides an ethylene-based polymer composition comprising (A) an ethylene / α-olefin / non-conjugated polyene polymer satisfying specific requirements and (B) an ethylene / α-olefin polymer having substituents derived from α,β-unsaturated carboxylic acids satisfying specific requirements, and uses thereof.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[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 rubber-coated fabrics. Among them, it is desired to be used for the carcass layer of a conveyor belt, and improvements for further improving productivity and lifespan are required. Therefore, improving the adhesiveness between an ethylene-α-olefin-non-conjugated polyene copolymer rubber and a synthetic fiber has been studied, and it has been proposed to use a sulfur vulcanization system ethylene propylene rubber composition containing zinc white obtained by blending a trans-polyoctenylene rubber with an ethylene-α-olefin-diene copolymer (Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to improve the adhesiveness between an ethylene-α-olefin-non-conjugated polyene copolymer rubber and a synthetic fiber, and further improve heat resistance, and further develop its use for laminating with synthetic fibers such as the carcass layer of a conveyor belt.

Means for Solving the Problems

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

[11] . [1] A composition containing an ethylene·α-olefin·non-conjugated polyene copolymer as component (A) and an ethylene·α-olefin copolymer having a substituent derived from an α,β-unsaturated carboxylic acid as component (B), wherein component (A) and component (B) are defined as follows, an ethylene-based copolymer composition. Component (A): Satisfies the following requirements (a1) to (a4). Requirement (a1): It 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] and 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 the structural unit derived from the non-conjugated polyene [N] is 0.1 to 6.0 mol% (however, the total of the structural units derived from [L], [M], and [N] is 100 mol%). Requirement (a3): The 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) (However, [E], [X], and [Y] represent the mole fractions of ethylene [L], an α-olefin [M] having 4 to 20 carbon atoms, and a non-conjugated polyene [N], respectively, and [EX] represents the dyad chain fraction of ethylene [L] - an α-olefin [M] having 4 to 20 carbon atoms.) Component (B): Satisfies the following requirements (b1) to (b2). Requirement (b1): The Brookfield viscosity (150°C) is 1 to 5,000 mPa·s. Requirement (b2): The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 1,000 to 100,000.

[0006] [2] The ethylene-based copolymer composition according to [1] above, wherein the α-olefin having 4 to 20 carbon atoms [M] constituting component (A) is 1-butene. [3] The ethylene-based copolymer composition according to [1] or [2] above, wherein the α,β-unsaturated carboxylic acid of component (B) is maleic acid. [4] The ethylene-based copolymer composition according to any one of [1] to [3] above, wherein the acid value of component (B) is 1 to 100 mgKOH / g.

[0007] [5] The ethylene-based copolymer composition according to any one of [1] to [4] above, containing 0.5 to 100 parts by mass of component (B) per 100 parts by mass of component (A). [6] The ethylene-based copolymer composition according to any one of [1] to [5] above, containing trans-polyoctenylene (C). [7] The ethylene-based copolymer composition according to any one of [1] to [6] above, containing 0.5 to 50 parts by mass of trans-polyoctenylene (C) per 100 parts by mass of component (A).

[0008] [8] A laminate, characterized in that a layer [I] composed of the ethylene-based copolymer composition according to any one of [1] to [7] above is in contact with a layer [II] containing a fiber material. [9] The laminate according to [8] above, wherein the ethylene-based copolymer composition is crosslinked.

[10] The laminate according to any one of [8] or [9] above, wherein the fiber material of the above layer [II] is canvas.

[11] An industrial belt having the laminate according to any one of [8] to

[10] above.

Advantages of the Invention

[0009] According to the present invention, the adhesiveness between an ethylene·α-olefin·non-conjugated polyene copolymer rubber and a synthetic fiber is improved, and further, the heat resistance of a laminate comprising the same is improved, and productivity and lifespan can be enhanced.

Mode for Carrying Out the Invention

[0010] The ethylene-based copolymer composition of the present invention contains an ethylene·α-olefin·non-conjugated polyene copolymer (A) as component (A) and an ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid as component (B). Component (A) will be described below.

[0011] <Ethylene·α-olefin·non-conjugated polyene copolymer (A)> The ethylene·α-olefin·non-conjugated polyene copolymer (A) as component (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] Requirement (a1) 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 the molar ratio [L] / [M] of the structural unit derived from ethylene [L] and the structural unit 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 is excellent in the 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, still more preferably 55 / 45, particularly preferably 60 / 40, and most preferably 65 / 35. The upper limit of [L] / [M] is preferably 80 / 20, more preferably 75 / 25, and still more preferably 70 / 30.

[0013] Requirement (a2) In the ethylene·α-olefin·non-conjugated polyene copolymer (A), the content ratio of the structural unit derived from the non-conjugated polyene [N] is 0.1 to 6.0 mol% based on 100 mol% of the total of the structural unit derived from the [L], the structural unit derived from the [M], and the structural unit derived from the [N]. The ethylene·α-olefin·non-conjugated polyene copolymer (A) with the content ratio within the above range has sufficient crosslinkability and flexibility. The lower limit of the content ratio of the structural unit derived from the [N] is preferably 0.5 mol%. The upper limit of the content ratio of the structural unit derived from the [N] is preferably 4.0 mol%, more preferably 3.5 mol%, and still more preferably 3.0 mol%. When the content of the structural unit derived from the non-conjugated polyene [N] is within the above range, an ethylene·α-olefin·non-conjugated polyene copolymer (A) having sufficient crosslinkability and flexibility can be obtained.

[0014] Requirement (a3) The Mooney viscosity ML(1+4) at 125 °C is in the range of 5 to 100, preferably 10 to 95, more preferably 10 to 60, still more preferably 3 to 40, and particularly preferably 15 to 30. When the Mooney viscosity is within the above range, the ethylene·α-olefin·non-conjugated polyene copolymer (A) has good processability and fluidity, and also shows good post-treatment quality (ribbon handling property) and excellent physical properties.

[0015] 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) (However, [E], [X], and [Y] represent the molar fractions of ethylene [L], α-olefin [M] having 4 to 20 carbon atoms, and non-conjugated polyene [N], respectively, and [EX] represents the dyad chain fraction of ethylene [L] - α-olefin [M] having 4 to 20 carbon atoms.) The B value is 1.20 or more, preferably in the range of 1.20 to 1.80, particularly preferably in the range of 1.22 to 1.40. For an ethylene copolymer with a B value of less than 1.20, the compression set at low temperature increases, and there is a risk that an ethylene copolymer excellent in the balance between rubber elasticity at low temperature and tensile strength at normal temperature cannot be obtained.

