Resin compositions for wire coverings, crosslinked molded articles, laminates, and wire covering materials

Abstract

To provide a resin composition for wire coatings that contains an ethylene-α-olefin-non-conjugated polyene copolymer and a reinforcing agent, and exhibits excellent mechanical properties. [Solution] A resin composition for wire coating comprising: a copolymer (S1) having constituent units derived from ethylene, constituent units derived from α-olefins having 3 to 20 carbon atoms, and constituent units derived from a non-conjugated polyene containing a total of two or more substructures selected from the group consisting of the following formulas (I) and (II) in one molecule; an ethylene-α-olefin copolymer (S2) having constituent units derived from ethylene and constituent units derived from α-olefins having 3 to 20 carbon atoms (excluding copolymers corresponding to (S1)); a reinforcing agent; and a mono- or polysulfide bond-containing phenolic crosslinking aid. TIFF2026078821000009.tif26150

Description

Technical Field

[0001] The present disclosure relates to a resin composition for wire coating, a crosslinked molded body, a laminate, and a wire coating material.

Background Art

[0002] Ethylene-α-olefin-nonconjugated polyene copolymers such as ethylene-propylene-nonconjugated diene copolymer (EPDM) usually do not have unsaturated bonds in the main chain of their molecular structure. Therefore, compared with general-purpose conjugated diene rubbers, the above copolymers are excellent in heat aging resistance, weather resistance, and ozone resistance, and are widely used in various applications.

[0003] The above copolymers are usually used after being crosslinked. The above copolymers are used, for example, in wire coating materials and cable coating materials (for example, Patent Document 1).

[0004] Since wire coating materials and cable coating materials are required to have a high electrical resistivity, talc or the like may be used in combination with the above copolymers as a reinforcing agent.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] A crosslinked molded body obtained by crosslinking a composition containing an ethylene-α-olefin-nonconjugated polyene copolymer and a reinforcing agent such as talc has an electrical resistivity suitable for use as a wire coating material, while there is room for improvement in its mechanical properties. Therefore, an object of the present disclosure is to provide a resin composition for wire coating that contains an ethylene-α-olefin-nonconjugated polyene copolymer and a reinforcing agent and has excellent mechanical properties.

Means for Solving the Problem

[0007] One aspect of the resin composition for wire coating of the present disclosure is a copolymer (S1) having a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing two or more of at least one partial structure selected from the group consisting of the following formulas (I) and (II) in total in one molecule, an ethylene·α-olefin copolymer (S2) having a structural unit derived from ethylene (D) and a structural unit derived from an α-olefin (E) having 3 to 20 carbon atoms (however, excluding the copolymer corresponding to the above (S1)), a reinforcing agent, a phenolic crosslinking coagent (F) containing a mono- or polysulfide bond, and.

Effect of the Invention

[0008] The resin composition for wire coating of the present disclosure contains an ethylene·α-olefin·non-conjugated polyene copolymer and a reinforcing agent, and has excellent mechanical properties.

Mode for Carrying Out the Invention

[0009] In this specification, the numerical range n1 to n2 means n1 or more and n2 or less when n1 < n2, and means n2 or more and n1 or less when n1 > n2. In this specification, when a lower limit value and an upper limit value are each described a plurality of times in the description of an element, a numerical range formed by combining a value arbitrarily selected from the described lower limit values and a value arbitrarily selected from the described upper limit values is also described.

[0010] In this specification, when the units of the numerical values described before and after "~" indicating a numerical range are the same, the unit of the numerical value described before "~" may be omitted. For example, "50 mol% to 85 mol%" may be described as "50 to 85 mol%".

[0011] In this specification, the amount of each component in a composition means the total amount of multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to that component in the composition.

[0012] In this specification, unless otherwise specified, each component in a composition, or each constituent unit in a polymer, may be present in one form or in two or more forms. In this specification, homopolymers and copolymers are sometimes referred to simply as "polymers." In other words, the term "polymer" can refer to either homopolymers or copolymers.

[0013] [Resin composition for electric wire coating] The wire coating resin composition disclosed herein comprises a copolymer (S1), a copolymer (S2), a reinforcing agent, and a crosslinking aid (F). Each component is described below.

[0014] <Copolymer (S1)> The copolymer (S1) comprises a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of the following formulas (I) and (II) in one molecule.

[0015] [ka]

[0016] Examples of α-olefins (B) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene, are preferred, with propylene being particularly preferred. Such α-olefins are preferred because their raw material costs are relatively low, the resulting resin compositions exhibit excellent mechanical properties, and molded articles with rubber elasticity can be obtained. α-olefin (B) may be used alone or in combination of two or more types.

[0017] Examples of non-conjugated polyenes (C) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, 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- Examples include ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-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-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, and dicyclopentadiene. The non-conjugated polyene (C) preferably contains VNB, and more preferably VNB, because it is readily available, the resulting copolymer has good crosslinkability, and the heat resistance of the resin composition is easily improved. The unconjugated polyene (C) may be used alone or in combination of two or more types.

[0018] The copolymer (S1) may further contain constituent units derived from a non-conjugated polyene (CX). The non-conjugated polyene (CX) is a non-conjugated polyene that contains only one substructure selected from the group consisting of formulas (I) and (II) in each molecule.

[0019] Examples of non-conjugated polyenes (CX) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(2-methyl-1-propenyl)-2-norbornene. Non-conjugated polyenes (CX) preferably contain ENB, and more preferably ENB, because they are readily available, the crosslinking rate of the resulting copolymer is easy to control, and good mechanical properties can be easily obtained. Non-conjugated polyenes (CX) may be used individually or in combination of two or more types.

[0020] The copolymer (S1) may contain at least one constituent unit derived from biomass-derived monomers. Examples of biomass-derived monomers include biomass-derived ethylene, biomass-derived α-olefins having 3 to 20 carbon atoms, and biomass-derived non-conjugated polyenes. An example of a biomass-derived α-olefin is biomass-derived propylene. Examples of biomass-derived non-conjugated polyenes include biomass-derived 5-vinyl-2-norbornene and biomass-derived 5-ethylidene-2-norbornene. The monomers used as raw materials for the copolymer (S1) may consist only of biomass-derived monomers, only of fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are obtained by known methods. It is preferable for the copolymer (S1) to contain constituent units derived from biomass-derived monomers from the viewpoint of reducing environmental impact.

[0021] The copolymer (S1) may contain at least one constituent unit derived from chemically recycled monomers. Examples of chemically recycled monomers include chemically recycled ethylene, chemically recycled α-olefins having 3 to 20 carbon atoms, and chemically recycled non-conjugated polyenes. The monomers used as raw materials for copolymer (S1) may consist solely of chemically recycled monomers, solely of fossil fuel-derived monomers, or both. Chemically recycled monomers can be obtained by known methods. It is preferable for copolymer (S1) to contain constituent units derived from chemically recycled monomers from the viewpoint of reducing environmental impact (mainly waste reduction).

[0022] The copolymer (S1) preferably contains an ethylene-propylene-VNB copolymer, and more preferably consists solely of an ethylene-propylene-VNB copolymer. If the copolymer (S1) contains an ethylene-α-olefin-non-conjugated polyene copolymer other than the ethylene-propylene-VNB copolymer, the mass fraction of the ethylene-propylene-VNB copolymer to the total mass of the copolymer (S1) is preferably greater than 50% by mass and less than 100% by mass, more preferably 60-99% by mass, even more preferably 65-98% by mass, and particularly preferably 70-97% by mass.

[0023] The copolymer (S1) preferably satisfies one or more of the following requirements (1) to (5), more preferably two or more, even more preferably three or more, even more preferably four or more, and particularly preferably all five.

[0024] Requirement (1): When the total constituent units contained in the copolymer (S1) are 100 mol%, the ratio [A] / [B], which is the ratio of the mole fraction [A] of constituent units derived from ethylene (A) to the mole fraction [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. The above ratio ([A] / [B]) is preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, even more preferably 55 / 45 to 80 / 20, even more preferably 55 / 45 to 78 / 22, and particularly preferably 60 / 40 to 75 / 25.

[0025] If the copolymer (S1) satisfies requirement (1), the crosslinked molded article obtained from the resin composition containing such copolymer tends to have excellent rubber elasticity, flexibility, and mechanical strength.

[0026] When the total constituent units contained in the copolymer (S1) are considered to be 100 mol%, the mole fraction [A] of constituent units derived from ethylene (A) is preferably 50 to 85 mol%, more preferably 55 to 80 mol%, and even more preferably 60 to 75 mol%.

[0027] Requirement (2): The mass fraction of constituent units derived from non-conjugated polyene (C) is 0.07 to 10% by mass of copolymer (S1) per 100% by mass. The mass fraction of constituent units derived from non-conjugated polyene (C) is preferably 0.1 to 8.0 mass%, more preferably 0.5 to 5.0 mass%, even more preferably 0.5 to 3.0 mass%, and particularly preferably 0.5 to 2.0 mass%.

