Ethylene-based copolymer composition, laminate, and industrial belt

Abstract

To provide an ethylene-based copolymer composition that exhibits excellent adhesion strength (peel strength) to other materials, for example, layers containing fibrous materials, and can maintain mechanical properties such as abrasion resistance when formed into a laminate, as well as a laminate.SOLUTION: There is provided an ethylene-based copolymer composition comprising: an ethylene-propylene-nonconjugated polyene copolymer (L) that comprises constitutional units derived from ethylene, constitutional units derived from propylene, and constitutional units derived from nonconjugated polyenes in specific proportions, satisfies a specific relationship among weight-average molecular weight (Mw) of the ethylene-propylene-nonconjugated polyene copolymer; mass fraction of the constitutional units derived from the nonconjugated polyene (C); and the molecular weight of the nonconjugated polyene (C), and satisfies a specific relationship among a ratio P (η*(ω=0.1) / η*(ω=100)) between a complex viscosity η*(ω=0.1) (Pa sec) at a frequency ω=0.1 rad / s and a complex viscosity η*(ω=100) (Pa sec) at a frequency ω=100 rad / s, obtained by linear viscoelasticity measurement (190°C) using a rheometer; an intrinsic viscosity [η]; and a mass fraction of a constitutional unit derived from a non-conjugated polyene (C); as well as trans-polyoctenylene (M); and a crosslinking agent (K) having two or more ethylenically double bonds.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

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

[0005] Furthermore, in order to improve compression set resistance, it has been proposed to compound a sulfur-vulcanized ethylene propylene rubber compound in which zinc oxide is compounded with ethylene-α-olefin-diene copolymer and trans-polyoctenylene rubber (Patent Document 2). [Prior art documents] [Patent documents]

[0006] [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]

[0007] One application of ethylene-α-olefin-non-conjugated polyene copolymers is industrial belts, which are often used in the form of laminates containing a layer containing ethylene-α-olefin-non-conjugated polyene copolymer and a layer containing a fibrous material, with these layers in direct contact with each other, and these layers are required to be resistant to peeling and have excellent abrasion resistance.

[0008] Therefore, an object of the present invention is to provide an ethylene copolymer composition and a laminate which have excellent adhesive strength (peel strength) with other materials, for example, layers containing fibrous materials, and which can maintain mechanical properties such as abrasion resistance when formed into a laminate. [Means for solving the problem]

[0009] As a result of investigations aimed at solving the above problems, the present inventors discovered that the above problems could be solved by adding trans-polyoctenylene to an ethylene-propylene-non-conjugated polyene copolymer, and thus completed the present invention.

[0010] The present invention relates to the following [1] to [9]. [1] An ethylene copolymer composition comprising the following components (1) to (3): Component (1): an ethylene-propylene-non-conjugated polyene copolymer (L) that satisfies the following requirements (i) to (iv); Component (2): trans polyoctenylene (M); Component (3): A crosslinking coagent (K) having two or more ethylenic double bonds. (i) The molar ratio of structural units derived from ethylene to structural units derived from propylene is 40 / 60 to 99.9 / 0.1. (ii) The mass fraction of the constitutional units derived from the non-conjugated polyene (C) is 0.07 mass % to 10 mass % in 100 mass % of the ethylene-propylene-non-conjugated polyene copolymer. (iii) The weight average molecular weight (Mw) of the ethylene-propylene-non-conjugated polyene copolymer, the mass fraction of the constituent unit derived from the non-conjugated polyene (C) (mass fraction (mass%) of (C)), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (1): 4.5≦Mw×(C) mass fraction / 100 / (C) molecular weight≦80 … Equation (1) (iv) Complex viscosity η at frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190 °C) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / s * (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η], and the mass fraction of the structural unit derived from the non-conjugated polyene (C) (mass fraction of (C)) satisfy the following formula (2): P / ([η] 2.9 )≦(C) mass fraction × 6 … Equation (2) [2] The ethylene copolymer composition according to [1], wherein the non-conjugated polyene constituting the ethylene-propylene-non-conjugated polyene copolymer (L) contains 5-vinyl-2-norbornene (VNB). [3] The ethylene copolymer composition according to [1] or [2], wherein the cross-linking coagent (K) having two or more ethylenic double bonds contains ethylene glycol dimethacrylate. [4] The ethylene-based copolymer composition according to any one of [1] to [3], characterized in that it further contains an organic peroxide as a crosslinking agent. [5] A laminate, characterized in that a layer [I] composed of the ethylene-based copolymer composition according to any one of [1] to [4] is in contact with a layer [II] containing a fiber material. [6] The laminate according to [5], wherein the ethylene-based copolymer composition is crosslinked. [7] The laminate according to [5] or [6], wherein the fiber material of the layer [II] contains fibers treated with resorcinol formaldehyde latex (RFL treatment). [8] The laminate according to any one of [5] to [7], wherein the fiber material of the layer [II] is canvas. [9] An industrial belt having the laminate according to any one of [5] to [8]. [Advantages of the Invention]

[0011] The ethylene-based copolymer composition of the present invention is excellent in the adhesive strength (peel strength) with other materials, for example, a layer containing a fiber material, and also excellent in wear resistance, and thus is suitable as a laminate such as an industrial belt. [Embodiments for Carrying Out the Invention]

[0012] Hereinafter, the present invention will be described in more detail. Here, in this specification, "~" indicating a numerical range means a numerical range including the lower limit value and the upper limit value unless otherwise specified. For example, when expressed as "M~N" (where M and N are numerical values satisfying M < N), it means "M or more and N or less" unless otherwise specified.

[0013] Furthermore, in this specification, "structural unit derived from ethylene" means a structural unit corresponding to ethylene, i.e., a structural unit represented by -CH2-CH2-. A "structural unit derived from propylene" is interpreted similarly and means a structural unit corresponding to propylene, i.e., a structural unit represented by -CH2-CH(-CH3)-. Furthermore, a "structural unit derived from non-conjugated polyene" means a structural unit corresponding to a non-conjugated polyene, i.e., a structural unit having one or more pairs of bonds formed by cleavage of the π bond that constitutes one or more of the double bonds possessed by the non-conjugated polyene.

[0014] [Ethylene-based copolymer composition] The ethylene copolymer composition according to the present invention (hereinafter sometimes abbreviated as "copolymer composition") contains the following components (1) to (3): Component (1): Ethylene-propylene-non-conjugated polyene copolymer (L); Component (2): trans polyoctenylene (M); Component (3): Crosslinking aid (K).

