Copolymer composition and its crosslinked product

Abstract

To provide a polymer composition and its crosslinked product that exhibits excellent color resistance, tensile fracture stress, and compression set. [Solution] A copolymer composition comprising 100 parts by mass of an ethylene-α-olefin-non-conjugated polyene copolymer (S) having constituent units derived from ethylene (A), constituent units derived from an α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from a non-conjugated polyene (C) containing a total of two or more specific substructures in one molecule, 0.5 to 50 parts by mass of a hydrosilyl group-containing compound (Y), and 10 to 300 parts by mass of a crystalline olefin polymer (T), wherein the copolymer (S) satisfies specific requirement (i) and at least a portion of it is crosslinked.

Description

[Technical Field]

[0001] This invention relates to copolymer compositions and their crosslinked products. [Background technology]

[0002] Olefin-based thermoplastic elastomers, which are obtained by crosslinking a composition of ethylene-α-olefin-non-conjugated polyene copolymer and a crystalline olefin polymer with an organic peroxide or phenolic resin, are lightweight and easily recyclable, making them energy-saving and resource-saving thermoplastic elastomers that are widely used, particularly as a substitute for vulcanized rubber, in automotive parts such as hoses, pipes, and boots (blow-molded products) (for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-294714 [Patent Document 2] Japanese Patent Publication No. 2011-202136 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, olefin-based thermoplastic elastomers crosslinked with organic peroxides had the problem of poor mechanical properties, and olefin-based thermoplastic elastomers crosslinked with phenolic resins had the problem of poor color resistance.

[0005] The object of the present invention is to provide a polymer composition and its crosslinked product that exhibits excellent color resistance, tensile fracture stress, and compression set. [Means for solving the problem]

[0006] The inventors of the present invention have diligently studied to solve the above problems and have found that the above problems can be solved according to the following embodiments, and have completed the present invention. Embodiments of the present invention are shown below.

[0007] [1] 100 parts by mass of an ethylene-α-olefin-non-conjugated polyene copolymer (S) having constituent units derived from ethylene (A), constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in one molecule, 0.5 to 50 parts by mass of a hydrosilyl group-containing compound (Y), It contains 10 to 300 mass of a crystalline olefin polymer (T), The copolymer (S) satisfies the following requirement (i): A copolymer composition in which at least a portion is crosslinked. [ka] Requirement (i): The number of long-chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. 1000C The natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following equation (1). LCB 1000C ≤1 - 0.07 × Ln(Mw)···Equation (1)

[0008] [2] The copolymer composition according to item [1], wherein the copolymer (S) satisfies the following requirements (ii) and (iii). Requirement (ii): 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-olefins (B) having 3 to 20 carbon atoms, is 40 / 60 to 90 / 10. Requirement (iii): The mass fraction of constituent units derived from the non-conjugated polyene (C) is 0.1 to 6.0 mass% of all constituent units of the copolymer (S).

[0009] [3] The copolymer composition according to item [1] or [2], wherein the copolymer (S) satisfies any one or more of the following requirements (iv) and (v). Requirement (iv): The weight average molecular weight (Mw) of the copolymer (S), the mass fraction of the structural unit 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 (2). 4.5 ≦ Mw × (mass fraction of (C)) / 100 / (molecular weight of (C)) ≦ 80 ··· Formula (2) Requirement (v): The ratio P [η * (ω=0.1) (Pa·s)] at a frequency ω = 0.1 rad / s to the complex viscosity η * (ω=100) (Pa·s) at a frequency ω = 100 rad / s, the intrinsic viscosity [η] of the copolymer (S), and the mass fraction of the said (C) satisfy the following formula (3). * (ω=0.1) / η * (ω=100) ] and the intrinsic viscosity [η] of the copolymer (S) and the mass fraction of the said (C) satisfy the following formula (3). P / ([η] 2.9 ) ≦ (mass fraction of (C)) × 6 ··· Formula (3)

[0010] [4] The copolymer composition according to any one of items [1] to [3], wherein the non-conjugated polyene (C) contains 5-vinyl-2-norbornene.

[0011] [5] The copolymer composition according to any one of items [1] to [4], wherein the hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule.

Chemical formula

[0012] [6] The copolymer composition further comprises a platinum-based catalyst, The copolymer composition according to any one of items [1] to [5], comprising 0.00001 to 0.030 parts by mass of the platinum-based catalyst per 100 parts by mass of the copolymer (S).

[0013] [7] The copolymer composition further comprises a reaction inhibitor, The copolymer composition according to any one of claims [1] to [6], comprising 0.01 to 10 parts by mass of the reaction inhibitor per 100 parts by mass of the copolymer (S).

[0014] [8] The copolymer composition further comprises an organic peroxide, A copolymer composition according to any one of claims [1] to [7], comprising 0.001 to 3.0 parts by mass of the organic peroxide per 100 parts by mass of the copolymer (S).

[0015] [9] The copolymer composition further comprises a crosslinking aid, The copolymer composition according to item [8], wherein the amount of the crosslinking aid is 0.5 to 10 moles per mole of the organic peroxide.

[0016]

[10] A method for producing a copolymer composition according to any one of items [1] to [9], comprising the step of dynamically crosslinking the copolymer (S) and the crystalline olefin polymer (T) in the presence of a hydrosilyl group-containing compound (Y).

[0017]

[11] A crosslinked copolymer composition according to any one of the items [1] to [9].

[0018] A molded article comprising the crosslinking material described in item

[12]

[11] .

[0019] Automotive parts containing the crosslinking material described in item

[13]

[11] .

[0020] Automotive surface materials including the crosslinking material described in item

[14]

[11] .

[0021] Automotive hoses containing the crosslinking material described in item

[15]

[11] .

[0022] Automotive boots containing the crosslinking material described in item

[16]

[11] . [Effects of the Invention]

[0023] The present invention provides polymer compositions and crosslinked products thereof that exhibit excellent color resistance, tensile fracture stress, and compression set. [Modes for carrying out the invention]

[0024] The present invention will be described in detail below.

[0025] <Copolymer composition> The copolymer composition of the present invention (hereinafter also referred to as "the composition of the present invention") comprises an ethylene-α-olefin-nonconjugated polyene copolymer (S), a hydrosilyl group-containing compound (Y), and a crystalline olefin polymer (T), and at least a portion of these is crosslinked.

[0026] <Ethylene-α-olefin-nonconjugated polyene copolymer (S)> The ethylene-α-olefin-non-conjugated polyene copolymer (S) (hereinafter also referred to as "polymer (S)") contains constituent units derived from ethylene (A), constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from non-conjugated polyene (C). The non-conjugated polyene (C) is 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. It is preferable that at least a portion of the copolymer (S) is crosslinked.

[0027] [ka]

[0028] 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 and 1-butene being more preferred, and propylene being particularly preferred. Such α-olefins are preferred because their raw material costs are relatively low, the resulting copolymers exhibit excellent mechanical properties, and crosslinked products with rubber elasticity can be obtained. The α-olefin (B) may be used alone or in combination of two or more types.

[0029] 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. Since they are readily available, the resulting copolymers have good crosslinkability, and the heat resistance of the composition is easily improved, it is preferable that the unconjugated polyene (C) contains VNB, and more preferably VNB, from the viewpoint of improving tensile fracture stress and compression set. The unconjugated polyene (C) may be used alone or in combination of two or more types.

[0030] The copolymer (S) may further contain constituent units derived from the non-conjugated polyene (D). The non-conjugated polyene (D) is a non-conjugated polyene that contains only one substructure selected from the group consisting of formulas (I) and (II) in each molecule.