[0028] When the copolymer (S1) satisfies requirement (2), the crosslinked molded article obtained from the resin composition containing such copolymer tends to have sufficient hardness and excellent mechanical properties. When the copolymer (S1) satisfies requirement (2), it tends to have excellent crosslinking properties and exhibit a high crosslinking rate.

[0029] If the copolymer (S1) further contains constituent units derived from a non-conjugated polyene (CX), the mass fraction of the constituent units is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8.0% by mass or less, and particularly preferably 0.01 to 8.0% by mass, out of 100% by mass of the copolymer (S1).

[0030] The mole fraction [A] of constituent units derived from ethylene (A), the mole fraction [B] of constituent units derived from α-olefins with 3 to 20 carbon atoms (B), the ratio ([A] / [B]), the mass fraction of constituent units derived from non-conjugated polyenes (C), and the mass fraction of constituent units derived from non-conjugated polyenes (CX) were determined using the apparatus and conditions described in the Examples section below. 13 It can be calculated by measuring the 1C-NMR spectrum.

[0031] Requirement (3): The weight-average molecular weight (Mw) of the copolymer (S1), the mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C) (mass%)), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (i). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 80 ···(i)

[0032] The equation (i) in requirement (3) is preferably the following equation (ia). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 75 ···(ia) The equation (i) in requirement (3) is more preferably the following equation (ib). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 70 ···(ib)

[0033] The above "Mw × (C) mass fraction / 100 / (C) molecular weight" represents the number of constituent units (n) derived from the unconjugated polyene (C) per Mw of the copolymer (S1). C ) represents n C The value is preferably 4.5 to 75, more preferably 4.5 to 70. c Because the value is above the lower limit, the resin composition exhibits sufficient crosslinking properties and tends to have a high crosslinking rate. c Because the value is below the above upper limit, excessive crosslinking is less likely to occur, and the resulting crosslinked molded article exhibits superior mechanical properties.

[0034] When the copolymer (S1) satisfies the requirement (3), the content of the structural unit derived from the non-conjugated polyene (C) in such a copolymer is appropriate. Therefore, the above resin composition exhibits sufficient crosslinkability and tends to have a high crosslinking speed. Further, the crosslinked molded body formed from the above resin composition tends to have excellent mechanical properties and heat aging resistance in good balance.

[0035] The weight average molecular weight (Mw) of the copolymer (S1) can be determined as a polystyrene equivalent value measured by gel permeation chromatography (GPC) under the apparatus and conditions described in the Examples section below. In this specification, specifically, it was determined as described in the Examples below using 3D-GPC.

[0036] Requirement (4): The ratio P(η * (ω=0.1) (Pa·s) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω=100) (Pa·s) at a frequency ω = 100 rad / s, the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene (C) ((mass fraction of (C) (mass%)) satisfy the following formula (ii). * (ω=0.1) / η * (ω=100) ) and the intrinsic viscosity [η] (dL / g) and the mass fraction of the structural unit derived from the non-conjugated polyene (C) ((mass fraction of (C) (mass%)) satisfy the following formula (ii). P / ([η] 2.9 ) ≤ (mass fraction of (C)) × 6 ··· (ii)

[0037] The formula (ii) of the requirement (4) is preferably the following formula (iia). P / ([η] 2.9 ) ≤ (mass fraction of (C)) × 5.7 ··· (iia)

[0038] The ratio P(η * (ω=0.1) / η * (ω=100) )(hereinafter also referred to as "P value") represents the frequency dependence of viscosity. Therefore, P / ([η] 2.9Although influenced by factors such as short-chain branching and molecular weight, the value tends to be high when there are many long-chain branches. Generally, ethylene-α-olefin-non-conjugated polyene copolymers tend to have more long-chain branches the more constituent units derived from non-conjugated polyenes they contain. However, copolymer (S1) has fewer long-chain branches than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, which is thought to allow it to satisfy equation (ii) or (iia).

[0039] The P-value is calculated by determining the ratio of the complex viscosity measured at 190°C, 1.0% strain, and 0.1 rad / second using a viscoelasticity measuring device (e.g., Ares (manufactured by Rheometric Scientific)) to the complex viscosity measured at 100 rad / second, which is obtained by changing only the measurement frequency. Intrinsic viscosity [η] refers to the value measured in decalin at 135°C.

[0040] Requirement (5): Complex viscosity η at frequency ω = 0.01 rad / sec, obtained by linear viscoelasticity measurement using a rheometer (190°C). * (ω=0.01) (Pa·seconds) and complex viscosity η at frequency ω = 10 rad / second * (ω=10) The (Pa·seconds) and the apparent iodine value derived from the unconjugated polyene (C) satisfy the following equation (iii). Log[η * (ω=0.01) ] / Log[η * (ω=10) ] ≤ 0.0753 × {apparent iodine value derived from unconjugated polyene (C)} + 1.42···(iii)

[0041] In equation (iii), the left side represents the shear rate dependence, which is an indicator of the long-chain branching content, and the right side represents an indicator of the content of unconjugated polyenes (C) that are not consumed as long-chain branches during polymerization. It is preferable that the copolymer (S1) satisfies equation (iii) because the degree of long-chain branching is not too high.

[0042] complex viscosity η * (ω=0.01) and complex viscosity η* (ω=10) The complex viscosity η in requirement (4) is * (ω=0.1) and complex viscosity η * (ω=100) It can be measured in the same way except for the measurement frequency. The apparent iodine value derived from unconjugated polyenes (C) can be calculated using the following formula (iv). The apparent iodine value derived from non-conjugated polyene (C) = mass fraction of (C) × 253.81 / molecular weight of (C) ... (iv)

[0043] In copolymer (S1), as described above, it is preferable that the non-conjugated polyene (C) contains VNB, and more preferably that the non-conjugated polyene (C) is VNB. That is, in formulas (i) and (ii), etc., it is preferable that the "mass fraction of (C)" is the "mass fraction of the constituent units derived from VNB".

[0044] As described above, when the copolymer (S1) contains constituent units derived from ethylene (A), α-olefins having 3 to 20 carbon atoms (B), non-conjugated polyenes (C), and non-conjugated polyenes (CX), the mass fraction of constituent units derived from non-conjugated polyenes (CX) is preferably 20% by mass or less (provided that the sum of the mass fractions of constituent units derived from ethylene (A), α-olefins having 3 to 20 carbon atoms (B), non-conjugated polyenes (C), and non-conjugated polyenes (CX) is 100% by mass). In this case, it is preferable that the copolymer (S1) satisfies the following requirement (6).

[0045] Requirement (6): The weight-average molecular weight (Mw) of the copolymer (S1), the mass fraction of constituent units derived from non-conjugated polyene (C) (mass fraction of (C) (mass%)), the mass fraction of constituent units derived from non-conjugated polyene (CX) (mass fraction of (CX) (mass%)), the molecular weight of non-conjugated polyene (C) (molecular weight of (C)), and the molecular weight of non-conjugated polyene (CX) (molecular weight of (CX)) satisfy the following formula (v) (wherein the total mass fraction of constituent units derived from ethylene (A), α-olefins with 3 to 20 carbon atoms (B), non-conjugated polyene (C), and non-conjugated polyene (CX) is 100% by mass). 4.5 ≤ Mw × {((mass fraction of (C) / 100 / molecular weight of (C)) + (mass fraction of (CX) / 100 / molecular weight of (CX))} ≤ 80 ···(v)

[0046] The equation (v) in requirement (6) is preferably the following equation (va). 4.5 ≤ Mw × {((mass fraction of (C) / 100 / molecular weight of (C)) + (mass fraction of (CX) / 100 / molecular weight of (CX))} ≤ 75 ···(va)

[0047] The above formula, "Mw × {((Mass fraction of (C) / 100 / Molecular weight of (C)) + (Mass fraction of (CX) / 100 / Molecular weight of (CX))}", represents the total number of constituent units derived from non-conjugated polyene (C) and non-conjugated polyene (CX) per Mw of copolymer (S1) (n C+CX ) represents n C+CX Preferably, it is between 4.5 and 78, and more preferably between 4.5 and 75. By providing a copolymer (S1) containing structural units derived from a non-conjugated polyene (CX) that satisfies requirement (6), a crosslinked molded article with excellent mechanical properties and heat aging resistance can be obtained.

[0048] The copolymer (S1) preferably satisfies the following requirement (7). Requirement (7): The mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C) (mass%)) and the natural logarithm of the weight-average molecular weight (Mw) of the copolymer (S1) [Ln(Mw)] satisfy the following equation (vi). 6 - 0.45 × Ln(Mw) ≤ (C) Mass fraction ≤ 10···(vi) If the copolymer (S1) satisfies requirement (7), such copolymer is preferable because it contains a sufficient amount of structural units derived from the unconjugated polyene (C).