[0015] Ethylene-propylene-non-conjugated polyene copolymer (L) The ethylene-propylene-non-conjugated polyene copolymer (L) (hereinafter sometimes abbreviated as "copolymer (L)"), which is component (1) contained in the ethylenic copolymer composition of the present invention, is a copolymer having structural units derived from ethylene, propylene, and a non-conjugated polyene (C), and satisfies the following requirements (i) to (iv): (i) The molar ratio of structural units derived from ethylene to structural units derived from propylene is 40 / 60 to 99.9 / 0.1. (ii) The mass fraction of the structural units derived from the non-conjugated polyene (C) is 0.07 mass % to 10 mass % in 100 mass % of the copolymer (L). (iii) The weight average molecular weight (Mw) of the copolymer (L), the mass fraction of the structural unit derived from the non-conjugated polyene (C) (mass fraction (mass%) of (C)), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (1): 4.5≦Mw×(C) mass fraction / 100 / (C) molecular weight≦80 … Equation (1) (iv) Complex viscosity η at frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190 °C) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / s * (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η], and the mass fraction of the structural unit derived from the non-conjugated polyene (C) (mass fraction of (C)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass fraction × 6 … Equation (2)

[0016] The non-conjugated polyene (C) constituting the copolymer (L) used in the present invention is 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethylethyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, and the like.

[0017] The non-conjugated polyene (C) preferably contains 5-vinyl-2-norbornene (VNB). That is, in one preferred embodiment of the present invention, the copolymer (L) used in the present invention contains a structural unit derived from 5-vinyl-2-norbornene (VNB) as a structural unit derived from the non-conjugated polyene (C). The copolymer (L) containing 5-vinyl-2-norbornene tends to have a faster crosslinking rate.

[0018] The non-conjugated polyene (C) may be one type alone or a combination of two or more types. The non-conjugated polyene (C) is more preferably composed solely of structural units derived from 5-vinyl-2-norbornene.

[0019] The ethylene, propylene and non-conjugated polyene (C) constituting the copolymer (L) may each be derived from biomass or from chemical recycling.

[0020] Examples of the copolymer (L) include ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-1-octene-1,4-hexadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, and ethylene-propylene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer. One or more types of copolymer (L) may be used as required. The copolymer (L) used in the present invention satisfies the following requirements (i) to (iv).

[0021] <Requirement (i)> Requirement (i) specifies that the molar ratio of ethylene-derived structural units to propylene-derived structural units in the copolymer (L) used in the present invention satisfies 40 / 60 to 99.9 / 0.1, and this molar ratio preferably satisfies 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, even more preferably 60 / 40 to 80 / 20, and particularly preferably 65 / 35 to 75 / 25. Such a copolymer (L) is preferred because the molded article obtained by crosslinking exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility. The ethylene content (content of structural units derived from ethylene) and the propylene content (content of structural units derived from propylene) in the copolymer (L) are 13 It can be determined by C-NMR.

[0022] <Requirement (ii)> Requirement (ii) specifies that in the copolymer (L) used in the present invention, the mass fraction of the structural units derived from the non-conjugated polyene (C) is in the range of 0.07 to 10 mass% based on 100 mass% of the copolymer (L) (i.e., based on 100 mass% of the total mass fractions of all structural units). The mass fraction of the structural units derived from the non-conjugated polyene (C) is preferably 0.1 to 8.0 mass%, more preferably 0.3 to 5.0 mass%, even more preferably 0.5 to 3.0 mass%, and particularly preferably 1.0 to 2.0 mass%.

[0023] If the copolymer (L) used in the present invention satisfies the requirement (ii), the molded article obtained from the ethylene copolymer composition of the present invention will have sufficient hardness and excellent mechanical properties, which is preferable, and when crosslinked, will exhibit a high crosslinking rate, which is preferable. The amount of non-conjugated polyene (C) in the copolymer (L) (the content of constituent units derived from non-conjugated polyene (C)) is 13 It can be determined by C-NMR.

[0024] <Requirement (iii)> Requirement (iii) specifies that in the copolymer (L) used in the present invention, the weight average molecular weight (Mw) of the copolymer (L), the mass fraction of the constituent units derived from the non-conjugated polyene (C) in the copolymer (mass fraction of (C): mass %), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following relational formula (1): 4.5≦Mw×(C) mass fraction / 100 / (C) molecular weight≦80 Equation (1)

[0025] When the copolymer (L) used in the present invention satisfies the requirement (iii), the content of the constituent units derived from the non-conjugated polyene (C) such as VNB is appropriate, and the copolymer (L) exhibits sufficient crosslinking performance. In addition, when a molded article is produced using the ethylene copolymer composition of the present invention, the crosslinking rate is excellent and the molded article after crosslinking exhibits excellent mechanical properties, which is preferable.

[0026] It is more preferable that the copolymer (L) used in the present invention satisfies the following relational formula (1'). 4.5≦Mw×(C) mass fraction / 100 / (C) molecular weight≦75 Equation (1') The weight average molecular weight (Mw) of the copolymer (L) means a value measured by 3D-GPC.

[0027] The copolymer (L) used in the present invention has an appropriate degree of crosslinking when the "mass fraction of Mw × (C) / 100 / molecular weight of (C)" satisfies the above formula (1) or (1'), and its use allows the production of molded articles with a good balance of mechanical properties and heat aging resistance. If the "mass fraction of Mw × (C) / 100 / molecular weight of (C)" is too low, the crosslinking may be insufficient and the crosslinking rate may be slow. Conversely, if it is too high, excessive crosslinking may occur, resulting in poor mechanical properties of the resulting molded article.

[0028] Here, when the copolymer (L) is a combination of two or more types, these copolymers (L) may all satisfy both of the formulas (1) and (1'), or may consist of a first copolymer (L1) that satisfies both of the formulas (1) and (1') and a second copolymer (L2) that satisfies the formula (1) but not the formula (1').