[0031] Examples of non-conjugated polyenes (D) 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 (D) 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. The non-conjugated polyene (D) may be used alone or in combination of two or more types.

[0032] The copolymer (S) 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 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 (S) 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 (S) to contain constituent units derived from biomass-derived monomers from the viewpoint of reducing environmental impact.

[0033] The copolymer (S) 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 the copolymer (S) 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 the copolymer (S) to contain constituent units derived from chemically recycled monomers from the viewpoint of reducing environmental impact (mainly waste reduction).

[0034] The copolymer (S) preferably satisfies requirement (i) below, and more preferably satisfies requirement (ii) and requirement (iii). In addition to satisfying requirement (ii) and requirement (iii), the copolymer (S) preferably satisfies one or more of requirement (iv) and requirement (v), and more preferably satisfies requirement (iv) and requirement (v).

[0035] The copolymer (S) preferably contains an ethylene-propylene-VNB copolymer, and more preferably consists solely of an ethylene-propylene-VNB copolymer. When the copolymer (S) contains an ethylene-α-olefin-non-conjugated polyene copolymer other than the ethylene-propylene-VNB copolymer, the content of the ethylene-propylene-VNB copolymer in 100% by mass of copolymer (S) is preferably more 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.

[0036] <Requirement (i)> The number of long-chain branches (LCB) per 1000 carbon atoms obtained using 3D-GPC. 1000C The natural logarithm of the weight-average molecular weight (Mw) (Ln(Mw)) satisfies the following equation (1). LCB 1000C ≦1-0.07×Ln(Mw)...Equation (1)

[0037] Formula (1) above specifies the upper limit of the long-chain branching content per unit carbon number of the copolymer. That is, requirement (i) means that the proportion of long-chain branching in the copolymer is small. When copolymer (S) satisfies requirement (i), it exhibits excellent curing properties when crosslinked with hydrosilicone. Furthermore, the crosslinked molded article obtained using it exhibits excellent heat aging resistance.

[0038] The copolymer (S) more preferably satisfies the following formula (1-1). LCB 1000C ≦1-0.071×Ln(Mw)...Equation (1-1) In equations (1) and (1-1) above, Mw and LCB 1000C This value was obtained by structural analysis using 3D-GPC. Specifically, in this specification, it is obtained as follows.

[0039] Using a 3D high-temperature GPC apparatus (PL-GPC220, manufactured by Polymer Laboratories), the absolute molecular weight distribution of ethylene-α-olefin-non-conjugated polyene copolymer (S) is determined, and the intrinsic viscosity is simultaneously determined using a viscometer. The main measurement conditions are 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 (manufactured by Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT x 2 bottles + TSKgel GMH HR -M(S)×1 piece (Each piece has an inner diameter of 7.8mmφ and a length of 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: Ca 1.5 mg / mL Sample filtration: Filtered using a 1.0 μm pore size sintered filter. The dn / dc value required to determine the absolute molecular weight is determined for each sample based on the dn / dc value (derivative value of refractive index n with respect to concentration c) of standard polystyrene (molecular weight 190,000), which is 0.053, and the response intensity of a differential refractometer per unit injection mass.

[0040] Long-chain branching parameter g' for each eluted component i This was calculated from equation (v-1) based on the relationship between the intrinsic viscosity measured in decalin at 135°C, obtained from a viscometer, and the absolute molecular weight obtained from a light scattering photometer.

[0041]

number

[0042] Here, [η] = KM v The relationship v = 0.725 was applied. This equation is called the Mark-Houwink-Sakurada equation, where K is the solvent constant, M is the absolute molecular weight, and v represents the morphology of the polymer chain at the measurement temperature in the measurement solvent (i.e., the shape of the molecule, the degree of bending, etc., and how the molecule spreads). Furthermore, the average values ​​for each value were calculated as g' using the following formulas (v-2), (v-3), and (v-4). Note that the Trendline, assuming only short-chain branching, was determined for each sample.

[0043]

number

[0044] Furthermore, the weight-average long-chain branching parameter g' is expressed by the above formula (v-3). w Using this, the number of branching points per molecular chain is BrNo, and the number of long-chain branches per 1000 carbon atoms is LCB. 1000CThe degree of branching λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer equation (v-5), and LCB was also calculated. 1000C The calculations for λ were performed using the following equations (v-6) and (v-7). g is a long-chain branching parameter derived from the radius of inertia Rg, and the following simple correlation is established between it and g', which is derived from the intrinsic viscosity. g=g' (1 / ε) Various values ​​have been proposed for ε in the above equation depending on the shape of the numerator. Here, we performed the calculation assuming ε = 1 (i.e., g' = g).

[0045]

number

[0046] λ = BrNo / M···(v-6) LCB 1000C =λ × 14000···(v-7) In equation (v-7), 14000 represents the molecular weight of 1000 methylene (CH2) units.

[0047] <Requirement (ii)> 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-olefins (B) with 3 to 20 carbon atoms, is between 40 / 60 and 90 / 10. The ratio [(A1) / (A2)] 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.

[0048] If the copolymer (S) satisfies requirement (ii), the crosslinked product obtained from the composition containing such copolymer tends to have excellent rubber elasticity, flexibility, and mechanical strength.

[0049] When the total constituent units contained in the copolymer (S) 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%.

[0050] <Requirement (iii)> The mass fraction of constituent units derived from non-conjugated polyene (C) is 0.1 to 6.0 mass% relative to the total constituent units of the copolymer (S). The mass fraction of constituent units derived from non-conjugated polyene (C) is preferably 0.1 to 5.5 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%.

[0051] When copolymer (S) satisfies requirement (iii), the crosslinked product obtained from the composition containing such copolymer tends to have sufficient hardness and excellent mechanical properties. When copolymer (S) satisfies requirement (iii), it tends to have excellent crosslinking properties and exhibit a large crosslinking rate.

[0052] If the copolymer (S) further contains constituent units derived from a non-conjugated polyene (D), the mass fraction of the constituent units is preferably 20% by mass or less, more preferably 8.0% by mass or less, and even more preferably 0.01 to 8.0% by mass, of 100% by mass of the copolymer (S).

[0053] 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 mole fraction of constituent units derived from non-conjugated polyene (C), the mass fraction of constituent units derived from ethylene (A), the mass fraction of constituent units derived from non-conjugated polyene (C), and the mass fraction of constituent units derived from non-conjugated polyene (D) were obtained using the apparatus and conditions described in the Examples section below. 13 It can be calculated by measuring the 1C-NMR spectrum.

[0054] <Requirement (iv)> The weight-average molecular weight (Mw) of the copolymer (S), 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 equation (2). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 80 ... (2)

[0055] The equation (2) in requirement (iv) is preferably the following equation (2a). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 75 ... (2a) The equation (2) of requirement (iv) is preferably the following equation (2b). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 70 ... (2b)

[0056] Requirement (iv) represents the content of non-conjugated polyene (C) constituent units per weight-average molecular weight (Mw) in the copolymer (S). When the copolymer (S) satisfies requirement (iv), the composition exhibits sufficient crosslinkability and tends to have a high crosslinking rate. Furthermore, the crosslinked product formed from the composition tends to have a good balance of mechanical properties and heat aging resistance.

[0057] The weight-average molecular weight (Mw) of the copolymer (S) refers to the value measured by 3D-GPC under the conditions described in the Examples section below.