[0016] Examples of the α-olefin [M] having 4 to 20 carbon atoms include linear structures without side chains, starting from 1-butene having 4 carbon atoms, passing through 1-nonene having 9 carbon atoms and 1-decene having 10 carbon atoms, to 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, etc. 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, particularly 1-butene, 1-hexene, 1-octene, etc. are preferred, and particularly 1-butene is suitable.

[0018] Examples of the non-conjugated polyene [N] include chain non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene.

[0019] These non-conjugated polyenes [N] can be used alone or in combination of two or more. Among these, chain non-conjugated dienes such as 1,4-hexadiene and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 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.

[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, 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-nonconjugated polyene copolymer (A) is used in one kind or two or more kinds as necessary.

[0021] <Method for Producing 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, by 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 International Publication No. 2015 / 122415 pamphlet, particularly the examples described in paragraphs

[0249] to

[0320] of the said publication can be adopted. Next, component (B) will be described.

[0022] <Ethylene·α-Olefin Copolymer (B) Having a Substituent Derived from α,β-Unsaturated Carboxylic Acid> The ethylene·α-olefin copolymer (B) having a substituent derived from α,β-unsaturated carboxylic acid as component (B) satisfies the following requirements (b1) to (b2).

[0023] Requirement (b1) The Brookfield viscosity (at 150 °C) is 1 to 5,000 mPa·s. The Brookfield (BF viscosity) of the ethylene·α-olefin copolymer (B) having a substituent derived from α,β-unsaturated carboxylic acid at 150 °C is in the range of 1 to 5,000 mPa·s, preferably in the range of 5 to 2,500 mPa·s, more preferably in the range of 10 to 1,000 mPa·s, still more preferably in the range of 30 to 500 mPa·s, particularly preferably in the range of 40 to 300 mPa·s, and especially preferably in the range of 50 to 200 mPa·s. If the BF viscosity of the ethylene·α-olefin copolymer (B) having a substituent derived from α,β-unsaturated carboxylic acid at 150 °C is lower than the above lower limit value, the tensile strength may decrease. On the other hand, if the BF viscosity is higher than the above upper limit value, the viscosity may become too high, resulting in a decrease in moldability or deterioration of the surface appearance. Thus, when the BF viscosity is within the above numerical range, a composition excellent in balance between tensile strength and moldability can be provided. The Brookfield viscosity can be measured by the method described in JIS K7117-1.

[0024] Requirement (b2) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 1,000 to 100,000. The Mw of the ethylene·α-olefin copolymer (B) having a substituent derived from the α,β-unsaturated carboxylic acid as component (B) is 1,000 to 100,000, preferably 1,500 to 90,000, more preferably 2,000 to 80,000, still more preferably 4,000 to 50,000, particularly preferably 5,000 to 30,000, and especially preferably 5,500 to 12,000.

[0025] When the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the above range, the processability when kneading with the ethylene·α-olefin·non-conjugated polyene copolymer (A) and the balance of the filler dispersibility of the resulting ethylene-based copolymer composition are improved.

[0026] The ethylene·α-olefin copolymer (B) having a substituent derived from the α,β-unsaturated carboxylic acid as component (B) used in the present invention satisfies the above requirements (b1) to (b2), preferably further satisfies one or more of the following requirements (b3) to (b6), more preferably two or more, still more preferably three or more, and particularly preferably all four.

[0027] Requirement (b3) The acid value of the ethylene·α-olefin copolymer (B) having a substituent derived from the α,β-unsaturated carboxylic acid as component (B) is preferably 1 to 100 mgKOH / g, more preferably 10 to 80 mgKOH / g, still more preferably 15 to 90 mgKOH / g, and particularly preferably 20 to 80 mgKOH / g. When the acid value of component (B) is in this range, the peel strength is good.

[0028] Requirement (b4) The density of the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid which is component (B), measured in accordance with JIS K 2249―3:2011 (ISO3838), is preferably 820~900 kg / m, more preferably 830~890 kg / m 3 , still more preferably 850~890 kg / m 3 , particularly preferably 850~880 kg / m 3 , most preferably 860~880 kg / m 3 . When the density is in such a range, the flexibility of the copolymer (B) is good.

[0029] Requirement (b5) In the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid which is component (B) used in the present invention, the skeletal unit derived from ethylene is preferably 40~75 mol%, more preferably 40~60 mol%, and the skeletal unit derived from α-olefin is preferably 25~60 mol%, more preferably 40~60 mol%. The ethylene content of the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid which is component (B) can be measured by the C-NMR method. For example, peak identification and quantification can be carried out according to the methods described later and the methods described in "Polymer Analysis Handbook" (published by Asakura Shoten, P163~170). 13

[0030] Requirement (b6) In the temperature range of -100°C to 150°C, the melting point measured by differential scanning calorimetry (DSC) is preferably not observed. It is preferable that the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid which is component (B) used in the present invention does not show a melting point measured by differential scanning calorimetry (DSC). ​Here, the fact that the melting point (Tm) is not observed means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. The fact that the heat of fusion (ΔH) is not substantially measured means that no peak is observed in the differential scanning calorimeter (DSC) measurement, or the observed heat of fusion is 1 J / g or less. The melting point (Tm) and heat of fusion (ΔH) of the ethylene·α-olefin polymer were determined by performing differential scanning calorimetry (DSC) measurement, cooling to -100 °C, and then heating to 150 °C at a heating rate of 10 °C / min, and analyzing the DSC curve with reference to JIS K7121.

[0031] <Process for producing an ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid> The ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid, which is the component (B) having the above physical properties, can be produced by various methods. For example, it can be obtained by carrying out a polymerization reaction in the presence of a monomer consisting of an α,β-unsaturated carboxylic acid and its derivative coexisting in the reaction system together with ethylene and an α-olefin. In this case, the polymerization reaction is usually carried out in the presence of a solvent, and the monomer consisting of an α,β-unsaturated carboxylic acid and its derivative is polymerized at a ratio of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on a total of 100 parts by mass of ethylene and an α-olefin having 3 to 20 carbon atoms. Alternatively, it can be obtained by graft copolymerizing a monomer consisting of an α,β-unsaturated carboxylic acid and its derivative with an already obtained ethylene·α-olefin copolymer.