[0029] <Requirement (iv)> Requirement (iv) is the complex viscosity η of the copolymer (L) used in the present invention at a frequency ω=0.1 rad / s, which is obtained by linear viscoelasticity measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / s * (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η], and the mass fraction of the structural unit derived from the non-conjugated polyene (C) (mass fraction of (C): mass%) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass fraction × 6 Equation (2)

[0030] Here, the complex viscosity η at frequency ω=0.1 rad / s * (ω=0.1) and the complex viscosity η at frequency ω=100rad / s * (ω=100) The ratio P(η * (ω=0.1) / η * (ω=100) ) represents the frequency dependence of viscosity, and is the left side of equation (2), P / ([η] 2.9) tends to show a high value when there is a lot of long-chain branching, although it is affected by factors such as short-chain branching and molecular weight. Generally, in an ethylene-propylene-non-conjugated polyene copolymer, the more structural units derived from non-conjugated polyenes it contains, the more long-chain branching it tends to have. However, the copolymer (L) used in the present invention has less long-chain branching than conventionally known ethylene-propylene-non-conjugated polyene copolymers, and is therefore thought to be able to satisfy the above formula (2). In the present invention, the P value is determined by calculating the ratio (η) of the complex viscosity at 0.1 rad / s and the complex viscosity at 100 rad / s, which are measured using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) under conditions of 190°C, 1.0% strain, and various frequencies. * The ratio was calculated.

[0031] The copolymer (L) used in the present invention preferably satisfies the following formula (2'). P / ([η] 2.9 ) ≦ (C) mass fraction × 5.7 Equation (2') The intrinsic viscosity [η] means the value measured in decalin at 135°C.

[0032] Other requirements The copolymer (L) used in the present invention may further satisfy the following requirement (v) in addition to the above requirements (i) to (iv).

[0033] Requirement(v) Requirement (v) is the number of long chain branches (LCB) per 1,000 carbon atoms of the copolymer (L) obtained by 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3). LCB 1000C ≦1-0.07×Ln(Mw) Equation (3) The upper limit of the content of long chain branches per unit carbon number of the copolymer (L) is determined by the above formula (3).

[0034] Such a copolymer (L) is preferred because it contains a small proportion of long chain branches, has excellent curing properties when crosslinked, and produces molded articles that are excellent in heat aging resistance.

[0035] The copolymer (L) used in the present invention preferably satisfies the following formula (3'). LCB 1000C ≦1-0.071×Ln(Mw)...Equation (3') Here, Mw and the number of long chain branches (LCB) per 1000 carbon atoms 1000C ) can be determined by a structural analysis method using 3D-GPC. In this specification, it was specifically determined as follows.

[0036] The absolute molecular weight distribution was determined using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was simultaneously determined using a viscometer. The main measurement conditions were as follows: Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Bridge-type viscometer PL-BV400 (Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT x 2 + TSKgel GMH HR -M(S)×1 piece (Each piece has an inner diameter of 7.8mm and a length of 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: ca 1.5mg / mL Sample filtration: Filtration through a sintered filter with a pore size of 1.0 μm The dn / dc value (differential value of refractive index n with respect to concentration c) required to determine the absolute molecular weight was determined for each sample from the dn / dc value of standard polystyrene (molecular weight 190,000) of 0.053 and the response intensity of the differential refractometer per unit injected mass. The long chain branching parameter g'i for each eluted component was calculated from the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer using equation (v-1).

[0037]

number

[0038] where [η]=KM v The relation v = 0.725 was applied. Further, the average values ​​of g' were calculated from the following formulas (v-2), (v-3), and (v-4): A trendline assuming only short chain branches was determined for each sample.

[0039]

number

[0040] Furthermore, using g'w, the number of branch points per molecular chain, BrNo, and the number of long chain branches per 1000 carbon atoms, LCB, are calculated. 1000C The branching degree λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer formula (v-5). 1000C Equations (v-6) and (v-7) were used to calculate λ. g is the long-chain branching parameter calculated from the radius of gyration Rg, and the following simple correlation is established between g' calculated from the intrinsic viscosity. Various values ​​have been proposed for ε in the equation depending on the shape of the molecule. Here, calculations were performed assuming ε = 1 (i.e., g' = g).

[0041]

number

[0042] λ=BrNo / M …(v-6) LCB 1000C =λ×14000 …(v-7) *In formula (v-7), 14,000 represents the molecular weight of 1,000 methylene (CH2) units.

[0043] Other requirements In addition to the above requirements (i) to (iv) and the optional requirement (v), the copolymer (L) used in the present invention preferably has an intrinsic viscosity [η] of 0.1 to 5.0 dL / g, more preferably 0.5 to 4.0 dL / g, even more preferably 0.8 to 3.5 dL / g, and particularly preferably 1.0 to 3.0 dL / g. Here, the intrinsic viscosity [η] means the value measured in decalin at 135°C.

[0044] The ethylene copolymer composition of the present invention may contain two or more copolymers (L) having different physical properties depending on the application, use conditions, and desired physical properties of the industrial belt. In one typical and exemplary embodiment of the present invention, the ethylene copolymer composition of the present invention contains, as the first copolymer (L), a copolymer (L1) having a relatively high intrinsic viscosity [η], and as the second copolymer (L), a copolymer (L2) having a lower intrinsic viscosity [η] than that of the copolymer (L1). In this case, the intrinsic viscosity [η] of the copolymer (L1) may be, for example, 2.0 to 3.5 dL / g (or 2.0 to 3.0 dL / g), and the intrinsic viscosity [η] of the copolymer (L2) may be, for example, 1.0 dL / g or more but less than 2.0 dL / g.

[0045] The ethylene copolymer composition of the present invention may contain, as the first copolymer (L), a copolymer (L1) having a relatively large weight-average molecular weight (Mw), and, as the second copolymer (L), a copolymer (L2) having a weight-average molecular weight (Mw) smaller than that of the copolymer (L1).

[0046] The copolymer (L) used in the present invention preferably has a weight-average molecular weight (Mw) of 10,000 to 800,000, more preferably 30,000 to 700,000, even more preferably 50,000 to 650,000, particularly preferably 70,000 to 600,000, and even more preferably 80,000 to 500,000. When the copolymer (L) used in the present invention is composed of two or more copolymers, the copolymer (L) may contain, as the first copolymer (L), a copolymer (L1) having a relatively large weight-average molecular weight (Mw), and as the second copolymer (L), a copolymer (L2) having a weight-average molecular weight (Mw) smaller than that of the copolymer (L1).

[0047] The copolymer (L) used in the present invention may be prepared by any method as long as it satisfies the above requirements (i) to (iv). However, it is more preferable that the copolymer (L) is obtained by copolymerizing ethylene, propylene, and a non-conjugated polyene (C) in the presence of a metallocene compound in the presence of a catalyst system containing a metallocene compound.

[0048] Specifically, the copolymer (L) used in the present invention can be produced, for example, by employing the method using a metallocene catalyst described in WO 2015 / 122495.