[0058] <Requirement(v)> The complex viscosity η at a frequency ω = 0.1 rad / sec was obtained by linear viscoelasticity measurement using a rheometer (190°C). * (ω=0.1) Complex viscosity η at frequency ω = 100 rad / s in Pa·s * (ω=100) P(η) is the ratio 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 (3). P / ([η] 2.9 ) ≤ (C) Mass fraction × 6 ... (3)

[0059] The equation (3) of requirement (v) is preferably the following equation (3a). P / ([η] 2.9 ) ≤ (C) Mass fraction × 5.7···(3a)

[0060] ratio P(η * (ω=0.1) / η * (ω=100) The P / ([η]) (hereinafter also referred to as the "P value") represents the frequency dependence of viscosity. Therefore, the left side of equations (3) and (3a) is P / ([η] 2.9 Although 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 (S) has fewer long-chain branches than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, and is therefore thought to satisfy equation (3) or (3a).

[0061] 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.

[0062] The copolymer (S) preferably satisfies the following requirement (vi). <Requirements (vi)> The complex viscosity η at a frequency ω = 0.01 rad / sec was 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 (4). Log[η * (ω=0.01) ] / Log[η * (ω=10) ] ≤ 0.0753 × {apparent iodine value derived from unconjugated polyene (C)} + 1.42···(4)

[0063] In equation (4), 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 (S) satisfies equation (4) because the degree of long-chain branching is not too high.

[0064] complex viscosity η * (ω=0.01) and complex viscosity η * (ω=10) The complex viscosity η in requirement (iv) 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 determined by formula (5). (C) Apparent iodine value derived from (C) = Mass fraction of (C) × 253.81 / Molecular weight of (C) ... (5)

[0065] In the copolymer (S), 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 (2) and (3), etc., it is preferable that the "mass fraction of (C)" is the "mass fraction of the constituent units derived from VNB".

[0066] As described above, when the copolymer (S) contains constituent units derived from ethylene (A), α-olefins having 3 to 20 carbon atoms (B), non-conjugated polyenes (C), and non-conjugated polyenes (D), the mass fraction of constituent units derived from non-conjugated polyenes (D) 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 (D) is 100% by mass).

[0067] The copolymer (S) preferably satisfies the following requirement (vii). <Requirement (vii)> 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 (S) [Ln(Mw)] satisfy the following equation (6). 6 - 0.45 × Ln(Mw) ≤ (C) Mass fraction ≤ 10···(6) When the copolymer (S) satisfies requirement (vii), such copolymer is preferable because it suppresses the formation of branched structures and yields a crosslinked product with sufficient crosslink density.

[0068] The copolymer (S) preferably satisfies the following requirement (viii). <Requirement (viii)> The B value, expressed by the following formula (7), is 1.00 or greater. B value=([AB]+2[C]) / [2×[A]×([B]+[C])]···(7) In equation (7), [A], [B], and [C] 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 [AB] represents the ethylene-α-olefin dyad chain fraction with 3 to 20 carbon atoms. The B value is preferably 1.00 to 1.80, more preferably 1.10 to 1.40, and even more preferably 1.15 to 1.30.

[0069] Copolymer (S), when meeting requirement (viii), 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 (S), where [A], [B], [C], and [AB] in equation (7) 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.

[0070] The intrinsic viscosity [η] of the copolymer (S) is preferably 0.1 to 5.0 dL / g, more preferably 0.5 to 4.5 dL / g, even more preferably 1.0 to 4.0 dL / g, even more preferably 1.5 to 3.5 dL / g, and particularly preferably 2.0 to 3.0 dL / g. If the intrinsic viscosity [η] of the copolymer (S) 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 (S) is below the upper limit, it is easier to obtain a copolymer composition with superior processability. The intrinsic viscosity [η] of the copolymer (S) can be adjusted by the amount of hydrogen feed during polymerization. The intrinsic viscosity [η] of the copolymer (S) is the value measured in decalin at 135°C.

[0071] The weight-average molecular weight (Mw) of copolymer (S) is preferably 10,000 to 900,000, more preferably 150,000 to 800,000, even more preferably 300,000 to 700,000, even more preferably 400,000 to 670,000, and particularly preferably 450,000 to 650,000. The weight-average molecular weight (Mw) of the copolymer (S) can be measured by 3D-GPC using the apparatus and conditions described in the Examples section.

[0072] It is preferable that the intrinsic viscosity [η] and weight-average molecular weight (Mw) of the copolymer (S) are both within the aforementioned range.

[0073] Mooney viscosity of copolymer (S) ML (1+4) 125°C is preferably 10-90°C, more preferably 40-80°C, even more preferably 50-75°C, and particularly preferably 60-75°C. Mooney viscosity ML (1+4) The composition containing copolymer (S) with a temperature of 125°C within the aforementioned range exhibits excellent roll processability even in high-hardness, oil-free formulations, good post-processing (ribbon handling properties), and tends to have excellent rubber properties. Details of the Mooney viscosity measurement conditions are described in the Examples section.

[0074] The glass transition temperature (Tg) of the copolymer (S) 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. The lower limit of the glass transition temperature (Tg) of the copolymer (S) is, for example, -80°C. When the glass transition temperature (Tg) of the copolymer (S) is within the above range, the resulting crosslinked product tends to have excellent low-temperature properties. Details of the Tg measurement conditions are described in the Examples section.

[0075] Copolymer (S) can be obtained, for example, by copolymerizing ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, a non-conjugated polyene (C), and optionally a non-conjugated polyene (D). It is preferable that copolymer (S) is obtained by copolymerizing the monomers in the presence of a metallocene compound, and more preferably by copolymerizing the monomers in the presence of a catalyst system containing a metallocene compound. Copolymer (S) can be produced, for example, by a production method using a metallocene catalyst described in Japanese Patent Application Publication No. 2018-119096 and International Publication No. 2015 / 122495.

[0076] The copolymer (S) may be used alone or in combination of two or more types. The content of copolymer (S) in the composition of the present disclosure is preferably 10% by mass or more, more preferably 10 to 50% by mass, even more preferably 15 to 45% by mass, and particularly preferably 20 to 40% by mass, based on 100% by mass of the composition.

[0077] <Hydrosilyl group-containing compound (Y)> The hydrosilyl group-containing compound (Y) (hereinafter also referred to as "compound (Y)") is preferably an organohydrogenpolysiloxane represented by the following formula (a). Compound (Y) preferably has at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in one molecule.

[0078] [ka]

[0079] The meanings of each symbol in equation (a) are as follows: n and p are independently either 0 or a positive number. m is between 1 and 20. The sum of n, m, and p is between 5 and 50. Multiple R 1 and R 2 Each of these is independently a monovalent alkyl group. There are multiple R 1 Each of these is an alkyl group independently. There are multiple R 2 These are each an alkyl group independently. 1 R 2 It may be the same alkyl group as before, or a different alkyl group. In the alkyl group, some of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms. R a This is an aralkyl group. The two Rs are R independently 1 , R 2 , hydrogen atom, and R a R is a group selected from the group consisting of the following, and the two Rs may be the same or different. However, when n=1, at least one of the two Rs is a hydrogen atom, and when n=0, both Rs are hydrogen atoms. 1 or R 2 It is preferable that this be the case.

[0080] A crosslinked product obtained by crosslinking a composition containing a copolymer (S) and a compound (Y) as a crosslinking agent tends to have low odor and excellent heat aging resistance. In addition, the composition can be handled in air. The crosslinked product is preferable in that it has excellent color resistance, tensile fracture stress, and compression set.

[0081] Compound (Y) is a linear organohydrogenpolysiloxane with a relatively low degree of siloxane polymerization and containing at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms within a single molecule.