[0032] As the α-olefin constituting the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid as component (B), α-olefins having 3 or more carbon atoms other than ethylene can be mentioned. Typical examples include α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. These α-olefins may be used alone or in combination of two or more. The above ethylene and α-olefin may contain ethylene and α-olefin derived from biomass.

[0033] Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferred, propylene and 1-butene are more preferred, and 1-butene is even more preferred, from the viewpoints that a liquid copolymer can be effectively obtained and a composition having the desired effects of the present invention can be easily obtained.

[0034] The substituent derived from the α,β-unsaturated carboxylic acid in component (B) is formed by incorporating a monomer composed of an α,β-unsaturated carboxylic acid or its derivative into a copolymer composed of ethylene and an α-olefin by copolymerization, graft copolymerization, or the like.

[0035] Examples of the α,β-unsaturated carboxylic acid and its derivative include the following. That is, there are acrylic acid, methacrylic acid, etc., and metal salts such as sodium salts thereof, α,β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, methyl methacrylate, ethyl methacrylate, etc., unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, etc. As the unsaturated dicarboxylic acid derivative, for example, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid; unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride; esters of unsaturated dicarboxylic acids such as dimethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid dimethyl, etc., hydroxyalkyl esters or hydroxyalkoxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, hydroxyethoxy methacrylate, etc. These α,β-unsaturated carboxylic acids and their derivatives may be used alone or in combination of two or more. Among these, as the α,β-unsaturated carboxylic acid and its derivative, maleic acid and maleic anhydride which is its derivative are preferable.

[0036] Component (B) is preferably prepared by graft copolymerizing a monomer composed of an α,β-unsaturated carboxylic acid or its derivative onto an ethylene·α-olefin copolymer. Examples of the graft copolymerization include a method of reacting an ethylene·α-olefin copolymer with a monomer composed of an α,β-unsaturated carboxylic acid or its derivative in the presence of a solvent or without a solvent. In order to efficiently graft copolymerize the monomer composed of the above-mentioned α,β-unsaturated carboxylic acid and its derivative, it is preferable to carry out the graft reaction in the presence of a radical initiator. In this case, the radical initiator is preferably used in a proportion of 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the ethylene·α-olefin copolymer.

[0037] As the radical initiator, organic peroxides, organic peresters, azo compounds, etc. can be used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(peroxide benzoate)-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 perphenylacetate, t-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl perpivalate, cumyl perpivalate, t-butyl perdiethylacetate; azobisisobutyronitrile, dimethyl azoisobutyrate, etc. Among 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, 1,4-bis(t-butylperoxyisopropyl)benzene are preferably used. The reaction temperature of the graft reaction using the radical initiator as described above, or the graft reaction carried out without using a radical initiator, is usually set within the range of 120°C to 350°C.

[0038] The substituent derived from the α,β-unsaturated carboxylic acid in component (B) is preferably a substituent containing a carbonyl group, and its content is preferably 0.01 to 10% by mass, more preferably in the range of 0.1 to 9% by mass, and even more preferably in the range of 0.4 to 8% by mass. When the content is within the above range, good peel strength can be obtained. The content of the substituent derived from the α,β-unsaturated carboxylic acid in component (B) is measured using a nuclear magnetic resonance apparatus with 1,1,2,2-tetrachloroethane-d2 as the solvent, a sample concentration of 20 mg / 0.6 mL, a measurement temperature of 120 °C and room temperature, and 1 H (400 MHz), single pulse as the sequence, pulse width of 6.5 μ / s (45° pulse), repetition time of 7.0 seconds, number of integrations of 512 times, and the peak of CHCl in 1,1,2,2-tetrachloroethane-d2 as the reference value of chemical shift 2 CHCl 2 Based on the 5.91 ppm of the peak, the measurement is obtained from the area ratio of the peak corresponding to the structure (polymer main chain) derived from ethylene·α-olefin and the peak corresponding to the structure derived from α,β-unsaturated carboxylic acid in the 1 1H-NMR spectrum.

[0039] <Trans-Polyoctenylene (C)> The ethylene-based copolymer composition of the present invention preferably contains trans-polyoctenylene (C). When the composition contains trans-polyoctenylene (C), the adhesiveness between the composition and other materials, such as a layer containing a fiber material like an industrial belt, is good, and the laminate obtained from the composition has excellent adhesion strength between the layer formed by cross-linking the composition and the layer containing the fiber 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. By containing trans-polyoctenylene (C), the ethylene-based copolymer composition of the present invention can improve the adhesiveness by improving the compatibility with the fiber material and the adhesion with the fiber material. Incidentally, trans - polyoctenylene (C) is manufactured and sold under the trade name of VESTENAMER by Evonik Industries.

[0040] <Ethylene - based copolymer composition> The ethylene - based copolymer composition of the present invention and the ethylene - based copolymer composition forming layer [I] of the laminate of the present invention are compositions containing ethylene·α - olefin·non - conjugated polyene copolymer (A) as component (A) and ethylene·α - olefin copolymer (B) having a substituent derived from α,β - unsaturated carboxylic acid as component (B). Preferably, per 100 parts by mass of component (A), component (B) is contained in the range of 0.5 to 100 parts by mass, more preferably 1 to 70 parts by mass, still more preferably 2 to 50 parts by mass, particularly preferably 4 to 30 parts by mass, and especially preferably 6 to 15 parts by mass.

[0041] Since the ethylene - based copolymer composition of the present invention contains component (A) and component (B), it has excellent adhesiveness to other materials, for example, a layer containing a fiber material such as an industrial belt. The molded body and the laminate obtained from the composition also have good mechanical properties.

[0042] The ethylene - based copolymer composition of the present invention preferably contains trans - polyoctenylene (C) in addition to the above - mentioned component (A) and component (B). When the ethylene - based copolymer composition of the present invention contains 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, still more preferably 1 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, and especially preferably 1 to 6 parts by mass per 100 parts by mass of component (A). The ethylene - based copolymer composition containing the above - mentioned trans - polyoctenylene (C) has good adhesiveness to other materials, for example, a layer containing a fiber material such as an industrial belt, and the cross - linked laminate has excellent adhesive strength to the layer containing the fiber material.