[0049] The copolymer (S1) preferably satisfies the following requirement (8). Requirement (8): The B value, expressed by the following formula (vii), is 1.00 or greater. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(vii) In equation (vii), [E], [X], and [Y] represent the mole fractions of constituent units derived from ethylene (A), α-olefins with 3 to 20 carbon atoms (B), and non-conjugated polyenes (C), respectively, while [EX] represents the ethylene-α-olefin dyad chain fraction with 3 to 20 carbon atoms. The B value is preferably 1.00 to 1.80, and more preferably 1.10 to 1.40.

[0050] Copolymer (S1), when meeting requirement (8), tends to exhibit a good balance between rubber elasticity at low temperatures and tensile strength at room temperature. The B value is an indicator of the randomness of the copolymer monomer chain distribution in copolymer (S1), where [E], [X], [Y], and [EX] in equation (vii) are: 13 The 1C-NMR spectrum can be measured and determined based on reports by J. C. Sandall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], et al.

[0051] The intrinsic viscosity [η] of the copolymer (S1), measured in decalin at 135°C, is preferably 0.1 to 5.0 dL / g, more preferably 0.5 to 5.0 dL / g, even more preferably 1.0 to 4.0 dL / g, even more preferably 1.5 to 3.5 L / g, and particularly preferably 2.0 to 3.0 L / g. If the intrinsic viscosity [η] of the copolymer (S1) is above the lower limit, it is easier to obtain a molded article with superior physical properties. If the intrinsic viscosity [η] of the copolymer (S1) is below the upper limit, it is easier to obtain a resin composition with superior processability. The intrinsic viscosity [η] of the copolymer (S1) can be adjusted by the amount of hydrogen feed during polymerization.

[0052] The weight-average molecular weight (Mw) of copolymer (S1) is preferably 10,000 to 600,000, more preferably 50,000 to 550,000, even more preferably 100,000 to 520,000, even more preferably 200,000 to 500,000, and particularly preferably 400,000 to 500,000. If the weight-average molecular weight (Mw) of copolymer (S1) is above the lower limit, it is easier to obtain better physical properties. If the weight-average molecular weight (Mw) of copolymer (S1) is below the upper limit, it is easier to obtain better processability. The weight-average molecular weight (Mw) of copolymer (S1) can be measured by GPC using the apparatus and conditions described in the Examples section.

[0053] The Mooney viscosity ML(1+4)125°C of copolymer (S1) is preferably 10-100, more preferably 30-90, even more preferably 50-80, and particularly preferably 65-75. When the Mooney viscosity ML(1+4) at 125°C is within the above range, a copolymer is obtained that exhibits excellent roll processability even with a high-hardness, oil-free formulation, as well as good post-treatment (ribbon handling properties) and superior rubber properties.

[0054] From the viewpoint of obtaining molded articles with excellent low-temperature properties, the glass transition temperature (Tg) of the copolymer (S1), as measured by differential scanning calorimetry (DSC), is preferably -50°C or lower, more preferably -53°C or lower, even more preferably -55°C or lower, and particularly preferably -57°C or lower. Tg is specifically determined by the method described in the Examples section below.

[0055] The content of copolymer (S1) in the above resin composition is preferably 5 parts by mass or more and less than 100 parts by mass, more preferably 20 to 80 parts by mass, even more preferably 30 to 70 parts by mass, and particularly preferably 40 to 60 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2) described later.

[0056] <Ethylene-α-olefin copolymer (S2)> Ethylene-α-olefin copolymer (S2) has constituent units derived from ethylene (D) and constituent units derived from α-olefin (E) having 3 to 20 carbon atoms. Ethylene-α-olefin copolymer (S2) is a copolymer other than copolymer (S1).

[0057] From the viewpoint of obtaining a wire coating material with excellent mechanical strength, the α-olefin (E) having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 12 carbon atoms, and more preferably an α-olefin having 3 to 8 carbon atoms. Examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Among these, propylene, 1-butene, 1-hexene, and 1-octene are preferred. These α-olefins may be used individually or in combination of two or more.

[0058] The content of constituent units derived from ethylene (D) in the copolymer (S2) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and the content of constituent units derived from α-olefins (E) having 3 to 20 carbon atoms is preferably 30 to 70% by mass, more preferably 40 to 60% by mass (provided that the total of constituent units derived from ethylene (D) and constituent units derived from α-olefins (E) having 3 to 20 carbon atoms is 100% by mass). When the content of constituent units derived from ethylene (D) and the content of constituent units derived from α-olefins (E) having 3 to 20 carbon atoms are within the above ranges, a resin composition with excellent compatibility with copolymer (S1) can be obtained.

[0059] The density of the copolymer (S2) is preferably 840-920 kg / m³. 3 More preferably 850-915 kg / m 3 More preferably 855-910 kg / m 3 Therefore, when the density is within this range, a wire coating material can be obtained that has a low molding shrinkage rate and excellent strength characteristics and abrasion resistance. The density of the copolymer (S2) can be measured by the method described in ASTM D1505.

[0060] The ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the copolymer (S2), as determined by gel permeation chromatography (GPC) analysis, is preferably in the range of 1.5 to 20.0. The weight-average molecular weight (Mw) of the copolymer (S2) determined by GPC analysis is preferably 10,000 to 500,000, more preferably 50,000 to 300,000, and even more preferably 100,000 to 250,000.

[0061] The number-average molecular weight (Mn) of the copolymer (S2) determined by GPC analysis is preferably 1,000 to 250,000, more preferably 3,000 to 150,000, and even more preferably 5,000 to 100,000. The copolymer (S2) is preferably solid at temperatures from room temperature to about 100°C, and more preferably at around 90°C.

[0062] When the weight-average molecular weight of the copolymer (S2) is within the above range, a wire coating material with low molding shrinkage and excellent abrasion resistance can be obtained. Furthermore, the low amount of low molecular weight components is preferable because the volatilization and leaching of these low molecular weight components are less likely to occur in the resulting wire coating material. The Mw, Mn, and Mw / Mn of copolymer (S2) can be measured in the same manner as the method for measuring the weight-average molecular weight of copolymer (S1) described in the following examples.

[0063] The Mooney viscosity ML(1+4)100°C of the copolymer (S2) is preferably 10 to 100, more preferably 20 to 80, even more preferably 30 to 60, and particularly preferably 35 to 50. Mooney viscosity ML(1+4) at 100°C can be determined by measuring it using a Mooney viscometer (for example, a Shimadzu SMV202 model) in accordance with JIS K6300 (1994).

[0064] Copolymer (S2) can be produced by copolymerizing ethylene and α-olefin using conventionally known methods, for example, with a vanadium-based catalyst, a Ziegler-Natta catalyst, or a metallocene catalyst. Methods using metallocene catalysts are preferred because they allow for easy acquisition of copolymers satisfying the above-mentioned properties. More specifically, methods using catalysts containing metallocene compounds and aluminum-containing compounds as described in International Publication No. 2008 / 152935, or catalysts consisting of metallocene compounds and organoaluminum oxy compounds or ionized ionic compounds as described in Japanese Patent Publication No. 9-40586, are preferred.

[0065] The content of copolymer (S2) in the above resin composition is preferably more than 0 parts by mass and 95 parts by mass or less, more preferably 20 to 80 parts by mass, even more preferably 30 to 70 parts by mass, and particularly preferably 40 to 60 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0066] <Reinforcement agent> Examples of reinforcing agents include inorganic fillers such as silica, barium sulfate, hydrotalcite, magnesium carbonate, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine talc, talc, fine silica, alumina, titanium dioxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, and clay. Examples of commercially available reinforcing agents include Hytron A (manufactured by Takehara Chemical Industry Co., Ltd., talc).

[0067] The reinforcing agent preferably includes an insulating inorganic filler, more preferably talc or clay, from the viewpoint of having high electrical resistivity and the resulting wire coating having electrical resistivity suitable for the application. Examples of insulating inorganic fillers include silica, barium sulfate, hydrotalcite, talc, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and boron nitride. From the viewpoint of low electrical resistivity, the reinforcing agent preferably does not contain carbon black. The reinforcing agent may be used alone or in combination of two or more types.

[0068] The reinforcing agent content in the above resin composition is preferably 10 to 250 parts by mass, more preferably 30 to 200 parts by mass, even more preferably 50 to 150 parts by mass, and particularly preferably 80 to 120 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). When the reinforcing agent content is within this range, the molded articles and crosslinked molded articles obtained from the resin composition have excellent mechanical strength and heat resistance, and the wire coatings and cable coatings obtained from the resin composition have suitable mechanical properties and electrical resistance. Furthermore, by adjusting the type and content of the reinforcing agent, mechanical properties such as tensile strength, tear strength and hardness can be adjusted, and the manufacturing cost of the crosslinked molded articles can be reduced.