[0082] In formula (a), m is the number of diorganosiloxy units having a silicon atom bonded aralkyl group. m is 1 to 20, preferably 2 to 10, more preferably 2 to 8, and even more preferably 3 to 6.

[0083] In equation (a), n is the number of organohydrogensiloxy units having silicon-bonded hydrogen atoms. n may be 0 or 1, but when n=1, at least one of the two R atoms is a hydrogen atom, and when n=0, both R atoms are hydrogen atoms. That is, the organohydrogenpolysiloxane represented by equation (a) has a structure containing at least two silicon-bonded hydrogen atoms in one molecule. Note that even if n is a number other than 0 or 1, it is not prevented that one or both of the R atoms at both ends of the molecular chain are silicon-bonded hydrogen atoms.

[0084] n is preferably a number other than 0 or 1, and more preferably a number such that n ≥ m. n is preferably 3 to 10, more preferably 3 to 9, and even more preferably 5 to 9.

[0085] In formula (a), p is the number of diorganosiloxy units that do not contain an aralkyl group or a silicon-bonded hydrogen atom. p may be 0, or may be a number obtained by subtracting the values of n and m from the total degree of polymerization of the siloxy units represented by the sum of the values of n, m, and p described below. p is preferably 0 to 12, more preferably 0 to 10, still more preferably 0 to 5, and particularly preferably 0 to 2.

[0086] In the organohydrogenpolysiloxane represented by formula (a), diorganosiloxy units (-[O-Si(R 1 )(R a )]-) having an aralkyl group bonded to a silicon atom, organohydrogensiloxy units (-[O-Si(R 1 )H]-) having a silicon-bonded hydrogen atom, and diorganosiloxy units (-[O-Si(R 1 )(R 2 )]-) that do not contain an aralkyl group or a silicon-bonded hydrogen atom, etc., may be arranged in a block form or may be arranged randomly. That is, the arrangement order of the siloxy units in formula (a) is not particularly limited.

[0087] Compound (Y) has a relatively small degree of siloxane polymerization. In formula (a), the sum of the values of n, m, and p is 5 to 50, preferably 5 to 20, and more preferably 5 to 15. In formula (a), it is preferable that m is 3 to 6, n is 5 to 9, and p is 0 to 2.

[0088] In formula (a), the number of carbon atoms of the alkyl group in R 1 and R 2 is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group is particularly preferred.

[0089] In formula (a), R aThe number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 15. Examples of aralkyl groups include the benzyl group, phenylethyl group, phenylpropyl group, and phenylbutyl group. a As such, an aralkyl group is preferred, which contains at least one branched unit represented by -CH(CH3)- in the alkanediyl group between an aryl group such as a phenyl group and a silicon atom. a As such, an aralkyl group represented by -CH2-CH(CH3)-C6H5 is particularly preferred.

[0090] The aralkyl group is a characteristic functional group that gives hydrosilyl group-containing compounds (Y) usefulness as crosslinking agents. In particular, when aralkyl groups are present together with silicon-bonded hydrogen atoms in compounds (Y) where n, m, and p are within the aforementioned ranges, the physical properties of the resulting crosslinked product tend to be significantly improved. By using compound (Y) in combination with copolymer (S), it is possible to obtain crosslinked products that have particularly excellent physical properties such as moldability, elongation at fracture, and compression molding strain.

[0091] Compound (Y) may be used alone or in combination of two or more types. In the compositions of the present disclosure, the content of compound (Y) is preferably 0.1 to 100 parts by mass, more preferably 0.3 to 75 parts by mass, even more preferably 0.5 to 50 parts by mass, even more preferably 0.8 to 30 parts by mass, particularly preferably 1 to 20 parts by mass, especially preferably 2 to 15 parts by mass, and most preferably 2.5 to 12 parts by mass, per 100 parts by mass of copolymer (S).

[0092] <Crystalline olefin polymer (T)> The crystalline olefin polymer (T) (hereinafter also referred to as "polymer (T)") is not particularly limited as long as it is a crystalline polymer obtained from an olefin, but it is preferably a polymer consisting of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. Examples of such polymers include isotactic monoolefin polymers and syndiotactic monoolefin polymers.

[0093] The polymer (T) may be synthesized by conventionally known methods, or a commercially available product may be used. Furthermore, the polymer (T) may be used alone or in combination of two or more types. Examples of monoolefins used as raw materials for polymer (T) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These olefins may be used individually or in mixtures of two or more.

[0094] Among polymers (T), propylene-based (co)polymers, which are propylene homopolymers or propylene copolymers obtained from monoolefins mainly composed of propylene, are preferred from the viewpoint of heat resistance and oil resistance. In the case of propylene copolymers, the content of propylene-derived constituent units is preferably 40 mol% or more, more preferably 50 mol% or more, and the monoolefins that become constituent units derived from monomers other than propylene are preferably the aforementioned monoolefins other than propylene, more preferably ethylene and butene.

[0095] Whether the polymerization mode is random or block-type, any polymerization mode is acceptable as long as a crystalline resinous material is obtained. The polymer (T) has an MFR (ASTM D1238-65T, 230°C, 2.16 kg load) of typically 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min, more preferably 0.10 to 30 g / 10 min, and particularly preferably 0.30 to 10 g / 10 min.

[0096] The polymer (T) typically has a melting point (Tm) of 100°C or higher, preferably 105°C or higher, as determined by differential scanning calorimetry (DSC). Differential scanning calorimetry is performed, for example, as follows: Approximately 5 mg of the sample is placed in a dedicated aluminum pan, and using a PerkinElmer DSCPyris1 or DSC7, the temperature is increased from 30°C to 200°C at 320°C / min, held at 200°C for 5 minutes, then cooled from 200°C to 30°C at 10°C / min, held at 30°C for another 5 minutes, and the melting point is determined from the endothermic curve when the temperature is increased at 10°C / min. If multiple peaks are detected during DSC measurement, the peak temperature detected on the highest side is defined as the melting point (Tm). The polymer (T) plays a role in improving the fluidity and heat resistance of the copolymer composition. When the MFR and melting point (Tm) of the polymer (T) are within the aforementioned range, the composition of the present invention tends to exhibit excellent fluidity and tensile fracture stress, which is preferable.

[0097] <Additives> The compositions of the present invention may optionally contain additives such as platinum-based catalysts, reaction inhibitors, softeners, heat stabilizers, antistatic agents, weather stabilizers, antioxidants, fillers, colorants, lubricants, crosslinking agents other than hydrosilyl group-containing compounds (Y), and crosslinking aids, to the extent that they do not impair the objectives of the present invention.

[0098] <Platinum-based catalyst> Platinum-based catalysts are addition reaction catalysts and can be used without particular limitations as long as they promote the addition reaction (hydrosilylation reaction of alkenes) between the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). Examples of platinum-based catalysts include elemental platinum (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or platinum supported on a support such as alumina or silica.

[0099] Specific platinum-based catalysts can be any known catalysts typically used in addition-hardening curing, such as the fine-powdered metal-platinum catalyst described in U.S. Patent No. 2,970,150, the chloroplatinic acid catalyst described in U.S. Patent No. 2,823,218, the platinum-hydrocarbon complex compounds described in U.S. Patent No. 3,159,601 and U.S. Patent No. 159,662, the chloroplatinic acid-olefin complex compounds described in U.S. Patent No. 3,516,946, and the platinum-vinylsiloxane complex compounds described in U.S. Patent No. 3,775,452 and U.S. Patent No. 3,814,780. The composition of the present invention may contain two or more platinum-based catalysts.