[0043] In addition to component (A), component (B), and trans - polyoctenylene (C), the ethylene - based copolymer composition of the present invention can be blended with other components within the range that does not impair the effects of the present invention according to the desired purpose. Examples of other components include at least one selected from cross - linking agents, cross - linking aids, vulcanization accelerators, vulcanization aids, fillers, softeners, antioxidants, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. Also, each additive may be used alone or in combination of two or more kinds.

[0044] <Cross - linking agents, cross - linking aids, vulcanization accelerators, and vulcanization aids> Examples of cross - linking agents include cross - linking agents generally used when cross - linking rubber, such as organic peroxides, phenol 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.

[0045] 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 - butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert - butyl cumyl peroxide.

[0046] When an organic peroxide is used as the crosslinking agent, its compounding amount 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 with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A). When the compounding amount of the organic peroxide is within the above range, the ethylene-based copolymer composition exhibits excellent crosslinking properties without bloom on the surface of the obtained molded article, which is preferable.

[0047] When an organic peroxide is used as the crosslinking agent, it is preferable to use a crosslinking aid in combination. Examples of the crosslinking aid include sulfur; quinone dioxime-based crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide-based crosslinking aids; divinylbenzene; metal oxides such as zinc oxide (for example, two types of zinc oxide (JIS standard (K-1410)), zinc oxide manufactured by Hakusuitech Co., Ltd.), magnesium oxide, and activated zinc white (for example, "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.) and other zinc oxides).

[0048] When a crosslinking aid is used, the compounding amount of the crosslinking aid in the ethylene-based copolymer composition is usually 0.5 to 10 moles, preferably 0.5 to 7 moles, and more preferably 1 to 6 moles with respect to 1 mole of the organic peroxide.

[0049] Examples of the sulfur-based compound (vulcanizing agent) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0050] When a sulfur-based compound is used as a crosslinking agent, its compounding amount 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 with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A) which is component (A). When the compounding 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 characteristics.

[0051] When a sulfur-based compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator in combination. Examples of the vulcanization accelerator include thiazole-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (e.g., Sanseler M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio) benzothiazole (e.g., Nocceler MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl) mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio) benzothiazole, and dibenzothiazyl disulfide (e.g., Sanseler DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, and diorthotolylguanidine; aldehydeamine-based vulcanization accelerators such as acetaldehyde aniline condensate and butyraldehyde aniline condensate; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; thiuram-based vulcanization accelerators such as tetramethylthiuram monosulfide (e.g., Sanseler TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (e.g., Sanseler TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (e.g., Sanseler TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutylthiuram disulfide (e.g., Sanseler TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Sanseler TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (e.g., Sanseler PZ, Sanseler BZ, and Sanseler EZ (trade names; manufactured by Sanshin Chemical Industry Co., Ltd.)), and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators such as ethylene thiourea (e.g., Sanseler BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sanseler 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea; and xanthate-based vulcanization accelerators such as zinc dibutylxanthate.

[0052] When using a vulcanization accelerator, the compounding amount of these vulcanization accelerators 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 with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A) which is component (A). When the compounding amount of the vulcanization accelerator is within the above range, the ethylene-based copolymer composition exhibits excellent crosslinking properties without bloom on the surface of the obtained molded article. When using a sulfur-based compound as a crosslinking agent, a vulcanization aid can be used in combination.

[0053] Examples of the vulcanization aid include zinc oxide (for example, two types of zinc oxide, ZnO#1 and zinc oxide manufactured by Hakusuitec Co., Ltd.), magnesium oxide, and activated zinc white (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Sekka Kogyo Co., Ltd.)). When using a vulcanization aid, the compounding amount of the vulcanization aid in the ethylene-based copolymer composition is usually 1 to 20 parts by mass with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A).

[0054] <Filler> The filler constituting the ethylene-based copolymer composition of the present invention is a known rubber reinforcing agent compounded in a rubber composition, and is usually carbon black or an inorganic substance called an inorganic reinforcing agent.

[0055] Specific examples of the filler according to the present invention include Asahi #55G, Asahi #60UG, Asahi #70 (all manufactured by Asahi Carbon Co., Ltd.), carbon black of Seast (V, SO, 116, 3, 6, 9, SP, TA, etc.) (manufactured by Tokai Carbon Co., Ltd.), those obtained by surface-treating these carbon blacks with a silane coupling agent, etc., and silica, activated calcium carbonate, fine powder talc, fine powder silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, etc.

[0056] These fillers may be used alone or as a mixture of two or more. As the filler according to the present invention, preferably, carbon black, silica, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are used.

[0057] When the copolymer composition of the present invention contains a filler, it may be usually blended in the range of 10 to 300 parts by mass, preferably 20 to 100 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A).

[0058] Since the ethylene-based copolymer composition of the present invention contains the component (B), it does not require a softening agent, but the following softening agents may be used in combination. <Softening agent> Examples of the softening agent include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petrolatum, etc.; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil, etc.; waxes such as beeswax, carnauba wax, etc.; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymer substances such as terpene resin, petroleum resin, coumarone-indene resin, etc.; ester-based softening agents such as dioctyl phthalate, dioctyl adipate, etc.; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sulfide (factice). Among these, petroleum-based softening agents are preferred, and process oil is particularly preferred.

[0059] When the ethylene-based copolymer composition contains a softening agent, the blending amount of the softening agent is generally 2 to 100 parts by mass, preferably 3 to 100 parts by mass, more preferably 4 to 40 parts by mass, and still more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A).

[0060] <Antioxidant (Stabilizer)> By blending an antioxidant (stabilizer) into the ethylene-based copolymer composition of the present invention, the lifespan of the seal packing to be formed therefrom can be extended. As such antioxidants, conventionally known antioxidants such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants are available.

[0061] Examples of antioxidants include aromatic secondary amine-based antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenol-based antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether-based antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; sulfur-based antioxidants such as 2-mercaptobenzoyl imidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, and distearyl thiodipropionate; and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0062] When the ethylene-based copolymer composition contains an antioxidant, the blending 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 with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A). When the blending amount of the antioxidant is within the above range, there is no bloom on the surface of the resulting molded article, and furthermore, the occurrence of vulcanization inhibition can be suppressed.