[0069] <Phenol-based crosslinking aid containing mono- or polysulfide bonds (F)> The mono- or polysulfide bond-containing phenolic crosslinking aid (F) is a phenolic crosslinking aid containing a monosulfide bond or a polysulfide bond. The number of sulfur atoms in the polysulfide bond is, for example, 2 to 8. The crosslinking aid (F) is preferably a crosslinking aid in which constituent units derived from phenol or hydrocarbon-substituted phenol, etc., are linked via a monosulfide bond or a polysulfide bond.

[0070] The crosslinking aid (F) preferably has a structure represented by the following formula (III).

[0071] [ka] (In formula (III), R represents a hydrocarbon group having 1 to 20 carbon atoms, n and n' represent identical or different integers from 1 to 8, and p represents an integer from 0 to 50.)

[0072] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms, cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms, alkylene groups having 1 to 20 carbon atoms, and arylene groups having 6 to 20 carbon atoms.

[0073] Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups and branched saturated hydrocarbon groups. Examples of linear saturated hydrocarbon groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decanyl group. Examples of branched saturated hydrocarbon groups include isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, isoamyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, and cyclopropylmethyl group. The alkyl group preferably has 1 to 6 carbon atoms.

[0074] Examples of cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norborneyl, 1-adamantyl, and 2-adamantyl groups. The above cyclic saturated hydrocarbon groups may also be groups in which the hydrogen atoms of these cyclic saturated hydrocarbon groups are replaced by hydrocarbon groups having 1 to 17 carbon atoms. Examples of such groups include 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, and 4-phenylcyclohexyl. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0075] Examples of chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups and alkynyl groups. Examples of alkenyl groups include ethenyl (vinyl) group, 1-propenyl group, 2-propenyl (allyl) group, and 1-methylethenyl (isopropenyl) group. Examples of alkynyl groups include ethynyl group, 1-propynyl group, and 2-propynyl (propargyl) group. The number of carbon atoms in the chain-like unsaturated hydrocarbon group is preferably 2 to 4.

[0076] Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopentadienyl, norbornyl, phenyl, naphthyl, indenyl, azlenyl, phenanthryl, and anthracenyl groups. These cyclic unsaturated hydrocarbon groups may also be groups in which the hydrogen atoms of these cyclic unsaturated hydrocarbon groups are replaced by hydrocarbon groups having 1 to 15 carbon atoms. Examples of such groups include 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl). Furthermore, these cyclic unsaturated hydrocarbon groups may also be groups in which the hydrogen atoms of a linear saturated hydrocarbon group or a branched saturated hydrocarbon group are replaced by cyclic unsaturated hydrocarbon groups having 3 to 19 carbon atoms. Examples of such groups include benzyl and cumyl groups. The cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.

[0077] Examples of alkylene groups having 1 to 20 carbon atoms include the methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, methylethylene group, and n-propylene group. The alkylene group preferably has 1 to 6 carbon atoms.

[0078] Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene groups, m-phenylene groups, p-phenylene groups, and 4,4'-biphenylene groups. The number of carbon atoms in the arylene group is preferably 6 to 12.

[0079] The above R is preferably an alkyl group having 1 to 20 carbon atoms. Examples of crosslinking aids (F) include alkylphenol disulfides.

[0080] The crosslinking aid (F) preferably comprises an alkylphenol disulfide polymer, more preferably an amylphenol disulfide polymer, and even more preferably an amylphenol disulfide polymer. Examples of commercially available crosslinking aids (F) containing amylphenol disulfide polymers include Suncellar AP (manufactured by Sanshin Chemical Industry Co., Ltd.) and Vultac5 (manufactured by Arkema Japan). The crosslinking aid (F) may be used alone or in combination of two or more types.

[0081] The resin composition containing the crosslinking aid (F) can form a crosslinked molded article with excellent mechanical properties, such as a good balance between tensile strength and elongation. In one embodiment, the crosslinked molded article formed from the resin composition containing the crosslinking aid (F) exhibits high values ​​for both tensile stress at break (TB) and tensile elongation at break (EB), demonstrating an excellent balance between tensile strength and elongation.

[0082] The content of the crosslinking aid (F) in the above resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, even more preferably 0.5 to 5 parts by mass, and particularly preferably 0.7 to 3 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). When the content of the crosslinking aid (F) is above the lower limit, the above resin composition has an excellent balance between tensile strength and elongation. When the content of the crosslinking aid (F) is below the upper limit, the above resin composition has excellent mechanical strength, and the wire coating material obtained from the above resin composition has flexibility suitable for the application.

[0083] <Other ingredients> The above resin composition may further contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include magnesium oxide, processing aids, antioxidants, softeners, crosslinking aids other than crosslinking aid (F), hygroscopic agents, crosslinking agents, crosslinking accelerators, activators, foaming agents, foaming aids, plasticizers, tackifiers, colorants, and polymers other than copolymers (S1) and copolymers (S2). Other components may be used individually or in combination of two or more.

[0084] (Magnesium oxide) The above resin composition may also contain magnesium oxide. By including magnesium oxide in the above resin composition, a crosslinked molded article with excellent mechanical strength and heat aging resistance can be produced. Furthermore, since copolymer (S1) has excellent compatibility with magnesium oxide, a crosslinked molded article containing magnesium oxide can be suitably produced with a small amount of crosslinking agent.

[0085] Examples of magnesium oxide include powdered magnesium oxide used for industrial purposes. Magnesium oxide can also be surface-treated with fatty acids (e.g., stearic acid, hydroxystearic acid, higher fatty acids, and their alkali metal salts), resin acids (e.g., abietic acid), fatty acid amides, or fatty acid esters.

[0086] Examples of commercially available magnesium oxide products include Kyowa Mag® 150 (manufactured by Kyowa Chemical Industry Co., Ltd.), Kyowa Mag® 30 (manufactured by Kyowa Chemical Industry Co., Ltd.), and Magsalat® 30 (surface-treated product, manufactured by Kyowa Chemical Industry Co., Ltd.).

[0087] When the above resin composition contains magnesium oxide, the magnesium oxide content in the above resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, even more preferably 1 to 8 parts by mass, and particularly preferably 3 to 7 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). When the magnesium oxide content is within this range, a crosslinked molded article with particularly excellent mechanical strength and heat aging resistance can be produced.

[0088] (Processing aid) The above resin composition may contain processing aids. Known processing aids that can be incorporated into general rubber compositions can be used as processing aids. Examples of processing aids include fatty acids such as ricinoleic acid, stearic acid, palmitic acid, and lauric acid, fatty acid salts such as zinc laurate, barium stearate, zinc stearate, and calcium stearate, and esters. Of these, stearic acid is preferred.

[0089] Examples of commercially available processing aids include Sakura (manufactured by NOF Corporation, powdered stearic acid). When the above resin composition contains a processing aid, the content of the processing aid in the above resin composition is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). When the content of the processing aid is within this range, the processability such as kneading processability, extrusion processability, and injection moldability is excellent.

[0090] (Anti-aging agent) The above resin composition may also contain an anti-aging agent. As the anti-aging agent, known anti-aging agents that can be incorporated into general rubber compositions can be used. Examples of anti-aging agents include amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

[0091] Examples of amine-based antioxidants include phenylbutylamine and aromatic second amine-based antioxidants such as N,N-di-2-naphthyl-p-phenylenediamine. Examples of phenolic antioxidants include dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane.

[0092] Examples of sulfur-based antioxidants include thioether-based antioxidants, dithiocarbamate-based antioxidants, and imidazole-based antioxidants. An example of a thioether-based antioxidant is bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl] sulfide. An example of a dithiocarbamate-based antioxidant is nickel dibutyldithiocarbamate. Examples of imidazole-based antioxidants include 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, and zinc salts of 2-mercaptobenzoimidazole. Other examples of sulfur-based anti-aging agents include dilauryl thiodipropionate and distearyl thiodipropionate.

[0093] Examples of commercially available anti-aging agents include Irganox 1010 (manufactured by BASF Japan Ltd., tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane) and Sandant MB (manufactured by Sanshin Chemical Industry Co., Ltd., 2-mercaptobenzimidazole).

[0094] If the above resin composition contains an anti-aging agent, the amount of the anti-aging agent in the above resin composition is preferably 0.5 to 7 parts by mass, more preferably 0.5 to 6 parts by mass, even more preferably 1 to 6 parts by mass, and particularly preferably 2 to 5 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). Anti-aging agents may be used individually or in combination of two or more types.