[0100] In the composition of the present invention, the amount of platinum-based catalyst blended per 100 parts by mass of copolymer (S) is preferably 0.00001 to 0.030 parts by mass, more preferably 0.0001 to 0.020 parts by mass, and even more preferably 0.001 to 0.010 parts by mass. Here, the platinum-based catalyst used in the present invention may be a commercially available product, and some commercially available platinum-based catalysts contain only a few percent of the active ingredient as a platinum-based catalyst. In such cases, the blending amount of platinum-based catalyst will be an amount that takes into account the amount of the active ingredient.

[0101] <Reaction inhibitor> The composition of the present invention preferably contains a reaction inhibitor. The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation addition reaction to an alkene) between the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). The inclusion of a reaction inhibitor is preferable in that it stabilizes the processability of the composition during kneading and molding.

[0102] Specific examples of reaction inhibitors include, for example, benzotriazole; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octin-3,6-diol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 1-ethynyl-1-cyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; acrylonitrile; N,N-diallyl acetylene alcohols. Examples of amide compounds include toamides, N,N-diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalate diamide, N,N,N',N'-tetraallyl-m-phthalate diamide, and N,N,N',N'-tetraallyl-p-phthalate diamide; and others such as sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, and tetramethyltetravinylcyclotetrasiloxane. Among these compounds, 1-ethynyl-1-cyclohexanol and 3,5-dimethyl-1-hexyn-3-ol are more preferred, and 1-ethynyl-1-cyclohexanol is particularly preferred. In one preferred and exemplary embodiment of the present invention, the reaction inhibitor is 1-ethynyl-1-cyclohexanol. The composition of the present invention may contain two or more reaction inhibitors.

[0103] In the composition of the present invention, the amount of reaction inhibitor blended per 100 parts by mass of copolymer (S) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 1.0 parts by mass, and even more preferably 0.1 to 0.5 parts by mass.

[0104] <Softener> Specific examples of the softening agent according to the present invention 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; fatty acids or their salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, and calcium stearate; 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). Petroleum-based softening agents are preferred, and process oils are particularly preferred. The amount of softener blended in the copolymer composition is usually 2 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 50 to 140 parts by mass, even more preferably 80 to 130 parts by mass, and particularly preferably 110 to 130 parts by mass, per 100 parts by mass of copolymer (S).

[0105] <Inorganic fillers> Specific examples of inorganic fillers according to the present invention include one or more types such as light calcium carbonate, heavy calcium carbonate, talc, and clay, of which heavy calcium carbonate such as "Whiteon SB" (product name; Shiraishi Calcium Co., Ltd.) is preferred. When the copolymer composition contains an inorganic filler, the amount of inorganic filler is usually 2 to 50 parts by mass, preferably 5 to 50 parts by mass, per 100 parts by mass of copolymer A. When the amount is within the above range, the kneadability of the copolymer composition is excellent.

[0106] <Reinforcement agent> Specific examples of the reinforcing agent according to the present invention include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine talc, and fine silicic acid. When blended, the amount is usually 30 to 200 parts by mass, preferably 50 to 180 parts by mass, per 100 parts by mass of copolymer (S).

[0107] <Anti-aging agent (stabilizer)> By incorporating an antioxidant (stabilizer) into the copolymer composition according to the present invention, the lifespan of the molded article formed therefrom can be extended. Examples of such antioxidants include conventionally known antioxidants such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0108] Furthermore, anti-aging agents include aromatic 2-amine anti-aging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic anti-aging agents such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether anti-aging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; and dithiocarbamate anti-aging agents such as dibutyldithiocarbamate nickel.

[0109] These antioxidants can be used individually or in combination of two or more, and their amount is usually 0.1 to 10 parts by mass, preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 3.0 parts by mass, per 100 parts by mass of copolymer (S). By keeping the amount within this range, blooming on the surface of the molded article obtained from the crosslinked product of the copolymer composition is eliminated, and the occurrence of vulcanization inhibition can be suppressed.

[0110] <Crosslinking agents other than hydrosilyl group-containing compounds (Y)> Other crosslinking agents besides the hydrosilyl group-containing compound (Y) may include, for example, organic peroxides and phenolic resin-based crosslinking agents. Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyn-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-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0111] Of these, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyn-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis(tert-butylperoxy)valerate are preferred in terms of odor and scorch stability, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane and 1,3-bis(tert-butylperoxyisopropyl)benzene are more preferred, and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane is even more preferred.

[0112] When the copolymer composition of the present invention contains an organic peroxide, the amount of the organic peroxide is preferably 0.001 to 3.0 parts by mass, more preferably 0.05 to 3.0 parts by mass, even more preferably 0.1 to 1.0 parts by mass, and particularly preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of copolymer (S).

[0113] The copolymer composition according to the present invention tends to have increased fluidity when it contains a specific amount of organic peroxide. The reason why the fluidity increases when a specific amount of organic peroxide is included is not clear, but the inventors believe it to be as follows: When organic peroxide is added, the crosslinking reaction of the copolymer (S) proceeds, but at the same time, the decomposition reaction of the crystalline olefin polymer (T) also proceeds. The contribution of the decomposition reaction of the crystalline olefin polymer (T) to increased fluidity is greater than the contribution of the crosslinking reaction of the copolymer (S) to decreased fluidity, so the copolymer composition as a whole is thought to have increased fluidity.

[0114] Phenolic resin crosslinking agents, also known as phenolic curatives, refer to vulcanizing agents containing phenolic curing resins. Preferably, a phenolic curative system consisting of a phenolic curing resin and a cure activator, as disclosed in U.S. Patent No. 4,311,628, is an example. An example of a phenolic resin crosslinking agent is SP-1055, manufactured by Schenectady Chemicals, Inc.

[0115] <Crosslinking agent> When using organic peroxides as crosslinking agents, it is preferable to use crosslinking aids in combination. Examples of crosslinking aids include quinone dioxime-based crosslinking aids such as sulfur, p-quinone dioxime, and p,p'-dibenzoylquinone dioxime; and polyfunctional methacrylate monomers such as N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane, N,N'-m-phenylenedimaleimide, divinylbenzene (e.g., DVB-810 (trade name; manufactured by Nippon Steel Chemical & Material Co., Ltd.)), triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. Examples include polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate; and metal oxides such as zinc oxide (e.g., ZnO#1, Zinc Oxide 2 types (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)). Of these, divinylbenzene is preferred as a crosslinking aid.

[0116] When a crosslinking aid is used, the amount of the crosslinking aid in the copolymer composition is preferably 0.5 to 10 moles, more preferably 0.5 to 7 moles, and even more preferably 0.5 to 6 moles per mole of organic peroxide.

[0117] <Processing aid> The processing aids according to the present invention can be broadly those that are generally used as processing aids in rubber. Specific examples of processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, and esters. Of these, stearic acid is preferred. The amount of processing aid added is usually 10 parts by mass or less, preferably 8.0 parts by mass or less, per 100 parts by mass of copolymer (S) contained in the copolymer composition.

[0118] <Activating agent> Specific examples of surfactants include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triaryl root melilate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide moduloides; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds. If an activator is included, the amount is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of copolymer (S).

[0119] <Desiccant> Specific examples of desiccants include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. If a desiccant is included, the amount is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass, per 100 parts by mass of copolymer (S).