[0063] <Processing Aid> As the processing aid, those generally compounded with rubber as processing aids can be widely used. Specifically, ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, esters, etc. can be mentioned. Among these, stearic acid is preferable.

[0064] When the copolymer composition contains a processing aid, it can be appropriately compounded usually in an amount of 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 compounding amount of the processing aid is within the above range, it is suitable because it is excellent in processability such as kneading processability, extrusion processability, injection moldability, etc. The said processing aid may be a single kind or two or more kinds.

[0065] <Activator> Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, monoethanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; zinc peroxide preparations; cetyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds.

[0066] When the copolymer composition contains an activator, the compounding 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).

[0067] <Laminate> The laminate of the present invention is a laminate in which layer [I] made of the ethylene-based copolymer composition of the present invention and layer [II] containing a fiber material are in contact with each other.

[0068] <Layer [I] made of an ethylene-based copolymer composition> The layer [I] composed of the ethylene-based copolymer composition constituting the laminate of the present invention is preferably a layer formed by crosslinking the ethylene-based copolymer composition.

[0069] <Layer [II] containing a fiber material> The layer [II] containing a fiber material constituting the laminate of the present invention contains a fiber material in at least a part of the layer.

[0070] <Fiber material> The fiber material forming the layer [II] according to the present invention includes various known fiber materials, for example, natural fibers such as cotton and wood cellulose fibers; organic fiber 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 fiber materials such as glass fibers, PAN-based carbon fibers, pitch-based carbon fibers, alumina fibers, silicon carbide fibers, aluminum borate fibers, and potassium titanate whiskers.

[0071] These fiber materials may be long fibers (filaments) or short fibers (staples). Further, the fiber material may be a cord yarn, a spun yarn, a woven fabric, a knitted fabric, a canvas, a non-woven fabric, or the like.

[0072] Examples of the above polyamide include aliphatic polyamides such as nylon 6, nylon 6,6, and nylon 6,10; semi-aromatic polyamides such as polymetaxylylene adipamide (MXD6), polyhexamethylene terephthalamide (6T), or copolymer polyamides containing these units; and wholly aromatic polyamides such as polybenzamide, poly-p-phenylene terephthalamide, and poly-m-phenylene isophthalamide.

[0073] Further, in order to improve the adhesiveness between these fiber materials or between the fiber materials and the layer [I] composed of the above ethylene-based copolymer composition, etc., they may be surface-treated by a known method such as resorcinol-formalin-latex treatment (RFL treatment).

[0074] <RFL treatment> The RFL treatment is to perform an adhesion treatment on the fiber material using a treatment liquid (RFL liquid) containing resorcinol-formalin-latex of the fiber material. This RFL liquid is a mixture of an initial condensate of resorcinol and formalin and a rubber latex. As the rubber latex, 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. can be used. These can be used alone or in combination of two or more.

[0075] <Method for manufacturing a laminate> To manufacture the laminate of the present invention, various known laminate manufacturing methods can be adopted. For example, after laminating a layer [I] composed of an uncrosslinked ethylene-based copolymer composition manufactured (formed) by a known method in advance and a layer [II] containing a fiber material, a method of crosslinking the layer [I] composed of the ethylene-based copolymer composition, a method of laminating a layer [I] composed of a crosslinked ethylene-based copolymer composition and a layer [II] containing a fiber material, or a method of extruding and coating a layer [I] composed of the ethylene-based copolymer composition on the layer [II] containing the fiber material and then crosslinking the layer [I] composed of the ethylene-based copolymer composition. For the layer [I] composed of the above ethylene-based copolymer composition, various known manufacturing methods can be adopted.

[0076] The above ethylene-based copolymer composition can be obtained by kneading component (A) and component (B), and optionally transpolyoctenylene (C), and further additives such as fillers, antioxidants, and processing aids, using various well-known kneading and mixing apparatuses, for example, internal mixers (sealed mixers) such as Banbury mixers, kneaders, and intermixers, rolls, and the like.

[0077] The uncrosslinked ethylene-based copolymer composition obtained by kneading can be shaped into a desired shape by various molding methods such as an extruder, calender roll, press, injection molding machine, and transfer molding machine, and then crosslinked to form layer [I] made of the ethylene-based copolymer composition, and laminated (bonded) with layer [II] containing a fiber material. Alternatively, the uncrosslinked ethylene-based copolymer composition can be shaped into a desired shape by the above method and then laminated (bonded) with layer [II] containing a fiber material and crosslinked.

[0078] As a method for crosslinking layer [I] made of the ethylene-based copolymer composition, either a method of heating using a crosslinking agent or a method by irradiation with light, γ-rays, or electron beams may be employed.

[0079] Also, when crosslinking, a mold may be used, or crosslinking may be carried out without using a mold. When not using a mold, the molding and crosslinking steps are usually carried out continuously. As a heating method in a crosslinking tank, heating tanks such as hot air, glass bead fluidized bed, UHF (extremely high frequency electromagnetic wave), and steam can be used.

[0080] <Applications of the laminate> A laminate in which layer [I] made of the ethylene-based copolymer composition of the present invention is in contact with layer [II] containing a fiber material is suitably used for automotive hoses, water supply hoses, gas hoses; industrial belts such as transmission belts and conveyor belts; and escalator handrails.

[0081] Examples of the above automotive hoses include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the above transmission belt include, for example, V-belts, flat belts, toothed belts, etc. Examples of the above conveyor belt include, for example, light conveyor belts, cylindrical belts, raftop belts, conveyor belts with flanges, conveyor belts with U-shaped guides, conveyor belts with V-shaped guides, etc.

Example

[0082] Next, examples of the present invention will be shown and described in more detail, but the present invention is not limited thereto. The ethylene·α-olefin·non-conjugated polyene copolymer (A) used in the examples and comparative examples is the following copolymer (A-1) and copolymer (A-2). Copolymer (A-1) [Ethylene·α-olefin·non-conjugated polyene copolymer] According to the description of [Synthesis Example C1] in International Publication No. 2015 / 122415, an ethylene·1-butene·5-ethylidene-2-norbornene (ENB) copolymer having the following physical properties was obtained. 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.