[0095] As an anti-aging agent, it is preferable to use a phenolic anti-aging agent and / or a sulfuric anti-aging agent, more preferably a phenolic anti-aging agent and a sulfuric anti-aging agent, and even more preferably a phenolic anti-aging agent and an imidazole anti-aging agent.

[0096] (Softener) The above resin composition may also contain a softening agent. As a softening agent, known softening agents that are incorporated into rubber compositions can be used. Examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymer substances such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softening agents such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factis). Of these, petroleum-based softening agents are preferred, and paraffin-based process oils are particularly preferred.

[0097] Examples of commercially available softening agents include Diana® Process PW-380 (manufactured by Idemitsu Kosan Co., Ltd., a paraffin-based process oil). The softening agent may be used alone or in combination of two or more types.

[0098] If the above resin composition contains a softening agent, the content of the softening agent in the resin composition is preferably 1 to 150 parts by mass, more preferably 3 to 100 parts by mass, even more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). If the amount of softening agent is within this range, a resin composition with low tack and excellent processability, heat aging resistance, and mechanical properties can be obtained.

[0099] (Crossing aids other than cross-linking aid (F)) The above resin composition may contain crosslinking aids other than crosslinking aid (F). Examples of crosslinking aids other than crosslinking aid (F) include quinoid crosslinking aids, sulfur-based crosslinking aids other than crosslinking aid (F), resin-based crosslinking aids, triazine-based crosslinking aids, polyol-based crosslinking aids, polyamine-based crosslinking aids, maleimide-based crosslinking aids, acrylic-based crosslinking aids, metal oxides, and unsaturated carboxylic acid metal salts.

[0100] Examples of quinoid crosslinking agents include p-quinone dioxime, p,p'-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, and poly-p-dinitrobenzene.

[0101] Examples of sulfur-based crosslinking aids other than crosslinking aid (F) include sulfur, ethylenethiourea, tellurium diethyldithiocarbamate, copper dimethyldithiocarbamate, bismuth dimethyldithiocarbamate, cadmium diethyldithiocarbamate, lead dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, 2,2'-dibenzothiazolyl disulfide, morpholine disulfide, thiuram polysulfide, N,N'-dithio-bis(hexahydro-2H-azepinone-2), and 2-(4'-morpholinodithio)benzothiazole. Examples of resin-based crosslinking aids include alkylphenol formaldehyde resins, triazine-formaldehyde condensates, and hexamethoxymethyl-melamine resins. An example of alkylphenol formaldehyde resin is octylphenol formaldehyde resin. An example of triazine-formaldehyde condensate is melamine-formaldehyde condensate.

[0102] Examples of polyamine-based crosslinking agents include hexamethylenediamine carbamate, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, 4,4'-methylenebis(cyclohexylamine) carbamate, N,N'-disinnamyridene-1,6-hexanediamine, and ammonium benzoate.

[0103] Examples of triazine-based crosslinking agents include 2,4,6-trimercapto-s-triazine, 2-di-n-butylamino-4,6-dimercapto-s-triazine, triallyl isocyanurate, and triallyl cyanurate.

[0104] Examples of polyol-based crosslinking agents include bisphenol A, bisphenol AF, hydroquinone, and pentaerythritol. Examples of maleimide-based crosslinking agents include N,N'-m-phenylenedimaleimide and trimethylolpropane-N,N'-m-phenylenedimaleimide.

[0105] Examples of acrylic crosslinking agents include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, and diethylene glycol dimethacrylate.

[0106] Examples of metal oxides include zinc oxide (e.g., ZnO#1, Zinc Oxide Type 2 (JIS K-1410), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., META-Z102, manufactured by Inoue Lime Industry Co., Ltd.).

[0107] Examples of unsaturated carboxylate metal salts include zinc acrylate, zinc dimethacrylate, and magnesium dimethacrylate.

[0108] Other crosslinking aids besides crosslinking aid (F) include, for example, diallyl phthalate and divinylbenzene.

[0109] Examples of commercially available crosslinking aids other than crosslinking aid (F) include Actor ZMA (manufactured by Kawaguchi Chemical Industry Co., Ltd., zinc dimethacrylate), Sunester EG (manufactured by Sanshin Chemical Industry Co., Ltd., ethylene glycol dimethacrylate), TAIC (manufactured by Nippon Chemical Corporation, triallyl isocyanurate), Highcross M (manufactured by Seiko Chemical Co., Ltd., trimethylolpropane trimethacrylate), and Valnock PM (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., N,N'-m-phenylene bismaleimide). Crosslinking aids other than crosslinking aid (F) may be used individually or in combination of two or more.

[0110] If the above resin composition contains a crosslinking aid other than crosslinking aid (F), the content of the crosslinking aid other than crosslinking aid (F) in the above resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2). The above resin composition may or may not contain a crosslinking aid other than crosslinking aid (F).

[0111] (Desiccant) The above resin composition may also contain a desiccant. Examples of desiccants include calcium oxide, silica gel, sodium sulfate, molecular sieves, and zeolites. Of these, calcium oxide is preferred.

[0112] Desiccant may be used individually or in combination of two or more types. If the above resin composition contains a desiccant, the content of the desiccant in the above resin composition is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 12 parts by mass, even more preferably 0.2 to 10 parts by mass, and particularly preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0113] (Crosslinking agent) The above resin composition preferably contains a crosslinking agent. Examples of crosslinking agents include organic peroxides, sulfur compounds, phenolic resins, hydrosilicone compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, epoxy compounds, and isocyanate compounds. The crosslinking agent is preferably an organic peroxide.

[0114] Examples of organic peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexine-3, and 2,5-dimethyl Examples include 2,5-di-(benzoylperoxy)hexane, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, n-butyl-4,4-bis(tert-butylperoxy)valerate, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and t-butylcumyl peroxide. Among these, dicumyl peroxide, di-t-butyl peroxide, and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferred. Examples of commercially available organic peroxides include DCP-40C (manufactured by NOF Corporation, dicumyl peroxide). The crosslinking agent may be used alone or in combination of two or more types.

[0115] If the above resin composition contains a crosslinking agent, the amount of the crosslinking agent in the above resin composition is preferably 1 to 10 parts by mass, more preferably 1.5 to 6 parts by mass, and even more preferably 2 to 4 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0116] (Activating agent) The above resin composition may also contain an activator. Examples of activators include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triaryl merilate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide moduloides; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds. The activator may be used alone or in combination of two or more types.

[0117] If the above resin composition contains an activator, the amount of the activator in the above resin composition is preferably 0.2 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0118] (Foaming agent) The above resin composition may also contain a foaming agent. Examples of foaming agents include physical foaming agents such as carbon dioxide, nitrogen, air, and water; inorganic foaming agents such as sodium bicarbonate (baking soda), sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; nitroso compounds such as N,N'-dimethyl-N,N'-dinitrosotelephthalamide and N,N'-dinitrosopentamethylenetetramine (DPT); azodicarbonamide (ADCA), azobisisobutyronitrile, azocyclohexylnitrile, and azodiaminobenzene. Examples include azo compounds such as barium azodicarboxylate; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p,p'-oxybis(benzenesulfonyl hydrazide), diphenylsulfon-3,3'-disulfonyl hydrazide, and 4,4'-oxybisbenzenesulfonyl hydrazide (OBSH); and azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulfonyl azide. Among these, inorganic blowing agents are preferred, and sodium bicarbonate is more preferred, because they enable the reduction of specific gravity and increase of crosslink density in foamed molded articles.

[0119] If the above resin composition contains a foaming agent, the amount of foaming agent in the above resin composition is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 10 parts by mass, even more preferably 0.1 to 10 parts by mass, and particularly preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0120] (Foaming agent) The above resin composition may optionally contain a foaming agent along with the foaming agent. The addition of a foaming agent is effective in regulating the decomposition temperature of the foaming agent and homogenizing the bubbles. Examples of foaming agents include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, as well as urea and its derivatives. If the above resin composition contains a foaming aid, the amount of foaming aid in the above resin composition is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, per 100 parts by mass of the foaming agent.

[0121] (polymers other than copolymer (S1) and copolymer (S2)) The above resin composition may also contain polymers other than copolymer (S1) and copolymer (S2). Polymers other than copolymers (S1) and copolymer (S2) include, for example, resins such as polyethylene, polypropylene, and polystyrene, as well as rubbers such as silicone rubber, natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, and chloroprene rubber.