[0049] When the copolymer (L) used in the present invention is obtained by a production method using a metallocene catalyst, its intrinsic viscosity [η] and intrinsic viscosity [η] can be adjusted by appropriately adjusting the amount of hydrogen supplied during the polymerization reaction.

[0050] <<Trans-polyoctenylene (M)>> The trans polyoctenylene (M), which is the component (2) constituting the ethylene copolymer composition of the present invention, is a polymer of octenylene having a trans structure, and is a metathesis polymer of cyclooctene having mainly trans double bonds.

[0051] The ethylene copolymer composition of the present invention contains the trans-polyoctenylene (M), which improves compatibility with fibrous materials, thereby improving tackiness and adhesion to fibrous materials, and also improves abrasion resistance.

[0052] Trans polyoctenylene (M) is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond (a polymer obtained by metathesis polymerization of trans double-bonded cyclooctene using a metal atom as a polymerization catalyst). The trans-polyoctenylene (M) used in the present invention is manufactured and sold by Evonik Industries under the trade name VESTENAMER.

[0053] Crosslinking aid (K) The crosslinking aid (K), which is the component (3) constituting the ethylene copolymer composition of the present invention, has two or more ethylenic double bonds. Specific examples of the crosslinking aid (K) include (meth)acrylic crosslinking aids such as ethylene glycol di(meth)acrylate and trimethylolpropane tri(meth)acrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; and vinyl crosslinking aids such as divinylbenzene. Among these, (meth)acrylic crosslinking aids are preferred, and ethylene glycol dimethacrylate is more preferred.

[0054] <Ethylene-based copolymer composition> The ethylene copolymer composition of the present invention is a composition comprising the ethylene-propylene-non-conjugated polyene copolymer (L) as component (1), the trans-polyoctenylene (M) as component (2), and the cross-linking coagent (K) as component (3), and preferably contains 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 2 to 10 parts by mass, and particularly preferably 3 to 7 parts by mass of the trans-polyoctenylene (M) and 0.1 to 20 parts by mass, more preferably 1.0 to 10 parts by mass, even more preferably 2.0 to 7.0 parts by mass, and particularly preferably 3.0 to 5.0 parts by mass of the cross-linking coagent (K) per 100 parts by mass of the copolymer (L).

[0055] The ethylene-based copolymer composition of the present invention contains the above-mentioned components in addition to the ethylene-propylene-non-conjugated polyene copolymer (L), and therefore the ethylene-based copolymer composition has excellent adhesive strength to other materials, for example, layers containing fibrous materials such as industrial belts, preferably layers containing fibrous materials, and also has excellent abrasion resistance.

[0056] In addition to components such as the copolymer (L), the ethylene copolymer composition of the present invention may contain other components depending on the desired purpose, provided that the effects of the present invention are not impaired. Examples of such other components include crosslinking agents. Furthermore, the ethylene copolymer composition of the present invention may contain, among the other components, at least one component other than the crosslinking agent, selected from the group consisting of vulcanization accelerators, vulcanization aids, fillers, softeners, antioxidants, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. Each of these additives may be used alone, or two or more may be used in combination.

[0057] <Crosslinking agent> The ethylene-based copolymer composition of the present invention may further contain a crosslinking agent in addition to the ethylene-propylene-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the crosslinking coagent (K). The ethylene-based copolymer composition of the present invention does not necessarily need to contain a crosslinking agent as long as the object of the present invention can be achieved. However, the ethylene-based copolymer composition of the present invention is often used in the form of a crosslinked product for industrial belts. Therefore, the ethylene-based copolymer composition of the present invention usually contains a crosslinking agent.

[0058] Examples of crosslinking agents include those commonly used in 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, and isocyanate-based compounds. Among these, organic peroxides and sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred. In one preferred exemplary embodiment of the present invention, the crosslinking agent is an organic peroxide.

[0059] Examples of the organic peroxide (J) include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0060] When organic peroxide (J) is used as a crosslinking agent, its amount in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1.0 to 7 parts by mass, and particularly preferably 2.0 to 4.0 parts by mass, per 100 parts by mass of copolymer (L). When the amount of organic peroxide (J) is within the above range, the copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article, which is suitable.

[0061] <Other crosslinking aids, vulcanization accelerators and vulcanization aids> The ethylene copolymer composition according to the present invention may further contain, in addition to the crosslinking aid (K), another crosslinking aid that does not fall under the category of the crosslinking aid (K). Examples of other crosslinking aids that may be used in combination with the crosslinking aid (K) include sulfur; quinonedioxime-based crosslinking aids such as p-quinonedioxime; and maleimide-based crosslinking aids. These other crosslinking aids may be used alone or in combination of two or more with the crosslinking aid (K).

[0062] Examples of sulfur-based compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0063] When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 1.0 to 10 mol, preferably 0.2 to 7.0 mol, more preferably 0.5 to 5.0 mol, and even more preferably 1.0 to 3.0 mol, per mol of the organic peroxide.

[0064] 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, per 100 parts by mass of copolymer (L). When the blending amount of the sulfur-based compound is within the above range, no blooming occurs on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties. When a sulfur-based compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator in combination.

[0065] Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N'-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (e.g., Suncerer M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noccelaer MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-dinitrophenyl)mercaptobenzothiazole, Thiazole-based vulcanization accelerators such as ethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (e.g., Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, and diorthotolylguanidine; aldehyde-amine-based vulcanization accelerators such as acetaldehyde-aniline condensation product and butyraldehyde-aniline condensation product; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; tetramethylthiuram monosulfide (e.g., Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); thiuram-based vulcanization accelerators such as Sancerer TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (e.g., Sancerer TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (e.g., Sancerer TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutylthiuram disulfide (e.g., Sancerer TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Sancerer TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, diethyldithio Examples of such vulcanization accelerators include dithioacid salt vulcanization accelerators such as zinc carbamate, zinc dibutyldithiocarbamate (for example, Sancerar PZ, Sancerar BZ, and Sancerar EZ (trade names; manufactured by Sanshin Chemical Industry Co., Ltd.)) and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators such as ethylenethiourea (for example, Sancerar BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sancerar 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea; and xanthate-based vulcanization accelerators such as zinc dibutylxatogenate.

[0066] 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, per 100 parts by mass of the copolymer (L). When the blending amount of the vulcanization accelerator is within the above range, the copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article. When a sulfur-based compound is used as the crosslinking agent, a vulcanization aid can be used in combination.