[0083] Corresponding requirements Item Copolymer (A-1) Copolymer (A-2) Structural unit derived from ethylene: 69.1 mol% 57.4 mol% Structural unit derived from 1-butene: 27.8 mol% - Structural unit derived from propylene: - 40.3 mol% Requirement (a1) molar ratio: 70 / 30 58.7 / 41.3 (structural unit derived from ethylene / structural unit derived from α-olefin) Requirement (a2) content ratio of structural unit derived from ENB : 2.2 mol% 2.3 mol%​ Mooney viscosity ML (1 + 4) 100 °C: 30 - 45 Requirement (a3) Mooney viscosity ML (1 + 4) 125 °C: 22 - Requirement (a4) B value: 1.3 -

[0084] The production methods of copolymer (B-1) and copolymer (B-2), which are ethylene·α-olefin copolymers (B) having substituents derived from α,β-unsaturated carboxylic acids used in the examples and comparative examples, are shown below.

[0085] [Production Example 1] 760 mL of heptane and 120 g of propylene were charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen. After raising the temperature inside the system to 150 °C, the total pressure was set to 3 MPaG by supplying 0.85 MPa of hydrogen and 0.19 MPa of ethylene. Next, 0.4 mmol of triisobutylaluminum, 0.0002 mmol of [methylphenylmethylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, and 0.002 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were pressured in with nitrogen, and polymerization was initiated by setting the stirring rotation speed to 400 rpm. Thereafter, the total pressure was maintained at 3 MPaG by continuously supplying only ethylene, and polymerization was carried out at 150 °C for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymerization solution was washed 3 times with 1000 mL of 0.2 mol / L hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and dried at 80 °C under reduced pressure overnight to obtain a crude ethylene·propylene copolymer.

[0086] A 1-L stainless steel autoclave was charged with 100 mL of a hexane solution of a 0.5 mass% Pd / alumina catalyst and 500 mL of a 30 mass% hexane solution of the obtained crude ethylene-propylene copolymer. After sealing the autoclave, nitrogen substitution was carried out. Subsequently, the temperature was raised to 140 °C with stirring, the system was purged with hydrogen, and then the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes to obtain an ethylene-propylene copolymer.

[0087] Subsequently, 100 g of the obtained ethylene-propylene copolymer was charged into a 200-mL glass reactor equipped with a stirrer equipped with a nitrogen blowing tube, a water-cooled condenser, a thermometer, and two dropping funnels. After raising the temperature, nitrogen bubbling was started at 120 °C, and the system was kept at 160 °C. Then, 6.6 g of maleic anhydride (heated to a liquid state at around 70 °C) and 1.3 g of di-tert-butyl peroxide, which had been previously charged into the two dropping funnels, were supplied over 5 hours, and the reaction was carried out for 1 hour after the supply was completed. Next, the temperature was further raised to 175 °C, the pressure in the system was reduced, and then nitrogen was gradually introduced with a vacuum pump while reducing the pressure for 1 hour to remove impurities (unreacted maleic anhydride and decomposition products of di-tert-butyl peroxide). By the above operations, a modified ethylene-propylene copolymer (B-1) was obtained. The 150 °C BF viscosity of the obtained ethylene-propylene copolymer (B-1) was 70 mPa·s, the content of substituents derived from maleic anhydride was 5 mass%, the ethylene content was 49 mol%, the melting point (melting peak) was not observed, Mw was 5600 g / mol, and the acid value was 60 mgKOH / g.

[0088] [Production Example 2] 1 L of dehydrated and purified hexane was placed in a 2-L continuous polymerization reactor equipped with a stirring blade that had been sufficiently purged with nitrogen. Thereto, a hexane solution of ethylaluminum sesquichloride (Al(C 2 H 5 ) 1.5 ·C 11.5 ) adjusted to 96 mmol / L was continuously supplied at a rate of 500 mL / h for 1 hour. Then, as a catalyst, VO(OC 2 H 5 )Cl adjusted to 16 mmol / L2 A hexane solution was continuously supplied at a rate of 500 mL / h, and hexane was continuously supplied at a rate of 500 mL / h. On the other hand, from the upper part of the reactor, the polymerization solution in the reactor was continuously withdrawn so that the volume of the polymerization solution always became 1 L.

[0089] Next, using a bubbling tube, ethylene gas was supplied at a rate of 36 L / h, propylene gas was supplied at a rate of 36 L / h, and hydrogen gas was supplied at a rate of 30 L / h. The copolymerization reaction was carried out at 35 °C by circulating a refrigerant through a jacket attached outside the reactor. As a result, a polymerization solution containing an ethylene-propylene copolymer was obtained.

[0090] The obtained polymerization solution was washed three times with 500 mL of 0.2 mol / L hydrochloric acid per 1 L of the polymerization solution, and then washed three times with 500 mL of distilled water per 1 L of the polymerization solution. After drying with magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained viscous liquid was dried at 130 °C under reduced pressure for 24 hours to obtain an ethylene-propylene copolymer.

[0091] Subsequently, 100 g of the copolymer was charged into a 200 mL glass reactor equipped with a stirrer equipped with a nitrogen blowing tube, a water-cooled condenser, a thermometer, and two dropping funnels. After raising the temperature, nitrogen bubbling was started at 120 °C, and the temperature inside the system was maintained at 160 °C. Then, 2.8 g of maleic anhydride (heated to a liquid state at around 70 °C) and 0.6 g of di-tert-butyl peroxide, which had been previously charged into the two dropping funnels respectively, were supplied over 2 hours, and the reaction was carried out for 1 hour after the supply was completed. Next, the temperature was further raised to 175 °C, the pressure inside the system was reduced, and then nitrogen was gradually introduced with a vacuum pump while reducing the pressure for 1 hour to remove impurities (undecomposed maleic anhydride and decomposition products of di-tert-butyl peroxide). By the above operations, a modified ethylene-propylene copolymer (B-2) was obtained. The 150 °C BF viscosity of the obtained ethylene-propylene copolymer (B-2) was 160 mPa / s, the content of substituents derived from maleic anhydride was 2% by mass, the ethylene content was 53 mol%, the melting point (melting peak) was not observed, Mw was 10300 g / mol, and the acid value was 25 mgKOH / g.