[0122] When the above resin composition contains polymers other than copolymer (S1) and copolymer (S2), the content of polymers other than copolymer (S1) and copolymer (S2) in the above resin composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0123] [Method for manufacturing resin composition for electric wire coating] The above resin composition can be manufactured using a method similar to that used for general rubber compositions. Specifically, it can be manufactured as follows: For example, copolymer (S1), copolymer (S2), reinforcing agent, and other components as needed are kneaded or mixed (first kneading), and then a crosslinking aid (F) and other components as needed are added to the resulting kneaded or mixed product and kneaded (second kneading). It is preferable to add the crosslinking agent during the second kneading. Specifically, copolymer (S1), copolymer (S2), reinforcing agent, and other components as needed are kneaded or mixed at 130 to 170°C for 1 to 10 minutes, preferably at 130 to 150°C for 1 to 8 minutes (first kneading), and then a crosslinking aid (F) and other components as needed are added to the resulting kneaded or mixed product and kneaded at 30 to 80°C for 1 to 20 minutes, preferably at 40 to 60°C for 5 to 15 minutes (second kneading), and then dispensed. The resin composition obtained in this way may be in the form of ribbons or sheets.

[0124] The reinforcing agent may be added during either the first or second mixing stage, but it is preferable to add it during the first mixing stage. When adding other components such as hygroscopic agents, antioxidants, fillers, processing aids, surfactants, plasticizers, thickeners, and tackifiers, it is preferable to add them during the first mixing stage, and it is preferable to add crosslinking aids other than crosslinking aid (F), crosslinking accelerators, and foaming agents during the second mixing stage.

[0125] For the first mixing stage, any known mixing device capable of processing at high temperatures can be used. Examples of mixing devices for the first mixing stage include Banbury mixers, kneaders, and extruders. Examples of mixing devices for the second mixing stage include rollers, kneaders, and extruders, which allow for easy temperature control.

[0126] By dividing the mixing of each component into a first and second mixing stage, the mixing time can be shortened compared to mixing all components together without separation. Furthermore, since cross-linking can be suppressed during the first mixing stage, the temperature during the first mixing stage can be increased, making it possible to remove moisture in a shorter time.

[0127] [Crosslinked molded product] The crosslinked molded article of this disclosure is obtained by crosslinking the above resin composition. The crosslinked molded articles of this disclosure can be obtained, for example, by introducing the resin composition into a crosslinking tank after or simultaneously with molding it into a desired shape using various molding methods, and then heating and crosslinking the molded article. If the resin composition contains a foaming agent, foaming will also proceed along with crosslinking, and a foamed crosslinked molded article will be obtained. Examples of molding methods include using an extrusion molding machine, a calender roll, a press molding machine, an injection molding machine, or a transfer molding machine. A mold may or may not be used during molding and crosslinking. If a mold is not used, the resin composition is usually molded and crosslinked continuously.

[0128] The heating temperature when crosslinking the above resin composition or molded article is preferably 140°C or higher, more preferably 150 to 260°C, and even more preferably 160 to 250°C. The heating time during the crosslinking treatment is preferably 1 to 60 minutes, more preferably 5 to 45 minutes, and even more preferably 8 to 20 minutes. In the crosslinking treatment, in addition to heating baths of heating types such as hot air vulcanization baths (HAV), steam vulcanization baths, glass bead fluidized beds, far-infrared heating furnaces, microwave vulcanization baths (UHF), or thermally molten salt baths (LCM), an electron beam crosslinking apparatus may also be used.

[0129] The above resin composition may be press-molded to perform primary crosslinking, and after obtaining a primary molded body by removing it from the mold, the obtained primary molded body may be secondary crosslinked in a heat transfer medium. Specifically, the above resin composition is press-molded to perform primary crosslinking, preferably at 120 to 200°C for 1 to 20 minutes, more preferably at 150 to 200°C for 10 to 18 minutes, and then removed from the mold to obtain a primary molded body. Next, the obtained primary molded body is secondary crosslinked in a heat transfer medium, preferably at 120 to 180°C for 1 to 24 hours, more preferably at 140 to 160°C for 3 to 12 hours. Examples of heat transfer mediums used for secondary crosslinking include air, water vapor, paraffinic process oil, and molten salt.

[0130] By using the above resin composition, a cross-linked molded article with excellent mechanical properties can be formed. Furthermore, by using the above resin composition, a cross-linked molded article having an electrical resistivity suitable for use as a wire coating material can be formed.

[0131] [Laminated structure] The laminate of this disclosure has a layer (L) including the crosslinked molded body. The above laminate may have layers other than layer (L). Examples of other layers include a semiconducting layer. The semiconductive layer has an resistivity that is greater than that of a conductor made of metal such as copper and aluminum, and less than that of the layer (L) containing the cross-linked molded body.

[0132] The above laminate preferably has a semiconducting layer. The above laminate may contain only one semiconducting layer or two or more semiconducting layers. The semiconducting layer is preferably adjacent to layer (L). The adjacency of layer (L) and the semiconducting layer includes all of the opposing surfaces of layer (L) and the semiconducting layer being in contact, and some of the opposing surfaces of layer (L) and the semiconducting layer being in contact.

[0133] Examples of materials constituting the semiconducting layer include conventionally known materials such as crosslinked polyethylene, polyolefin elastomer, ethylene copolymer, polyolefin rubber, nylon, and polyester. The semiconducting layer may also contain copolymer (S1) and / or copolymer (S2). The semiconductive layer may be composed of only one type of material, or it may be composed of two or more types of materials.

[0134] The semiconductive layer may contain a conductive filler. Examples of conductive fillers include carbon black and carbon nanotubes. Examples of carbon black include furnace black, channel black, acetylene black, and thermal black. The conductive filler may be used alone or in combination of two or more types.

[0135] The semiconductive layer may be uncrosslinked or crosslinked. The above laminate can be manufactured by various known molding methods. Examples of molding methods include co-extrusion molding, in which multiple resins or the above resin composition are simultaneously extruded in a molten state by inflation molding or T-die molding; a method of extruding and laminating the above resin composition onto a single-layer sheet; and a method of stacking single-layer sheets and melt-pressing them together by hot pressing or hot rolling. A semiconductive tape may be used as the semiconductive layer.

[0136] The laminate may be manufactured by crosslinking the resin composition to produce a layer (L), then overlapping and pressing layer (L) with other layers, or by overlapping a layer containing the uncrosslinked resin composition with other layers, and then crosslinking each layer.

[0137] [Applications of cross-linked molded articles and laminates] The above-mentioned cross-linked molded articles and laminates can be used, for example, as wire covering materials such as high-voltage wire covering materials, low-voltage wire covering materials, and marine wire covering materials, as well as as cable covering materials such as ignition cables, cabtyre cables, and high-tension cables. The wire covering materials and cable covering materials are used to cover conductors made of metals such as copper and aluminum.

[0138] The wire and cable coverings may have only an insulating layer, or they may have an internal semiconducting layer, an insulating layer, and an external semiconducting layer. In the wire and cable coverings, the conductor may be covered in this order by the internal semiconducting layer, the insulating layer, and the external semiconducting layer. The cross-linked molded body can be used as an insulating layer.

[0139] One method for manufacturing a wire covering material from the above-mentioned resin composition is to crosslink the composition (molded body) after molding it into a shape that covers a conductor, or simultaneously with the molding process. During the molding process, the resin composition is molded into a shape that covers a conductor using an extrusion molding machine, calender roll, press molding machine, injection molding machine, or transfer molding machine, etc.

[0140] Examples of methods for the above crosslinking treatment include the following methods (a) and (b). (a) A batch-type crosslinking method such as a steam crosslinking method, in which an uncrosslinked resin composition (molded body) molded into a shape that covers a conductor is wound onto a roll and crosslinked in a high-temperature steam oven. (b) (i) the Hien crosslinking method, in which the molded body is crosslinked by immersing it in a high-temperature, pressurized lead bath; (ii) PLCM (Pressure Immersion Crosslinking), in which the molded body is crosslinked by immersing it in a high-temperature, pressurized liquid; (iii) the horizontal continuous crosslinking method, in which the molded body is crosslinked by immersing it in high-temperature, pressurized steam; (iv) continuous crosslinking methods such as the catenary continuous crosslinking method; or (v) crosslinking methods that combine these crosslinking methods.

[0141] When the above laminate is used as a wire covering or cable covering, the wire covering or cable covering may be manufactured, for example, by co-extruding a layer containing the resin composition, an internal semiconducting layer, and an external semiconducting layer into a shape that covers a conductor using an extrusion molding machine, and then by crosslinking the extrusion process. Alternatively, it may be manufactured by wrapping a semiconducting tape around a conductor to form an internal semiconducting layer, then extruding a layer containing the resin composition to cover the internal semiconducting layer, and after further crosslinking the extrusion process, wrapping a semiconducting tape around the conductor to form an external semiconducting layer. Furthermore, it may be manufactured by co-extruding a layer containing the resin composition and an internal semiconducting layer into a shape that covers a wire using an extrusion molding machine, and after crosslinking the extrusion process, wrapping a semiconducting tape around the conductor to form an external semiconducting layer.