[0067] When a vulcanization aid is used, the amount of the vulcanization aid blended in the ethylene copolymer composition is usually 1 to 20 parts by mass per 100 parts by mass of the copolymer (L).

[0068] Filler The ethylene copolymer composition of the present invention may further contain a filler. The filler is a known rubber reinforcing agent blended into a rubber composition, and is usually an inorganic substance called carbon black or an inorganic reinforcing agent.

[0069] Specific examples of fillers that can be used in the present invention include Asahi #55G, Asahi #60UG, and Asahi #70 (all manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, and other carbon blacks) (manufactured by Tokai Carbon Co., Ltd.), carbon blacks surface-treated with a silane coupling agent or the like, activated calcium carbonate, finely divided talc, finely divided silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, zinc oxide (e.g., ZnO#1 / zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0070] These fillers may be used alone or in combination of two or more. Preferred fillers used in the present invention include carbon black, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. Zinc oxide is also one of the fillers that can be suitably used in the present invention.

[0071] 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 15 to 150 parts by mass, more preferably 20 to 100 parts by mass, even more preferably 30 to 80 parts by mass, and particularly preferably 40 to 65 parts by mass, per 100 parts by mass of copolymer (L).

[0072] <Softener> The ethylene copolymer composition of the present invention may further contain a softener. Examples of the softener include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, and derivatives thereof; synthetic polymers such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub(factice). Of these, petroleum-based softeners and hydrocarbon-based synthetic lubricating oils are preferred, process oil and liquid ethylene-propylene copolymers are more preferred, and process oil is even more preferred.

[0073] When the liquid ethylene-propylene copolymer is used as the softener, the liquid ethylene-propylene copolymer has a dynamic viscosity at 40°C of 1 to 80,000 mm 2 / s is preferred.

[0074] Kinematic viscosity at 40°C is 1mm 2 Ethylene-propylene copolymers with a viscosity of less than 80,000 mm / s contain a large amount of easily volatile low-molecular-weight components, which may result in a deterioration in the heat resistance of the resulting ethylene copolymer composition. 2 If the viscosity exceeds 1 / s, the amount of high molecular weight components increases, which may result in insufficient viscosity, and the effect of improving the tackiness of the resulting copolymer composition for a conveyor belt may be reduced.

[0075] When the liquid ethylene-propylene copolymer is used as the softener, the liquid ethylene-propylene copolymer has excellent compatibility with the copolymer (L), and therefore the copolymer composition containing the liquid ethylene-propylene copolymer has good adhesiveness.

[0076] When the ethylene copolymer composition contains a softener, the amount of the softener to be blended is generally 2 to 100 parts by mass, preferably 4 to 80 parts by mass, more preferably 6 to 50 parts by mass, even more preferably 8 to 30 parts by mass, and particularly preferably 10 to 20 parts by mass, per 100 parts by mass of the copolymer (L).

[0077] <Anti-aging agent (stabilizer)> The life of a seal packing formed from the ethylene copolymer composition of the present invention can be extended by blending an antioxidant (stabilizer). Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0078] Examples of antioxidants include aromatic secondary amine antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate antioxidants such as nickel dibutyldithiocarbamate; and sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0079] When the ethylene copolymer composition contains an antioxidant, the blending amount of the antioxidant is usually 0.3 to 10 parts by mass, preferably 0.5 to 8.0 parts by mass, more preferably 1.0 to 7.0 parts by mass, even more preferably 1.5 to 5.0 parts by mass, and particularly preferably 2.0 to 4.0 parts by mass, per 100 parts by mass of copolymer (L). When the blending 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.

[0080] <Processing aids> As the processing aid, a wide variety of processing aids that are generally compounded in rubber can be used. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters thereof. Of these, stearic acid is preferred.

[0081] When the copolymer composition contains a processing aid, it can be blended in an amount of usually 0.1 to 10 parts by mass, preferably 0.2 to 5.0 parts by mass, more preferably 0.4 to 3.0 parts by mass, even more preferably 0.6 to 2.0 parts by mass, and particularly preferably 0.8 to 1.5 parts by mass, per 100 parts by mass of copolymer (L). When the blending amount of the processing aid is within the above range, it is preferable because it provides excellent processability such as kneading processability, extrusion processability, and injection moldability. The processing aid may be used alone or in combination of two or more kinds.

[0082] <Activator> Examples of the surfactant include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0083] When the copolymer composition contains an activator, the amount of the activator added is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the copolymer (L).

[0084] <Method for producing ethylene copolymer composition> The ethylene copolymer composition of the present invention can be obtained by a production method including a step of kneading the ethylene-propylene-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and, if necessary, a processing aid, a crosslinking aid, etc., using an internal mixer (internal mixer) such as a Banbury mixer, a kneader, or an intermix, for example, at 80 to 160°C for 1 to 3 minutes. In the production method, the crosslinking aid (K) may be added during or after the kneading step. Here, the ethylene copolymer composition containing the crosslinking agent can be prepared by mixing additives such as the crosslinking agent and the crosslinking aid (K) into the blend (compound) obtained by the kneading step using rolls such as open rolls or a kneader, and optionally adding a vulcanization accelerator and a crosslinking aid; kneading the mixture at a roll surface temperature of 40 to 80°C for 5 to 30 minutes, preferably 40 to 70°C for 6 to 25 minutes, more preferably 45 to 65°C for 7 to 20 minutes, and even more preferably 45 to 60°C for 8 to 15 minutes, and then further performing a separating step.

[0085] In addition, when the kneading temperature in an internal mixer is low, the crosslinking agent and the crosslinking aid (K) may be kneaded simultaneously with components other than the crosslinking agent, such as the ethylene-propylene-non-conjugated polyene copolymer (L) and the trans-polyoctenylene (M).

[0086] <Physical Properties of Uncrosslinked Ethylene Copolymer Composition> Mooney viscosity ML of the uncrosslinked ethylene copolymer composition of the present invention (1+4) The temperature at 100°C is preferably 20 to 80, more preferably 30 to 70, even more preferably 40 to 60, and particularly preferably 50 to 55. Mooney viscosity ML(1+4) When 100°C is within the above range, the ethylene copolymer composition has good processability and flowability. Mooney viscosity ML (1+4) 100°C can be measured in accordance with JIS K 6300 (1994).

[0087] <Laminate> The laminate of the present invention is a laminate in which a layer [I] made of the ethylene copolymer composition and a layer [II] containing a fibrous material are in contact with each other. That is, the laminate of the present invention includes a layer [I] made of the ethylene copolymer composition and a layer [II] containing a fibrous material, and the layer [I] and the layer [II] are in contact with each other.