[0120] <Copolymer composition> The composition of the present invention comprises 100 parts by mass of ethylene-α-olefin-nonconjugated polyene copolymer (S), 0.5 to 50 parts by mass of a hydrosilyl group-containing compound (Y), and 10 to 300 parts by mass of a crystalline olefin polymer (T).

[0121] The content of compound (Y) is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, even more preferably 3 to 20 parts by mass, and particularly preferably 3.5 to 15 parts by mass, per 100 parts by mass of copolymer (S). A compound (Y) content within this range is preferable because it provides an excellent balance between tensile fracture stress and compression set.

[0122] The polymer (T) content is preferably 30 to 200 parts by mass, more preferably 40 to 150 parts by mass, even more preferably 50 to 100 parts by mass, and particularly preferably 60 to 80 parts by mass, per 100 parts by mass of copolymer (S). A polymer (T) content within the above range is preferable in that it provides an excellent balance between fluidity and tensile fracture point.

[0123] The composition of the present invention is crosslinked in at least a portion thereof. Preferably, at least a portion of the copolymer (S) is crosslinked.

[0124] A method for producing the composition of the present invention preferably includes a step of dynamically crosslinking a copolymer (S) and a polymer (T) in the presence of a compound (Y). In the present invention, "dynamic crosslinking" refers to crosslinking a mixture containing a polymer and a crosslinking agent by melt kneading.

[0125] One method for (dynamic) crosslinking is to mix a copolymer (S), a polymer (T), and a compound (Y), and then knead them using a conventionally known kneading apparatus. Examples of kneading apparatuses include open-type mixing rolls, closed-type Banbury mixers, extruders, kneaders, and continuous mixers. Of these, closed-type kneading apparatuses are preferred, and kneading is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide.

[0126] The mixing temperature is typically 150-280°C, preferably 160-240°C, and the mixing time is typically 1-20 minutes, preferably 1-10 minutes. The applied shear force is a shear rate of 10-50,000 seconds. -1 Preferably 100 to 20,000 seconds -1 It will be determined within the range.

[0127] The crosslinked material of the composition of the present invention is preferably subjected to static heat treatment in hot air after being kneaded (dynamically) crosslinked as described above. Here, "static heat treatment" means leaving the material at a temperature below its melting point for a certain period of time while standing or being stirred.

[0128] At that time, the static heat treatment is carried out under the following conditions: Q ≥ 0.1 and t ≥ 2 -(T-110) / 10 (However, Q represents the amount of hot air per unit weight of the object to be processed supplied during drying (m 3 / (hour·kg)), t represents the heat treatment time (hour), and T represents the temperature of the hot air immediately before hitting the object to be processed (°C).) By carrying out the treatment in this way, most of the low molecular weight components are removed, and a copolymer composition with better fogging resistance can be obtained. The composition of the present invention may be completely crosslinked, but is preferably partially crosslinked.

[0129] <Uses of the copolymer composition> The composition of the present invention can obtain a molded article containing a crosslinked product by generally used molding methods, such as injection molding, extrusion molding, blow molding, compression molding, etc. As uses, there are automotive parts (weatherstrip, ceiling material, interior seat, bumper mold, side mold, air spoiler, air duct hose, cup holder, side brake grip, shift knob cover, seat adjustment knob, flapper door seal, wire harness grommet, rack and pinion boot, suspension cover boot, glass guide, inner belt line seal, roof guide, trunk lid seal, mold dead quarter window gasket, corner molding, glass encapsulation, hood seal, glass run channel, secondary seal, automotive skin material, automotive hose, automotive boot, various packings, etc.), civil engineering and building materials parts (waterstop material, joint material, building window frame, etc.), sports goods (golf club, tennis racket grips, etc.), industrial parts (hose tube, gasket, etc.), household electrical appliance parts (hose, packings, etc.), medical equipment parts, electric wires, sundries, etc., and it is used as a material in a wide range of fields.

Examples

[0130] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples in any way.

[0131] <Method for measuring physical properties of copolymer (S)> The physical properties of the copolymer (S) were measured as follows.

[0132] <Composition of copolymer (S)> The content of each structural unit in the copolymer (S) was 13 calculated from the C-NMR spectrum. Using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.), the C-NMR spectrum of the copolymer (S) was measured under the conditions of a measurement temperature of 120 °C, a measurement solvent of ortho-dichlorobenzene / deuterated benzene = 4 / 1, and an integration number of 8000 times. 13 C-NMR spectrum was measured.

[0133] <Mooney viscosity> The Mooney viscosity ML of the copolymer (S) at 125 °C (1+4) was measured using a Mooney viscometer (SMV-301 type manufactured by Shimadzu Corporation) in accordance with JIS K6300-1:2013.

[0134] The B value of the copolymer (S) was measured 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 C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured and calculated based on the following formula. B value = ([AB] + 2[C]) / [2 × [A] × ([B] + [C])] The meanings of [A], [B], [C], and [AB] are as described above.

[0135] <Limiting viscosity> The limiting viscosity [η] of the copolymer (S) was measured using an automatic limiting viscometer (manufactured by Rhesco Co., Ltd.) under the conditions of a temperature of 135 °C and a measurement solvent of decalin.

[0136] <Weight average molecular weight (Mw)> The weight-average molecular weight (Mw) of the copolymer (S) is a polystyrene-converted value measured by 3D-GPC. The measurement equipment and conditions are as follows. The dn / dc value (dn / dc value, which is the derivative of refractive index n with respect to concentration c) necessary for determining the absolute molecular weight was determined for each sample using the dn / dc value of standard polystyrene (molecular weight 190000), which is 0.053, and the response intensity of the differential refractometer per unit injection mass. Equipment: 3D high-temperature GPC system PL-GPC220 model (manufactured by Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT x 2 bottles + 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.

[0137] <complex viscosity η * > Using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) as the rheometer, the complex viscosity η was measured at a frequency ω = 0.01 rad / sec 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) The following was measured. From the obtained results, 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.

[0138] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of copolymer (S) 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, before being 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).

[0139] <Copolymer> The copolymers used in each example were prepared using the method described in the following production example.

[0140] <Ethylene-α-olefin-nonconjugated polyene copolymer (S)> In the examples, the ethylene-propylene-VNB copolymer (S-1) obtained in the following manufacturing example was used.

[0141] [Manufacturing Example 1] [Production of ethylene-propylene-VNB copolymer (S-1)] In a 300-liter polymerization reactor, 58.3 L / h of dehydrated and purified hexane solvent was continuously supplied from line 1, 4.5 mmol / h of triisobutylaluminum (TiBA), 0.150 mmol / h of (C6H5)3CB(C6F5)4, and 0.030 mmol / h of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride was continuously supplied from line 2. Simultaneously, 6.6 kg / h of ethylene, 9.3 kg / h of propylene, 18 L / h of hydrogen, and 340 g / h 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. The physical properties of copolymer (S-1) are shown in Table 1.

[0142] [Table 1]

[0143] <Ethylene-propylene-ENB copolymer (R) (EPDM)> Ethylene content: 65% by mass, ENB content: 4.6% by mass, Mooney viscosity: ML (1+4) Ethylene-propylene-ENB copolymer (manufactured by Mitsui Chemicals, Inc., trade name: Mitsui EPT3092M) (R-1), with a 125°C:61 ratio, was used.

[0144] <Crystalline olefin polymer (T)> As the crystalline olefin polymer (T), a propylene homopolymer [manufactured by Prime Polymer Co., Ltd., trade name: Prime PolyPro E-200GP] (T-1) with an MFR of 2.0 g / 10 min (230°C, 2.16 kg load) and a melting point of 165°C was used.