[0142] [Example of behavior] This disclosure relates, for example, to the following [1] to

[13] . [1] A copolymer (S1) having a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of the following formulas (I) and (II) in one molecule, An ethylene-α-olefin copolymer (S2) having constituent units derived from ethylene (D) and constituent units derived from α-olefins (E) having 3 to 20 carbon atoms (excluding copolymers corresponding to (S1) above), Reinforcement agent, A phenolic crosslinking aid (F) containing a mono or polysulfide bond is included. Resin composition for covering electric wires. [ka]

[0143] [2] The wire coating resin composition according to claim 1, wherein the crosslinking aid (F) has a structure represented by the following formula (III). [ka] (In formula (III), R represents a hydrocarbon group having 1 to 20 carbon atoms, n and n' represent identical or different integers from 1 to 8, and p represents an integer from 0 to 50.)

[0144] [3] The wire coating resin composition according to [1] or [2], wherein the crosslinking aid (F) comprises an amylphenol disulfide polymer.

[0145] [4] A wire coating resin composition according to any one of [1] to [3], comprising 0.1 to 10 parts by mass of the crosslinking aid (F) per 100 parts by mass of the copolymer (S1) and the copolymer (S2) in total.

[0146] [5] The resin composition for covering electric wires according to any one of [1] to [4], wherein the copolymer (S1) satisfies one or more requirements selected from the following requirements (1) to (5). (1) When the total constituent units contained in the copolymer (S1) are assumed to be 100 mol%, the ratio [A] / [B], which is the ratio of the mole fraction [A] of constituent units derived from ethylene (A) to the mole fraction [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. (2) The mass fraction of constituent units derived from non-conjugated polyene (C) is 0.07 to 10% by mass of copolymer (S1) per 100% by mass. (3) The weight-average molecular weight (Mw) of the copolymer (S1), the mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C) (mass%)), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (i). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 80 ···(i) (4) Complex viscosity η at frequency ω = 0.1 rad / sec, obtained by linear viscoelasticity measurement using a rheometer (190°C). * (ω=0.1) (Pa·seconds) and complex viscosity η at frequency ω = 100 rad / second * (ω=100) The ratio P(η) of (Pa·seconds) * (ω=0.1) / η * (ω=100) The intrinsic viscosity [η] (dL / g) and the mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C) (mass%)) satisfy the following equation (ii). P / ([η] 2.9 ) ≤ (C) Mass fraction × 6 ... (ii) (5) Complex viscosity η at frequency ω = 0.01 rad / sec, obtained by linear viscoelasticity measurement using a rheometer (190°C). * (ω=0.01) (Pa·seconds) and complex viscosity η at frequency ω = 10 rad / second * (ω=10) The (Pa·seconds) and the apparent iodine value derived from the unconjugated polyene (C) satisfy the following equation (iii). Log[η * (ω=0.01) ] / Log[η * (ω=10) ] ≤ 0.0753 × {apparent iodine value derived from unconjugated polyene (C)} + 1.42···(iii)

[0147] [6] A wire coating resin composition according to any one of [1] to [5], wherein the α-olefin (B) having 3 to 20 carbon atoms is propylene.

[0148] [7] The wire coating resin composition according to any one of [1] to [6], wherein the non-conjugated polyene (C) is 5-vinyl-2-norbornene (VNB).

[0149] [8] The resin composition for covering electric wires according to any one of [1] to [7], wherein the copolymer (S1) consists solely of an ethylene-propylene-VNB copolymer.

[0150] [9] The wire coating resin composition according to any one of [1] to [8], wherein the content of copolymer (S1) is 5 parts by mass or more and less than 100 parts by mass relative to 100 parts by mass of the total of copolymer (S1) and copolymer (S2).

[0151]

[10] A crosslinked molded article obtained by crosslinking a wire coating resin composition described in any of [1] to [9].

[0152]

[11] A laminate having a layer (L) containing the crosslinked molded article described in

[10] .

[0153]

[12] The laminate according to

[11] , having a semiconducting layer adjacent to the aforementioned layer (L).

[0154]

[13] A wire covering material comprising the cross-linked molded body described in

[10] . [Examples]

[0155] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0156] [Physical properties of copolymers (S1) and (S2)] The physical properties of copolymers (S1) and (S2) were measured as follows. <Composition of copolymers (S1) and (S2)> The mass fraction (mass%) and the number of moles (mol%) of each constituent unit in the copolymer are as follows: 13 The results were calculated by 13C-NMR. Using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.), the copolymer (S1) was analyzed under the following conditions: measurement temperature: 120°C, measurement solvent: orthodichlorobenzene / deuterated benzene = 4 / 1, and number of integration cycles: 8000.13 The 13C-NMR spectrum was measured.

[0157] <Mooney viscosity> The Mooney viscosity ML(1+4) at 125 °C of the copolymer (S1) was measured using a Mooney viscometer (SMV-301 type manufactured by Shimadzu Corporation) in accordance with JIS K6300-1:2013 under the condition of 125 °C.

[0158] The B value of the copolymer (S1) was calculated based on the following formula using o-dichlorobenzene-d4 / benzene-d6 (4 / 1 [v / v]) as the measurement solvent under the condition of a measurement temperature of 120 °C. 13 The 13C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured and calculated based on the following formula. B value = ([EX] + 2[Y]) / {2 × [E] × ([X] + [Y])} The meanings of [E], [X], [Y], and [EX] are as described above.

[0159] <Limiting viscosity [η]> The limiting viscosity [η] of the copolymer (S1) was measured using an automatic limiting viscometer (manufactured by Separation Co., Ltd.) under the conditions of a temperature of 135 °C and a measurement solvent of decalin.

[0160] <Weight-average molecular weight (Mw)> The weight-average molecular weight (Mw) of the copolymer (S1) is a value in terms of polystyrene measured by 3D-GPC. The measuring apparatus and conditions are as follows. The dn / dc value (differential value of the refractive index n with respect to the concentration c, dn / dc value) required for the determination of 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 injection mass. Apparatus: 3D-High Temperature GPC Apparatus PL-GPC220 type (manufactured by Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT × 2 pieces + TSKgel GMH HR -M(S) × 1 piece (Each piece has an inner diameter of 7.8mmφ and a length of 300mm) Column temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Detector: Differential refractometer (RI) / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Injection volume: 0.5mL Sample concentration: Ca 1.0 mg / mL Sample filtration: Filtered using a 1.0 μm pore size sintered filter.

[0161] <complex viscosity η * > Using an Ares viscoelasticity measuring device (manufactured by Rheometric Scientific) as the rheometer, the complex viscosity η was measured at a frequency ω = 0.01 rad / second under conditions of 190°C and 1.0% strain. * (ω=0.01) Complex viscosity η at frequency ω = 0.1 rad / sec * (ω=0.1) Complex viscosity η at frequency ω = 10 rad / s * (ω=10) and complex viscosity η at frequency ω = 100 rad / sec * (ω=100) (All units are Pa·seconds) were measured. From the results obtained, η * (ω=0.1) and η * (ω=100) The P value (η) is the ratio of the complex viscosity to that of * (ω=0.1) / η * (ω=100) ), and Log[η * (ω=0.01) ] / Log[η * (ω=10) The result was calculated.

[0162] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of copolymer (S1) was determined by measurement using a differential scanning calorimeter (DSC) under the following conditions. Using a differential scanning calorimeter (RDC220, SII Corporation), approximately 10 mg of the sample was heated from 30°C to 200°C at a heating rate of 50°C / min under a nitrogen atmosphere and held at 200°C for 10 minutes. It was then cooled to -100°C at a heating rate of 10°C / min and held at -100°C for 5 minutes, after which it was heated to 200°C at a heating rate of 10°C / min. The temperature based on the glass transition at this time was defined as the glass transition temperature (Tg).

[0163] [Copolymer (S1-1)] In the following examples and comparative examples, copolymer (S1-1) obtained in Production Example 1 was used as copolymer (S1).

[0164] <Manufacturing Example 1> In a 300 L polymerizer equipped with stirring blades, 58.3 L / hr of dehydrated and purified hexane solvent was continuously supplied from line 1, 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 was continuously supplied from 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 supplied to the polymerization reactor from separate lines. Copolymerization was carried out under conditions of a polymerization temperature of 87°C, a total pressure of 1.6 MPaG, and a residence time of 1.0 hour. In this way, a solution containing 20% ​​by mass of an ethylene-propylene-VNB copolymer formed from ethylene, propylene, and VNB was obtained. A small amount of methanol was added to the polymerization reaction solution withdrawn from the bottom of the polymerizer to stop the polymerization reaction, and the ethylene-propylene-VNB copolymer was separated from the solvent by steam stripping. After that, it was dried under reduced pressure at 80°C overnight. Through the above procedure, an ethylene-propylene-VNB copolymer (S1-1) was obtained. The physical properties of the obtained copolymer (S1-1) were measured using the method described above. The results are shown in Table 1.