[0088] <<Layer [I] Made of Ethylene-Based Copolymer Composition>> The layer [I] constituting the laminate of the present invention is a layer made of the above ethylene copolymer composition, and is preferably a layer made by crosslinking the above ethylene copolymer composition.

[0089] <Layer containing fibrous material [II]> The layer [II] constituting the laminate of the present invention contains a fibrous material. This layer [II] contains a fibrous material in at least a part of the layer.

[0090] <Textile materials> Examples of the fiber material forming the layer [II] used in the present invention include various known fiber materials, such as natural fibers such as cotton, hemp, flax (linen), and wood cellulose fibers; organic fiber materials such as fibers made of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymers; and inorganic fiber materials such as glass fiber, PAN-based carbon fiber, pitch-based carbon fiber, alumina fiber, silicon carbide fiber, aluminum borate fiber, and potassium titanate whisker.

[0091] These fiber materials may be long fibers (filaments) or short fibers (staples), and may be cord yarns, spun yarns, woven fabrics, knitted fabrics, canvas, nonwoven fabrics, etc.

[0092] Examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 6,6, and nylon 6,10; semi-aromatic polyamides such as polymetaxylylene adipamide (MXD6), polyhexamethylene terephthalamide (6T), and copolymer polyamides containing these units; and wholly aromatic polyamides such as polybenzamide, poly-p-phenylene terephthalamide, and poly-m-phenylene isophthalamide.

[0093] In one preferred and exemplary embodiment of the present invention, the fiber material forming the layer [II] is canvas. Canvas is a thick cloth woven in a plain weave, and is often made from cotton, hemp, or flax (linen). In another preferred and exemplary embodiment of the present invention, the fiber material forming the layer [II] is a woven fabric of nylon fibers.

[0094] Furthermore, these fiber materials may be surface-treated by a known method such as resorcinol-formaldehyde latex treatment (RFL treatment) in order to improve adhesion between the fiber materials themselves or between the fiber materials and the layer [I] made of the ethylene copolymer composition.

[0095] <RFL treatment> The fiber material forming the layer [II] used in the present invention may contain fibers that have been treated with resorcinol formaldehyde latex (RFL treatment). RFL treatment involves the adhesive treatment of textile materials using a treatment liquid (RFL liquid) containing resorcinol, formalin, and latex. This RFL liquid is a mixture of the initial condensation product of resorcinol and formalin and rubber latex. Rubber latex can be styrene-butadiene-vinylpyridine terpolymer (VP), styrene-butadiene copolymer (SBR), chloroprene (CR), acrylonitrile-butadiene copolymer (NBR), hydrogenated NBR (H-NBR), chlorosulfonated ethylene (CSM), natural rubber, etc. These can be used alone or in a blend of two or more.

[0096] <Method of manufacturing laminate> The laminate of the present invention can be produced by various known methods for producing laminates, such as a method of laminating a layer [I] made of an uncrosslinked ethylene copolymer composition previously produced (molded) by a known method with a layer [II] containing a fibrous material, a method of crosslinking the layer [I] made of the ethylene copolymer composition after laminating them, a method of laminating the layer [I] made of the crosslinked ethylene copolymer composition with a layer [II] containing a fibrous material, a method of extrusion coating the layer [I] made of the ethylene copolymer composition onto the layer [II] containing a fibrous material, or a method of extrusion coating and then crosslinking the layer [I] made of the ethylene copolymer composition. The layer [I] made of the ethylene copolymer composition can be produced by various known methods.

[0097] The ethylene copolymer composition can be obtained by kneading the copolymer (L), the trans-polyoctenylene (M), the crosslinking aid (K), and further a crosslinking agent, and optionally additives such as a filler, a softener, 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, a roll, or the like.

[0098] The uncrosslinked ethylene copolymer composition obtained by kneading may be molded into an intended shape by various molding methods such as an extruder, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then crosslinked to form a layer [I] made of the ethylene copolymer composition, which may then be laminated (bonded) with a layer [II] containing a fibrous material; alternatively, the uncrosslinked ethylene copolymer composition may be molded into an intended shape by the above-mentioned method, and then laminated (bonded) with a layer [II] containing a fibrous material, followed by crosslinking.

[0099] The layer [I] made of the ethylene copolymer composition may be crosslinked by either a method of heating using a crosslinking agent or a method of irradiating with light, γ rays or electron beams. Furthermore, crosslinking may be performed using a mold or without a mold. When a mold is not used, the molding and crosslinking steps are usually performed continuously. Heating methods that can be used in the crosslinking tank include hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, and other heating tanks.

[0100] <<Uses of laminates>> A laminate in which a layer [I] made of the ethylene copolymer composition of the present invention and a layer [II] containing a fibrous material are in contact with each other is suitably used for an industrial belt, that is, it can be said that the industrial belt of the present invention has the laminate. The laminate is also suitable for use in automobile hoses, water hoses, gas hoses; industrial belts such as transmission belts and conveyor belts; and escalator handrails.

[0101] Examples of the automotive hose include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the transmission belt include a V-belt, a flat belt, a toothed belt, etc. Examples of the conveyor belt include a light conveyor belt, a cylindrical belt, a rough-top belt, a flanged conveyor belt, a U-shaped guided conveyor belt, a V-guided conveyor belt, etc. [Example]

[0102] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" means "parts by mass" unless otherwise specified. The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0103] [Measurement and evaluation method] In the following examples and comparative examples, the methods for measuring and evaluating the various physical properties and characteristics are as follows.

[0104] (1) Ethylene-propylene-non-conjugated polyene copolymer (L) [Composition of ethylene-propylene-non-conjugated polyene copolymer (L)] The molar ratio and mass fraction (mass%) of each structural unit of the ethylene-propylene-non-conjugated polyene copolymer (L) are: 13 The measured values ​​were obtained by C-NMR using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.), with a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an accumulation number of 8000. 13 The C-NMR spectrum was obtained.

[0105] <Intrinsic viscosity> The intrinsic viscosity [η] was measured using a fully automatic intrinsic viscometer manufactured by Rigo Co., Ltd. at a temperature of 135° C. and in decalin as a measurement solvent.