[0145] <Crosslinking agent> As the crosslinking agent, crosslinking agent 1, crosslinking agent 2, or compound (Y-1) obtained in the following manufacturing example was used. Crosslinking agent 1: Manufactured by SIGroupInc., product name: SP1055 Crosslinking agent 2: Manufactured by NOF Corporation, product name: Perhexa 25B-40

[0146] [Manufacturing Example 2] [Production of compound (Y-1)] 536 g of methylhydrogenpolysiloxane represented by the following formula (a-1-1) was charged into the reactor and heated to 40°C while stirring under a nitrogen flow. 0.4 g of a toluene solution of platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex (Pt concentration: 0.3 wt%) was added, and 265 g of α-methylstyrene was added dropwise while maintaining the reaction temperature at 40-90°C.

[0147] [ka]

[0148] After the dropwise addition was complete, the mixture was stirred at 85°C for 2 hours. Then, 0.5 g of the reaction solution was taken, and the reaction rate of the Si-H groups was confirmed to be approximately 36% by the alkaline decomposition gas generation method (decomposing the remaining Si-H groups with an ethanol / aqueous solution of KOH, and calculating the reaction rate of the Si-H groups from the volume of hydrogen gas generated). Next, the reaction solution was heated under reduced pressure to 135°C and the low-boiling components were removed by distillation for 2 hours to obtain 673 g of compound (Y-1).

[0149] The resulting compound (Y-1) is, 29 Si-NMR confirmed that the compound was represented by the formula (a-1) below. The viscosity of the obtained compound (Y-1) was measured at 25°C using an Ubbelohde viscous tube in accordance with JIS Z8803:2011, and it was found to be 26 mmHg. 2 It was / s.

[0150] [ka]

[0151] <Other ingredients> Anti-aging agent: Manufactured by BASF Japan Ltd., product name: Irganox 1010 Softener: Manufactured by Idemitsu Kosan Co., Ltd., Product name: Diana Process Oil PW-100 Reaction inhibitor: 1-ethynyl-1-cyclohexanol, manufactured by Nisshin Chemical Industry Co., Ltd. Platinum-based catalyst: Manufactured by Dow Toray, product name: SRX212Catalyst, a complex salt of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane, a product containing 1% to less than 3% by mass of the 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complex. Crosslinking aid 1: Two types of zinc oxide manufactured by Hakusui Tech Co., Ltd. Crosslinking agent 2: Manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name: DVB810

[0152] [Example 1] <Preparation of composition> Using a Toyo Seiki Manufacturing Laboplast Mill [4C150, Model: R60H mixer, Capacity: approx. 60cc (Effective mixing volume: 48cc)], the mixing temperature was set to 170°C and the rotation speed to 10 rpm. 100 parts by mass of copolymer (S-1) and 71.4 parts by mass of polymer (T-1) were added. The rotation speed was then rapidly increased from 10 rpm (10 seconds) to 30 rpm (10 seconds) to 50 rpm (10 seconds) to 70 rpm (10 seconds) to 90 rpm (10 seconds), and this was repeated three times. Next, at a rotation speed of 10 rpm, 114.3 parts by mass of the softening agent was added dropwise, taking care not to let the rotor spin freely. The rotation speed was then rapidly increased from 10 rpm (10 seconds) to 30 rpm (10 seconds) to 50 rpm (10 seconds) to 70 rpm (10 seconds) to 90 rpm (10 seconds). Finally, the rotation speed was reduced to 10 rpm, and 0.4 parts by mass of the anti-aging agent was added to obtain the composition.

[0153] <Manufacturing of copolymer compositions> Next, 9.5 parts by mass of compound (Y-1), 0.2 parts by mass of platinum-based catalyst, and 0.4 parts by mass of reaction inhibitor were added to the composition, which was maintained at a temperature of 170°C. The rotation speed was then rapidly increased from 10 rpm to 30 rpm to 50 rpm to 70 rpm to 90 rpm. After the torque reached its peak, the mixture was kneaded at 90 rpm for 3 minutes to obtain a copolymer composition.

[0154] [Preparation of sheet-like cross-linked molded articles] Each copolymer composition was pre-pressed in a mold at 190°C for 6 minutes using a press molding machine, followed by a main press for 4 minutes, and then cooled and pressed at room temperature for 5 minutes to produce a 2 mm thick press sheet. The physical properties of the resulting sheet-like crosslinked molded articles were evaluated. The evaluation results are shown in Table 2.

[0155] [Examples 2 and 3] A copolymer composition was prepared under the same conditions as in Example 1, except that the content of compound (Y-1) was changed as shown in Table 2, and a sheet-like crosslinked molded article was produced. The physical properties of the obtained sheet-like crosslinked molded article were evaluated. The evaluation results are shown in Table 2.

[0156] [Comparative Examples 1-3] A copolymer composition was prepared under the same conditions as in Example 1, except that copolymer (R-1) was used instead of copolymer (S-1), and crosslinking agent 1 and crosslinking aid 1 were used instead of compound (Y-1), platinum-based catalyst, and reaction inhibitor, and the compositions were blended in the amounts shown in Table 2. A sheet-like crosslinked molded article was then produced. The physical properties of the obtained sheet-like crosslinked molded article were evaluated. The evaluation results are shown in Table 2.

[0157] [Comparative Example 4 and Comparative Example 5] A copolymer composition was prepared under the same conditions as in Example 1, except that copolymer (R-1) was used instead of copolymer (S-1), and crosslinking agent 2 and crosslinking aid 2 were used instead of compound (Y-1), platinum-based catalyst, and reaction inhibitor, and the compositions were blended in the amounts shown in Table 2. A sheet-like crosslinked molded article was then produced. The physical properties of the obtained sheet-like crosslinked molded article were evaluated. The evaluation results are shown in Table 2.

[0158] [Comparative Example 6 and Comparative Example 7] A copolymer composition was prepared under the same conditions as in Example 1, except that crosslinking agent 2 and crosslinking aid 2 were used instead of compound (Y-1), platinum-based catalyst, and reaction inhibitor, and the compounds were blended in the amounts shown in Table 2. A sheet-like crosslinked molded article was then produced. The physical properties of the obtained sheet-like crosslinked molded article were evaluated. The evaluation results are shown in Table 2.

[0159] [Example 4] <Preparation of composition> Using a Toyo Seiki Manufacturing Laboplast Mill [4C150, Model: R60H mixer, Capacity: approx. 60cc (Effective mixing volume: 48cc)], the mixing temperature was set to 170°C and the rotation speed to 10 rpm. 100 parts by mass of copolymer (S-1) and 71.4 parts by mass of polymer (T-1) were added. The rotation speed was then rapidly increased from 10 rpm (10 seconds) to 30 rpm (10 seconds) to 50 rpm (10 seconds) to 70 rpm (10 seconds) to 90 rpm (10 seconds), and this was repeated three times. Next, at a rotation speed of 10 rpm, 114.3 parts by mass of the softening agent was added dropwise, taking care not to let the rotor spin freely. The rotation speed was then rapidly increased from 10 rpm (10 seconds) to 30 rpm (10 seconds) to 50 rpm (10 seconds) to 70 rpm (10 seconds) to 90 rpm (10 seconds). Finally, the rotation speed was reduced to 10 rpm, and 0.4 parts by mass of the anti-aging agent was added to obtain the composition.