[0165] [Table 1]

[0166] The raw materials used in the examples are listed below. • Copolymer (S2-1): Manufactured by Mitsui Chemicals, Inc., Mitsui EPT 0045, ethylene-propylene copolymer, Mooney viscosity (ML(1+4)100℃): 40, ethylene-derived component content: 51% by mass, density: 860 kg / m³ 3 , Weight average molecular weight (Mw): 213,000, Number average molecular weight (Mn): 11,500 • Magnesium oxide: Manufactured by Kyowa Chemical Industry Co., Ltd., Kyowa Mag® (registered trademark) 150 • Processing aid: Powdered stearic acid (Sakura variety), manufactured by NOF Corporation, stearic acid • Reinforcement agent: Hytron A, manufactured by Takehara Chemical Industry Co., Ltd., talc • Anti-aging agent (1): BASF Japan Ltd., Irganox 1010, Tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane • Anti-aging agent (2): Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd., 2-mercaptobenzimidazole • Softener: Diana® Process PW-380, manufactured by Idemitsu Kosan Co., Ltd., paraffin-based process oil ·Organic peroxide: NOF Corporation, DCP-40C, Dicumyl peroxide (purity: 40% by mass), Half-life temperature at 1 minute: 171°C, Half-life temperature at 10 hours: 117°C

[0167] • Crosslinking agent (1): Manufactured by Kawaguchi Chemical Industry Co., Ltd., Actor ZMA, zinc dimethacrylate • Crosslinking agent (2): Sanshin Chemical Industry Co., Ltd., Sunester EG, ethylene glycol dimethacrylate • Crosslinking agent (3): TAIC, manufactured by Nippon Chemical Corporation, triallyl isocyanurate (triallyl isocyanurate content: 100% by mass) • Crosslinking agent (4): Highcross M, manufactured by Seiko Chemical Co., Ltd., trimethylolpropane trimethacrylate • Crosslinking agent (5): Valnock PM, N,N'-m-phenylenebismaleimide, manufactured by Ouchi Shinko Chemical Industry Co., Ltd. • Crosslinking aid (6): Sanshin Chemical Industry Co., Ltd., Suncellar AP, amylphenol disulfide polymer (amylphenol disulfide polymer content: 75% by mass, white carbon content: 25% by mass)

[0168] [Example 1] <Preparation of uncrosslinked composition> In the first stage, the raw materials shown in Raw Materials 1 of Table 2 were kneaded at 140°C for 2 minutes using a BB-L1800 Banbury mixer (manufactured by Kobe Steel, Ltd.). After that, the ram was raised and cleaned, and kneaded for another minute, then discharged at approximately 150°C to obtain the first stage mixture (A kneading). Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C and a rear roll surface temperature of 50°C, a front roll rotation speed of 15 rpm and a rear roll rotation speed of 18 rpm), and the raw materials shown in Raw Materials 2 of Table 2 were added to it, and the mixture was kneaded for 10 minutes to obtain an uncrosslinked copolymer composition (B kneading).

[0169] [Example 2, Comparative Examples 1-9] The procedure was carried out in the same manner as in Example 1, except that the types and amounts of raw materials 1 and 2 used in Example 1 were changed to those shown in Table 2.

[0170] [Hardness Test: Hardness (Durometer-A (shore-A))] The compositions of the examples or comparative examples were press-molded in a mold at 180°C for 10 minutes using a press molding machine to produce sheets with a thickness of 2 mm. The hardness of the sheets was measured in accordance with the description of "hardness test" in item 7 of JIS K7312 (1996) "Physical test methods for thermosetting polyurethane elastomer molded articles" and the description of test type A of "durometer hardness test" in item 6 of JIS K6253 (2006) "Vulcanized rubber and thermoplastic rubber - Method for determining hardness".

[0171] [Tensile test: Modulus, tensile stress at fracture, tensile elongation at fracture] A 2mm thick sheet was punched out to prepare a Type 3 dumbbell test specimen as described in JIS K6251;1993. Using this specimen, a tensile test was performed according to the method specified in Section 3 of JIS K6251, under the conditions of a measurement temperature of 25°C and a tensile speed of 500 mm / min. The tensile stress (100% modulus (M100)), tensile stress at fracture (TB), and tensile elongation at fracture (EB) at 100% elongation were measured.

[0172] [Electrical properties: Volume resistivity] The compositions of the examples or comparative examples were press-molded in a mold at 180°C for 10 minutes using a press molding machine to produce sheets with a thickness of 1 mm. A volume resistivity test was performed in accordance with JIS K6911:1995, under the conditions of applied voltage: 500V and charging time: 1 minute, and the volume resistivity of the above 1 mm thick sheets was measured. Table 2 shows the average values.

[0173] [Table 2]

Claims

1. A copolymer (S1) having a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of the following formulas (I) and (II) in one molecule, An ethylene-α-olefin copolymer (S2) having constituent units derived from ethylene (D) and constituent units derived from α-olefins (E) having 3 to 20 carbon atoms (excluding copolymers corresponding to (S1) above), Reinforcement agent, A phenolic crosslinking aid (F) containing a mono or polysulfide bond is included. Resin composition for covering electric wires. 【Chemistry 1】

2. The wire coating resin composition according to claim 1, wherein the crosslinking aid (F) has a structure represented by the following formula (III). 【Chemistry 2】 (In formula (III), R represents a hydrocarbon group having 1 to 20 carbon atoms, n and n' represent the same or different integers from 1 to 8, and p represents an integer from 0 to 50.)

3. The wire coating resin composition according to claim 1, wherein the crosslinking aid (F) comprises an amylphenol disulfide polymer.

4. The wire coating resin composition according to claim 1, comprising 0.1 to 10 parts by mass of the crosslinking aid (F) with respect to a total of 100 parts by mass of the copolymer (S1) and the copolymer (S2).

5. The wire coating resin composition according to claim 1, wherein the copolymer (S1) satisfies one or more of the following requirements (1) to (5). (1) When the total number of constituent units contained in the copolymer (S1) is 100 mol%, the ratio [A] / [B], which is the ratio of the mole fraction [A] of constituent units derived from ethylene (A) to the mole fraction [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. (2) The mass fraction of constituent units derived from non-conjugated polyene (C) is 0.07 to 10% by mass of the copolymer (S1) in 100% by mass. (3) The weight-average molecular weight (Mw) of the copolymer (S1), the mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C) (mass%)), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (i). 4.5 ≤ Mw × mass fraction of (C) / 100 / molecular weight of (C) ≤ 80 ... (i) (4) Complex viscosity η at frequency ω = 0.1 rad / sec, obtained by linear viscoelasticity measurement using a rheometer (190°C) ＊ (ω=0.1) (Pa·seconds) and the complex viscosity η at frequency ω = 100 rad / second ＊ (ω=100) The ratio P(η) to (Pa·seconds) ＊ (ω=0.1) / η ＊ (ω=100) The intrinsic viscosity [η] (dL / g) and the mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C) (mass%)) satisfy the following equation (ii). P / ([η] 2.9 ) ≤ mass fraction of (C) × 6... (ii) (5) Complex viscosity η at frequency ω = 0.01 rad / second, obtained by linear viscoelasticity measurement using a rheometer (190°C) * (ω=0.01) (Pa·seconds) and the complex viscosity η at frequency ω = 10 rad / second * (ω=10) The (Pa·second) and the apparent iodine value derived from the unconjugated polyene (C) satisfy the following equation (iii). Log[η] * (ω=0.01) ] / Log[η * (ω=10) ] ≤ 0.0753 × {Apparent iodine value derived from unconjugated polyene (C)} + 1.42 ... (iii)

6. The wire coating resin composition according to claim 1, wherein the α-olefin (B) having 3 to 20 carbon atoms is propylene.

7. The wire coating resin composition according to claim 1, wherein the non-conjugated polyene (C) comprises 5-vinyl-2-norbornene (VNB).

8. The wire coating resin composition according to claim 1, wherein the copolymer (S1) consists solely of an ethylene-propylene-VNB copolymer.

9. The wire coating resin composition according to claim 1, wherein the content of copolymer (S1) is 5 parts by mass or more and less than 100 parts by mass relative to a total of 100 parts by mass of copolymer (S1) and copolymer (S2).

10. A crosslinked molded article obtained by crosslinking the wire coating resin composition described in any one of claims 1 to 9.

11. A laminate having a layer (L) containing the crosslinked molded article described in claim 10.

12. The laminate according to claim 11, further comprising a semiconducting layer adjacent to the aforementioned layer (L).

13. A wire covering material comprising a crosslinked molded body as described in claim 10.

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