[0092] Corresponding requirements Item Copolymer (B-1) Copolymer (B-2) Structural unit derived from ethylene: 49 mol% - 53 mol% Structural unit derived from propylene: 51 mol% - 47 mol% Acid value: 60 mgKOH / g - 25 mgKOH / g Requirement (b1) BF viscosity (150 °C): 70 mPa·s - 160 mPa·s Requirement (b2) Mw by GPC: 5,600 - 10,300

[0093] The physical properties of copolymer (A-1) and copolymer (A-2) were determined by the following method. Molar amounts of structural units derived from ethylene, structural units derived from α-olefin, and structural units derived from non-conjugated polyene These molar amounts were 1 determined by measuring the intensity with an H-NMR spectrometer. Details of the measurement conditions are described in International Publication No. 2015 / 122415.

[0094] Mooney viscosity Mooney viscosity (ML(1+4) 100 °C) and Mooney viscosity (ML(1+4) 125 °C ) were measured in accordance with JIS K6300 (1994) using a Mooney viscometer (Model SMV202 manufactured by Shimadzu Corporation).

[0095] B value o-dichlorobenzene-d 4 / benzene-d 6 (4 / 1 [v / v]) was used as the measurement solvent, and the measurement was carried out at a measurement temperature of 120 °C, 13 a 13C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured and calculated based on the following formula (i). B value = ([EX] + 2[Y]) / {2 × [E] × ([X] + [Y])} ··· (i) [Here, [E], [X], and [Y] respectively represent the 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-olefin [A2] having 4 to 20 carbon atoms diad chain fraction.]

[0096] Also, the physical properties of the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid were determined by the following method.

[0097] Brookfield viscosity (150 °C) The Brookfield (BF) viscosity (mPa·s) at 150°C was measured by the method described in JIS K7117-1.

[0098] Content of substituent derived from maleic anhydride The content of the substituent derived from maleic anhydride in the ethylene·α-olefin copolymer (B) was measured using a JEOL Ltd. ECX400P nuclear magnetic resonance apparatus, with 1,1,2,2-tetrachloroethane-d2 as the solvent, a sample concentration of 20 mg / 0.6 mL, measurement temperatures of 120°C and room temperature, 1H (400 MHz) as the observed nucleus, a single pulse as the sequence, a pulse width of 6.5 μ / s (45° pulse), a repetition time of 7.0 seconds, an integration number of 512 times, and using the peak at 5.91 ppm based on CHCl 2 CHCl 2 in 1,1,2,2-tetrachloroethane-d2. The content of the substituent derived from maleic anhydride in the ethylene·α-olefin copolymer (B) was calculated from the area ratio of the peak corresponding to the structure (polymer main chain) derived from ethylene·α-olefin and the peak corresponding to the structure derived from maleic anhydride in the 1 1H-NMR spectrum measured as described above.

[0099] Weight average molecular weight (Mw) The molecular weight (Mw) of the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid was determined by the following high-speed GPC measuring apparatus. High-speed GPC measuring apparatus: HLC8320GPC manufactured by Tosoh Corporation Mobile phase: THF (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free, liquid chromatography grade) Column: Two TSKgel Super Multipore HZ-M manufactured by Tosoh Corporation Connected in series Sample concentration: 5 mg / mL Mobile phase flow rate: 0.35 mL / min Measurement temperature: 40 °C Standard sample for calibration curve: PStQuick MP-M manufactured by Tosoh Corporation

[0100] Ethylene content (mol%) The ethylene content of the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid was measured using a JNM-ECP500 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., with an ortho-dichlorobenzene / heavy benzene (80 / 20% by volume) mixed solvent as the solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120 °C, 13C (125 MHz) as the observed nucleus, a single-pulse proton decoupling as the sequence, a pulse width of 4.7 μ / s (45° pulse), a repetition time of 5.5 seconds, an integration number of 10,000 or more, and 27.50 ppm as the reference value of the chemical shift. The ethylene content of the ethylene·α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid was measured as described above. 13 From the C-NMR spectrum, it was determined based on the reports of "Polymer Analysis Handbook" (published by Asakura Shoten, P163 - 170), G.J. Ray (Macromolecules, 10, 773 (1977)), J.C. Randall (Macromolecules, 15, 353 (1982)), K. Kimura (Polymer, 25, 4418 (1984)), etc.

[0101] [Modified polybutadiene] As the modified polybutadiene, maleic anhydride-modified polybutadiene (N-1) of Ricon131MA17 [trade name, Cray Valley] was used.

[0102] [Transpoly(octenylene)] As the transpoly(octenylene), VESTENAMER 8012 with the trade name of Evonik Industries was used.

[0103] The method for obtaining the physical properties of the ethylene-based copolymer composition (non-crosslinked product) is as follows.

[0104] Measurement of adhesiveness Using a probe tack tester, the tackiness = Peak Value (gf) was evaluated under the following conditions. Using an uncrosslinked sheet with a thickness of 1 mm, the measurement was carried out under the following conditions. Stainless steel probe with a diameter of 5 mm φ Entry speed: 120 mm / min. Pressing force: 100 g Pressing time: 20 sec. Pull-off speed: 120 mm / min. Temperature for placing the probe and the test piece (uncrosslinked sheet): 50 °C.

[0105] The method for obtaining the physical properties of the crosslinked ethylene-based copolymer composition is as follows.

[0106] Durometer A hardness In accordance with JIS K 6253, the measurement of the hardness of the sheet (Type A durometer, HA) was carried out using six sheet-shaped crosslinked products with a smooth surface and a thickness of 2 mm. The flat parts were stacked to a thickness of about 12 mm. However, those with foreign matter mixed in the test piece, those with air bubbles, and those with scratches were not used. Also, the dimensions of the measurement surface of the test piece were set to a size such that the tip of the pressing needle could be measured at a position more than 12 mm away from the edge of the test piece.

[0107] Tensile break point stress (TB), tensile break point elongation (EB) The tensile break point stress and the tensile break point elongation of the sheet were measured by the following method. The sheet was punched out to prepare dumbbell test pieces of No. 3 shape described in JIS K 6251 (1993). Using these test pieces, a tensile test was conducted in accordance with the method specified in Paragraph 3 of JIS K6251 under the conditions of a measurement temperature of 25°C and a tensile speed of 500 mm / min. to measure the tensile break point stress (TB) and the tensile break point elongation (EB).