[0106] <Complex viscosity η * and P value The rheometer used was a viscoelasticity measuring device, Ares (manufactured by Rheometric Scientific), and the complex viscosity η was measured at a frequency of ω = 0.01 rad / s under the conditions of 190°C and 1.0% strain. * (ω=0.01) , complex viscosity η at frequency ω=0.1rad / s * (ω=0.1) , complex viscosity η at frequency ω=10 rad / s *(ω=10) and the complex viscosity η at frequency ω = 100 rad / s * (ω=100) (All units are Pa·sec) were measured. * (ω=0.1) and η * (ω=100) The ratio of the complex viscosity to * P-value (η * (ω=0.1) / η * (ω=100) ) was calculated.

[0107] <Weight average molecular weight (Mw)> The Mw was determined by the structural analysis method using 3D-GPC described above.

[0108] <Mooney viscosity> Mooney viscosity (ML (1+4) The viscosity at temperatures of 100°C and 125°C was measured using a Mooney viscometer (Model SMV-301 manufactured by Shimadzu Corporation) in accordance with JIS K6300 (1994).

[0109] The measurement solvent was o-dichlorobenzene-d4 / benzene-d6 (4 / 1 [v / v]) at a measurement temperature of 120°C. 13 A C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured, and the value was calculated based on the following formula (i). B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i)

[0110] Here, [E], [X], and [Y] represent the mole fractions of constituent units derived from ethylene (A), propylene (B), and non-conjugated polyene (C), respectively, and [EX] represents the ethylene (A)-propylene (B) dyad sequence fraction.

[0111] (2) Physical Properties of Uncrosslinked Ethylene Copolymer Composition <Mooney viscosity> Mooney viscosity ML of uncrosslinked ethylene copolymer composition (1+4)The viscosity was measured at 100°C using a Mooney viscometer (Model SMV-301 manufactured by Shimadzu Corporation) in accordance with JIS K 6300 (1994).

[0112] <Adhesion (probe tack integral value)> Using a tack tester (TAC-II) manufactured by Rhesca Co., Ltd., a 200 gf load was applied to a 5 mm diameter stainless steel probe, which was pressed for 5 seconds against each of the resins in Example 1 and Comparative Examples 1 and 2. The peak value (gf) and stress integral value (gf·sec) were measured when the probe was peeled off at a speed of 120 mm / min. This measurement was carried out 10 times at 50°C, and the average integral value (probe tack integral value) was calculated and used as an index of adhesiveness.

[0113] (3) Physical Properties of Ethylene-Based Copolymer Composition (Crosslinked Product) <Hardness test (Durometer-A)> The flat portions of the 2 mm thick crosslinked sheets produced in the examples were stacked to form a 12 mm thick sheet, and the hardness (JIS-A) was measured in accordance with JIS K 6253 (2012).

[0114] <Tensile test: modulus, tensile stress at break, tensile elongation at break> The crosslinked sheets prepared in the examples and the like were punched out to prepare No. 3 dumbbell test pieces described in JIS K 6251 (1993). Using these test pieces, tensile tests were carried out according to the method specified in JIS K 6251, paragraph 3, at a measurement temperature of 170°C and a tensile speed of 500 mm / min, and the tensile stress (25% modulus (M25) to 200% modulus (M200)), tensile stress at break (TB), and tensile elongation at break (EB) were measured.

[0115] (DIN friction test (amount of wear loss)) In accordance with JIS-K6264-2:2005, three 2 mm thick crosslinked sheets were stacked to prepare a disk-shaped test piece with a diameter of 16.0±0.2 mm and a thickness of 6 mm. Using a DIN abrasion tester, the test piece was measured for the amount of wear (DIN abrasion amount: unit: mg) when a drum with a diameter of 150.0±0.2 mm and a length of 500 mm was rotated at 40 rpm under a load of 1 kgf over an abrasion distance of 40.0±0.2 m.

[0116] <Peel test (peel strength)> The peel strength (adhesion strength) between the layer [I] made of the crosslinked ethylene copolymer composition and the layer [II] containing a fibrous material was measured by the following method.

[0117] A 3 mm thick uncrosslinked sheet was placed on top of an RFL-treated nylon fiber woven fabric (manufactured by Ayaha Kogyo Co., Ltd.) and pressed at 170°C for 15 minutes using a 200-ton press molding machine to crosslink the uncrosslinked sheet and obtain a laminate. A 25 mm wide test piece was punched out of the laminate and subjected to a T-peel test at a tensile speed of 50 mm / min. The peel test was performed three times, and the average value was taken as the peel strength.

[0118] In the examples and comparative examples, the following copolymers were used. The ethylene-propylene-non-conjugated polyene copolymer (L) used was the ethylene-propylene-VNB copolymer (copolymer (L-1)) obtained in Production Example 1 and the ethylene-propylene-VNB copolymer (copolymer (L-2)) obtained in Production Example 2.

[0119] [Manufacturing Example 1] A 300-liter polymerization reactor was continuously fed with 58.3 L / hr of dehydrated and purified hexane solvent through line 1, and 4.5 mmol / hr of triisobutylaluminum (TiBA), 0.150 mmol / hr of (C6H5)3CB(C6F5)4, and 0.030 mmol / hr of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride through line 2. Simultaneously, 6.6 kg / hr of ethylene, 9.3 kg / hr of propylene, 18 L / hr of hydrogen, and 340 g / hr of VNB were continuously fed into the polymerization reactor through separate lines, and copolymerization was carried out under the conditions of a polymerization temperature of 87°C, a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

[0120] The ethylene-propylene-VNB copolymer solution produced in the polymerization reactor was continuously discharged at a flow rate of 88.0 L / hr, heated to 170°C (pressure increased to 4.1 MPaG), and fed to a phase separator. At this time, ethanol, a polymerization inhibitor, was continuously introduced into the discharge line in an amount of 0.1 mol times the TiBA in the liquid component extracted from the polymerization reactor.

[0121] In the phase separator, the ethylene-propylene-VNB copolymer solution separated into a dense phase (lower phase) containing the majority of the ethylene-propylene-VNB copolymer and a dilute phase (upper phase) containing a small amount of the polymer.

[0122] The separated thick phase was introduced into a heat exchanger at a rate of 85.4 L / hr and then into a hopper where the solvent was evaporated and separated, yielding an ethylene-propylene-VNB copolymer at a rate of 7.8 kg / hr.

[0123] The physical properties of the obtained ethylene-propylene-VNB copolymer (L-1) were evaluated by the methods described below. The results are shown in Table 1. The molecular weight distribution of the obtained copolymer (L-1) was bimodal, and the chart obtained by GPC measurement showed two or more peaks, with the area of ​​the peak appearing on the side with the lowest molecular weight accounting for 5% of the total peak area.