[0160] <Manufacturing of copolymer compositions> Next, to the composition, which was kept at a temperature of 170°C, 6.5 parts by mass of compound (Y-1), 0.2 parts by mass of platinum-based catalyst, and 0.4 parts by mass of reaction inhibitor were added, and the mixture was kneaded at 10 rpm for 30 seconds. Then, 0.26 parts by mass of crosslinking agent 2 and 0.065 parts by mass of crosslinking aid 2 were added, and the rotation speed was rapidly increased from 10 rpm → 30 rpm → 50 rpm → 70 rpm → 90 rpm. After the torque reached its peak, the mixture was kneaded at 90 rpm for 3 minutes to obtain the copolymer composition.

[0161] [Example 5] A copolymer composition was prepared under the same conditions as in Example 4, except that the content of compound (Y-1) was changed as shown in Table 2, and a sheet-like crosslinked molded article was produced. The physical properties of the obtained sheet-like crosslinked molded article were evaluated. The evaluation results are shown in Table 2.

[0162] <Method for evaluating physical properties> [Colorability] The appearance of the obtained sheet was observed visually. <Evaluation Criteria> A: No brownish discoloration was observed; only a white color derived from the copolymer was seen. B: A brownish discoloration was observed.

[0163] [Durometer A hardness] In accordance with JIS K6253, the hardness of the sheets (Type A durometer, HA) was measured using six 2mm thick crosslinked sheets with smooth surfaces, stacked with their flat surfaces to a total thickness of approximately 12mm. However, test specimens containing foreign matter, air bubbles, or scratches were not used. Furthermore, the dimensions of the measurement surface of the test specimen were such that measurement could be taken with the indenter tip at a distance of 12mm or more from the edge of the specimen.

[0164] [Modus (MPa), Tensile stress at fracture (MPa), Tensile elongation at fracture (%)] A No. 3 dumbbell test specimen, as described in JIS K6251 (1993), was prepared by punching out sheets. 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 modulus at 25% elongation (M25), 50% elongation (M50), 100% elongation (M100), 200% elongation (M200), 300% elongation (M300), tensile stress at fracture (TB), and tensile elongation at fracture (EB) were measured.

[0165] [Melt flow rate (MFR) of copolymer composition] In accordance with JIS K7210, the melt flow rate (MFR) of the copolymer composition was measured under a temperature of 230°C and a load of 2.16 kg.

[0166] [Oil resistance (weight change rate)] Using the obtained sheets, the weight change rate after treatment was measured at 80°C for 24 hours using liquid paraffin (soft type) (manufactured by Nakalai Tesque Co., Ltd., code number: 26132-35) as the test lubricant, in accordance with JIS K6258.

[0167] [Compression set (CS) of sheet-like molded articles] The obtained 2mm sheets were stacked to a thickness of 12mm, and the compression set was measured after processing at a predetermined temperature for a predetermined time in accordance with JIS K6262:2013. Compression set (%) = {(t0-t1) / (t0-t2)} × 100 t0: Height of the test specimen before testing. t1: Height after treating the test specimen under the above conditions and leaving it at room temperature for 30 minutes. t2: Height of the test specimen when it is attached to the measuring mold.

[0168] [Table 2]

Claims

1. 100 parts by mass of an ethylene-α-olefin-non-conjugated polyene copolymer (S) 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 following formulas (I) and (II) in one molecule, 0.5 to 50 parts by mass of a hydrosilyl group-containing compound (Y), It contains 10 to 300 mass of a crystalline olefin polymer (T), The copolymer (S) satisfies the following requirement (i): A copolymer composition in which at least a portion is crosslinked. 【Chemistry 1】 Requirement (i): The number of long chain branches per thousand carbon atoms (LCB) obtained using 3D-GPC. 1000C The natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following equation (1). LCB 1000C ≦1-0.07×Ln(Mw)・・・Formula (1)

2. The copolymer composition according to claim 1, wherein the copolymer (S) satisfies the following requirements (ii) and (iii). Requirement (ii): 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-olefins (B) having 3 to 20 carbon atoms, is between 40 / 60 and 90 / 10. Requirement (iii): The mass fraction of constituent units derived from non-conjugated polyene (C) is 0.1 to 6.0% by mass relative to the total constituent units of the copolymer (S).

3. The copolymer composition according to claim 1, wherein the copolymer (S) satisfies one or more of the following requirements (iv) and (v). Requirement (iv): The weight-average molecular weight (Mw) of the copolymer (S), 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 (2). 4.5 ≤ Mw × mass fraction of (C) / 100 / molecular weight of (C) ≤ 80 ... Equation (2) Requirement (v): The ratio P[η * / η (ω=0.1) ] of the complex viscosity η * (Pa·s) at a frequency ω = 0.1 rad / s to the complex viscosity η (ω=0.1) (Pa·s) at a frequency ω = 100 rad / s, obtained by linear viscoelastic measurement (at 190°C) using a rheometer, the intrinsic viscosity [η] of the copolymer (S), and the mass fraction of the component (C) satisfy the following formula (3). * (ω=0.1) (Pa·s), to the complex viscosity η (ω=0.1) * (ω=100) (Pa·s) is P[η * (ω=0.1) / η * (ω=100) , the intrinsic viscosity [η] of the copolymer (S), and the mass fraction of the component (C) satisfy the following formula (3). P / ([η] 2.9 ) ≤ (C) Mass fraction × 6 ... Equation (3)

4. The copolymer composition according to claim 1, wherein the non-conjugated polyene (C) comprises 5-vinyl-2-norbornene.

5. The copolymer composition according to claim 1, wherein the hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a), having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. 【Chemistry 2】 (In equation (a), n and p are each independently 0 or a positive number, m is between 1 and 20, the sum of n, m and p is between 5 and 50, and multiple R 1 and R 2 Each of these is independently a monovalent alkyl group, and R a It is an aralkyl group, and the two Rs are each independently R 1 , R 2 , hydrogen atom, and R a Selected from the group consisting of -[O-Si(R 1 ) (Caution a )]-,-[O-Si(R 1 )H]- and -[O-Si(R 1 ) (Caution 2 The constituent units of )- may be arranged in a block-like manner or randomly, provided that when n=1, at least one of the two R atoms is a hydrogen atom, and when n=0, both R atoms are hydrogen atoms.

6. The copolymer composition further comprises a platinum-based catalyst. The copolymer composition according to claim 1, comprising 0.00001 to 0.030 parts by mass of the platinum-based catalyst per 100 parts by mass of the copolymer (S).

7. The copolymer composition further comprises a reaction inhibitor. The copolymer composition according to claim 1, comprising 0.01 to 10 parts by mass of the reaction inhibitor per 100 parts by mass of the copolymer (S).

8. The copolymer composition further comprises an organic peroxide, The copolymer composition according to claim 1, comprising 0.001 to 3.0 parts by mass of the organic peroxide per 100 parts by mass of the copolymer (S).

9. The copolymer composition further comprises a crosslinking aid, The copolymer composition according to claim 8, wherein the amount of the crosslinking aid is 0.5 to 10 moles per mole of the organic peroxide.

10. A method for producing a copolymer composition according to any one of claims 1 to 9, comprising the step of dynamically crosslinking the copolymer (S) and the crystalline olefin polymer (T) in the presence of a hydrosilyl group-containing compound (Y).

11. A crosslinked copolymer composition according to any one of claims 1 to 9.

12. A molded article comprising the crosslinked material described in claim 11.

13. Automotive part comprising the crosslinking material described in claim 11.

14. Automotive surface material comprising the crosslinked material described in claim 11.

15. An automobile hose comprising the crosslinking material described in claim 11.

16. Automotive boot comprising the crosslinking material described in claim 11.

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