[0108] Peel strength The peel strength (adhesion strength) between layer [I] made of a crosslinked ethylene copolymer composition and layer [II] containing a fiber material was measured by the following method.

[0109] An uncrosslinked sheet with a thickness of 3 mm was placed on a woven fabric of nylon fiber (manufactured by Ayaba Kogyo Co., Ltd.) that had been subjected to RFL treatment, and pressure was applied at 170°C for 15 minutes using a 200-ton press molding machine to crosslink the uncrosslinked sheet and obtain a laminate. A test piece with a width of 25 mm was punched out from the laminate, and a T-peel test was conducted at a tensile speed of 50 mm / min. to determine the peel strength (adhesion strength) (N / cm). The peel test was conducted three times, and the average value was taken as the peel strength.

[0110] 〔Example 1〕 The copolymer (A-1) was kneaded for 30 seconds. To 100 parts by weight of the kneaded copolymer (A-1), 5 parts by mass of zinc oxide (ZnO#1) as a crosslinking aid, 1 part by weight of stearic acid as a lubricant, tetrakis[methylene(3,5- di-t-butyl-4-hydroxy)hydrocinnamate] methane [trade name Irganox 1010 BASFF manufactured by BASF Japan Ltd.] 4 parts by mass, 2-mercaptobenzimidazole (trade name Sandant MB manufactured by Sanshin Chemical Industry Co., Ltd.) 8 parts by mass, carbon black [manufactured by Asahi Carbon Co., Ltd., trade name Asahi #70] 40 parts by mass, silica [manufactured by Evonik, trade name ULTRASIL VN2] 10 parts by mass, softening agent [trade name Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd.] 10 parts by mass, and as transpoly(octenylene)(M), Evonik (Evonik Industries) trade name: VESTENAMER 8012 5 parts by mass were kneaded for 2 minutes in a Banbury mixer [(manufactured by Kobe Steel, Ltd.) with a capacity of 1.7 liters]. Then, the ram was raised for cleaning, and further kneading was carried out for 1 minute, and discharged at about 150 °C to obtain a formulation (formulation-1). This kneading was carried out at a filling rate of 70%.

[0111] Next, 172 parts by weight of this formulation (formulation-1) was wound around an 8-inch roll (the surface temperature of the front roll was 50 °C, the surface temperature of the rear roll was 50 °C, the rotational speed of the front roll was 16 rpm, and the rotational speed of the rear roll was 18 rpm). After adding 8 parts by mass of component (B-1) and 6.8 parts by weight of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP-40C) as a cross-linking agent and kneading for 10 minutes to obtain a formulation (formulation-2), they were separated into sheet shapes according to the test pieces, and uncrosslinked sheets with thicknesses of 1 mm, 2 mm, and 3 mm were prepared.

[0112] Using the obtained uncrosslinked sheet with a thickness of 1 mm, the adhesiveness (gf) was measured by the method described above. The results are shown in Table 1. Also, the obtained uncrosslinked sheet with a thickness of 2 mm was pressed at 170 °C for 15 minutes using a 100-ton press molding machine to produce a crosslinked sheet. The physical properties of the obtained crosslinked sheet were measured by the method described above. The results are shown in Table 1.

[0113] [Example 2] Regarding component (A-1) and component (B-2) of Example 2 shown in Table 1, uncrosslinked sheets and crosslinked sheets were produced in the same manner as in Example 1. The physical properties of the obtained crosslinked sheet were measured in the same manner as in Example 1.

[0114] 〔Comparative Examples 1 to 4〕 In the case where neither the copolymer (B-1) nor the copolymer (B-2) was used, an uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1 except that the composition shown in Table 2 was used, and the physical properties and the like were evaluated by the same method. However, in Comparative Example 3, instead of dicumyl peroxide, the compound shown in Table 3 was added and vulcanization with sulfur was carried out. The evaluation results are shown in Table 2. The compounds used in the examples and comparative examples are shown in Table 1.

[0115]

Table 1

[0116]

Table 2

[0117]

Table 3

Claims

1. A composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A) as component (A) and an ethylene-α-olefin copolymer (B) having a substituent derived from an α,β-unsaturated carboxylic acid as component (B), wherein component (A) and component (B) are defined as follows, an ethylene-based copolymer composition. Component (A): Satisfies the following requirements (a1) to (a4). Requirement (a1): It 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 of the structural unit derived from ethylene [L] to the structural unit derived from an α-olefin [M] having 4 to 20 carbon atoms, [L] / [M], is 40 / 60 to 90 / 10. Requirement (a2): The content of the structural unit derived from the non-conjugated polyene [N] is 0.1 to 6.0 mol% (however, the total of the structural units derived from [L], [M], and [N] is 100 mol%). Requirement (a3): The 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) (However, [E], [X], and [Y] represent the molar fractions of ethylene [L], an α-olefin [M] having 4 to 20 carbon atoms, and a non-conjugated polyene [N], respectively, and [EX] represents the dyad chain fraction of ethylene [L] - an α-olefin [M] having 4 to 20 carbon atoms.) Component (B): Satisfies the following requirements (b1) to (b2). Requirement (b1): The Brookfield viscosity (150°C) is 1 to 5,000 mPa·s. Requirement (b2): The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 1,000 to 100,000.

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

3. The ethylene-based copolymer composition according to claim 1, wherein the α,β-unsaturated carboxylic acid of component (B) is maleic acid.

4. The ethylene-based copolymer composition according to claim 1, wherein the acid value of component (B) is 1 to 100 mgKOH / g.

5. The ethylene-based copolymer composition according to claim 1, comprising 0.5 to 100 parts by mass of component (B) per 100 parts by mass of component (A).

6. The ethylene-based copolymer composition according to claim 1, comprising trans-polyoctenylene (C).

7. The ethylene-based copolymer composition according to claim 6, comprising 0.5 to 50 parts by mass of trans-polyoctenylene (C) per 100 parts by mass of component (A).

8. A laminate, characterized in that a layer [I] composed of the ethylene-based copolymer composition according to any one of claims 1 to 7 is in contact with a layer [II] containing a fiber material.

9. The laminate according to claim 8, wherein the ethylene-based copolymer composition is crosslinked.

10. The laminate according to claim 8, wherein the fiber material of the layer [II] is canvas.

11. An industrial belt comprising the laminate according to claim 8.

Images