[0124] [Manufacturing Example 2] Ethylene-propylene-VNB copolymer (L-2) was produced in accordance with Production Example 1, except that the molecular weight of the resulting copolymer was controlled by the amount of hydrogen fed. The results are shown in Table 1. [Table 1]

[0125] [Trans-polyoctenylene (M)] In the examples and comparative examples, the following octenylene polymer (M-1): trade name: VESTENAMER 8012, manufactured by Evonik Industries, was used as the trans polyoctenylene (M).

[0126] [Organic peroxide (J)] In the examples and comparative examples, the following organic peroxide (J-1) was used as the organic peroxide (J): dicumyl peroxide (J-1) (Percumyl D (manufactured by NOF Corporation; purity 98% or more (industrially pure product)).

[0127] [Crosslinking aid (K)] In the examples and comparative examples, the following crosslinking aid (K-1): ethylene glycol dimethacrylate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunester EG) was used as the crosslinking aid (K).

[0128] [Example 1] Fifty parts by mass of the ethylene-propylene-VNB copolymer [copolymer (L-1)] obtained in Production Example 1 and 50 parts by mass of the ethylene-propylene-VNB copolymer [copolymer (L-2)] obtained in Production Example 2 were masticated for 30 seconds, and 100 parts by mass of the resulting mixture was mixed with 1 part by mass of stearic acid as a lubricant (processing aid), 1 part by mass of tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane (H-1) [trade name Irganox 1010, manufactured by BASF Japan Ltd.] and 2 parts by mass of 2-mercaptobenzimidazole (H-2) [trade name Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.] as antioxidants, 5 parts by mass of zinc oxide (ZnO#1) and 50 parts by mass of carbon black (G-1) [trade name Asahi #70, manufactured by Asahi Carbon Co., Ltd.] as fillers, and a softener [trade name 51 parts by mass of Diana Process Oil PW-380 (Idemitsu Kosan Co., Ltd.) and 5 parts by mass of octenylene polymer (M-1) (trade name: VESTENAMER 8012, Evonik Industries) as trans-polyoctenylene (M) were added and mixed in a 1.7-liter Banbury mixer (Kobe Steel, Ltd.) at 150°C for 2 minutes. The ram was then raised and cleaned, and the mixture was mixed for another 1 minute and discharged at approximately 150°C to obtain a blend (Blend-1). This blending was performed at a filling rate of 70%.

[0129] Next, 179 parts by mass of this blend was wound around an 8-inch roll (surface temperature of front roll: 50°C, surface temperature of rear roll: 50°C, rotation speed of front roll: 16 rpm, rotation speed of rear roll: 18 rpm), and 2.7 parts by mass of dicumyl peroxide (J-1) (Percumyl D (NOF Corporation; purity 98% or higher (industrially pure product)) as the organic peroxide (J) and 4 parts by mass of ethylene glycol dimethacrylate (K-1) (manufactured by Sanshin Chemical Industry Co., Ltd., trade name Sunester EG) as the crosslinking aid (K) were added and kneaded for 10 minutes to obtain a composition, which was then cut into sheets according to the test pieces, and uncrosslinked sheets with thicknesses of 2 mm and 3 mm were prepared.

[0130] The adhesive strength (gf) of the resulting 2 mm thick uncrosslinked sheet was measured by the method described above. The results are shown in Table 2. Next, the resulting 2 mm-thick uncrosslinked sheet was pressed at 170°C for 15 minutes using a 100-ton press molding machine to produce a crosslinked sheet. The physical properties of the resulting crosslinked sheet were measured using the methods described above. The results are shown in Table 2.

[0131] Comparative Example 1 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, except that a copolymer composition not containing trans-polyoctenylene (M) was used instead of the copolymer composition used in Example 1, and the physical properties and the like were evaluated by the methods described above. The results are shown in Table 2.

[0132] Comparative Example 2 An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, except that a copolymer composition containing neither trans-polyoctenylene (M) nor crosslinking aid (K) was used instead of the copolymer composition used in Example 1, and the physical properties and the like were evaluated by the methods described above. The results are shown in Table 2.

[0133] [Table 2]

Claims

1. An ethylene copolymer composition comprising the following components (1) to (3): Component (1): an ethylene-propylene-non-conjugated polyene copolymer (L) satisfying the following requirements (i) to (iv): Component (2): trans polyoctenylene (M); Component (3): A crosslinking coagent (K) having two or more ethylenic double bonds. (i) The molar ratio of the structural units derived from ethylene to the structural units derived from propylene is 40 / 60 to 99.9 / 0.

1. (ii) The mass fraction of the constituent units derived from the non-conjugated polyene (C) is 0.07% by mass to 10% by mass in 100% by mass of the ethylene-propylene-non-conjugated polyene copolymer. (iii) The weight average molecular weight (Mw) of the ethylene-propylene-non-conjugated polyene copolymer, the mass fraction of the constituent unit derived from the non-conjugated polyene (C) (mass fraction (mass%) of (C)), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (1): 4.5≦Mw×mass fraction of (C) / 100 / molecular weight of (C)≦80 ... Formula (1) (iv) Complex viscosity η at frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190°C) using a rheometer * (ω=0.1) (Pa sec) and the complex viscosity η at a frequency ω = 100 rad / s * (ω=100) (Pa sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η], and the mass fraction of the structural unit derived from the non-conjugated polyene (C) (mass fraction of (C)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ mass fraction of (C) × 6 ... Equation (2)

2. 2. The ethylene copolymer composition according to claim 1, wherein the non-conjugated polyene constituting the ethylene-propylene-non-conjugated polyene copolymer (L) comprises 5-vinyl-2-norbornene (VNB).

3. The ethylene-based copolymer composition according to claim 1, wherein the crosslinking coagent (K) having two or more ethylenic double bonds comprises ethylene glycol dimethacrylate.

4. The ethylene copolymer composition according to claim 1, further comprising an organic peroxide as a crosslinking agent.

5. A laminate comprising a layer [I] made of the ethylene copolymer composition according to any one of claims 1 to 4 and a layer [II] containing a fibrous material in contact with each other.

6. The laminate according to claim 5 , wherein the ethylene copolymer composition is crosslinked.

7. The laminate according to claim 5, wherein the fiber material of the layer [II] comprises resorcinol-formaldehyde latex-treated (RFL-treated) fiber.

8. The laminate according to claim 5, wherein the fiber material of the layer [II] is canvas.

9. An industrial belt comprising the laminate of claim 5.

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