Composition, crosslinked body, and hose product

Abstract

To provide a composition that contains an ethylene-α-olefin-non-conjugated polyene copolymer and a hydrosilyl group-containing compound, exhibits excellent scorch resistance, and is capable of forming a crosslinked body having high electrical resistance.SOLUTION: A composition containing a specific ethylene-α-olefin-non-conjugated polyene copolymer (A), a specific hydrosilyl group-containing compound (Y), a platinum-based catalyst, heavy calcium carbonate, and light calcium carbonate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to compositions, crosslinked bodies, and hose products. [Background technology]

[0002] Ethylene-α-olefin-non-conjugated polyene copolymers, such as ethylene-propylene-non-conjugated diene copolymer (EPDM), typically do not have unsaturated bonds in the main chain of their molecular structure. Therefore, compared to general-purpose conjugated diene rubbers, these copolymers have superior heat aging resistance, weather resistance, and ozone resistance, making them widely used in a variety of applications.

[0003] The copolymer is usually crosslinked before use. For example, a copolymer composition containing the copolymer and a hydrosilyl group-containing compound is known (see, for example, Patent Document 1). Also, for use in automotive water hoses, a rubber composition containing the copolymer and a reinforcing agent such as carbon black is known (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2023 / 136287 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-072291 Summary of the Invention [Problem to be solved by the invention]

[0005] For example, from the viewpoints of ensuring safety and suppressing corrosion degradation, it is desirable for vehicle hoses to have high electrical resistance (high electrical insulation). The present inventors investigated the production of a crosslinked product with high electrical resistance using a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer and a hydrosilyl group-containing compound. Furthermore, in order to ensure moldability, they investigated the improvement of the scorch resistance of the above composition.

[0006] An object of the present disclosure is to provide a composition that contains an ethylene-α-olefin-non-conjugated polyene copolymer and a hydrosilyl group-containing compound, and that has excellent scorch resistance and is capable of forming a crosslinked product with high electrical resistance. [Means for solving the problem]

[0007] One embodiment of the composition of the present disclosure is a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer (A), a hydrosilyl group-containing compound (Y), a platinum-based catalyst, heavy calcium carbonate, and light calcium carbonate, The copolymer (A) contains a structural unit derived from ethylene [A1], a structural unit derived from an α-olefin [A2] having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures in total, at least one of which is selected from the group consisting of formula (I) and formula (II) described below; The hydrosilyl group-containing compound (Y) is represented by the formula (Y1) described below, and is an organohydrogenpolysiloxane having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in one molecule. [Effects of the Invention]

[0008] The composition of the present disclosure contains an ethylene-α-olefin-non-conjugated polyene copolymer and a hydrosilyl group-containing compound, and is a composition that has excellent scorch resistance and can form a crosslinked product with high electrical resistance. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this specification, when the numerical range is n1~n2, if n1 < n2, it means n1 or more and n2 or less; if n1 > n2, it means n2 or more and n1 or less. In this specification, when a plurality of lower limit values and upper limit values are described for 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 regarded as 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%~85 mol%" may be described as "50~85 mol%".

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

[0012] [[ID=十二]]In this specification, unless otherwise specified, each component in the composition or each structural unit in the polymer may be included in one kind or two or more kinds. In this specification, the term "polymer" may be used without particularly distinguishing between homopolymers and copolymers. That is, the term "polymer" is used in a sense that it may be a homopolymer or a copolymer.

[0013] [[ID=十八]][Composition] The composition of the present disclosure contains an ethylene·α-olefin·non-conjugated polyene copolymer (A), a hydrosilyl group-containing compound (Y), a platinum-based catalyst, heavy calcium carbonate, and light calcium carbonate.

[0014] <Ethylene·α-olefin·non-conjugated polyene copolymer (A)> It should be noted that there is an error in the line number "[[ID=十二]]", which should be corrected to "" in the translation for consistency.The ethylene-α-olefin-non-conjugated polyene copolymer (A) (hereinafter also referred to as "copolymer (A)") contains structural units derived from ethylene [A1], structural units derived from an α-olefin having 3 to 20 carbon atoms [A2], and structural units derived from a non-conjugated polyene [A3]. The non-conjugated polyene [A3] is a non-conjugated polyene containing a total of two or more partial structures per molecule, each of which is at least one type selected from the group consisting of the following formulas (I) and (II):

[0015] [ka]

[0016] Examples of the α-olefin [A2] 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 they are relatively inexpensive in terms of raw material cost, the resulting copolymers exhibit excellent mechanical properties, and crosslinked products having rubber elasticity can be obtained. The α-olefins [A2] may be used alone or in combination of two or more.

[0017] Examples of the non-conjugated polyene [A3] 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 of suitable non-conjugated polyenes include 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, and dicyclopentadiene. The non-conjugated polyene [A3] preferably contains VNB, and more preferably is VNB, because it is readily available, the resulting copolymer has good crosslinkability, and the heat resistance of the composition is easily improved. The non-conjugated polyene [A3] may be used alone or in combination of two or more.

[0018] The copolymer (A) may further contain structural units derived from a non-conjugated polyene [A4]. The non-conjugated polyene [A4] is a non-conjugated polyene containing only one partial structure selected from the group consisting of formula (I) and formula (II) per molecule.

[0019] Examples of the non-conjugated polyene [A4] 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. Because of its high availability, ease of controlling the crosslinking rate of the resulting copolymer, and ease of obtaining good mechanical properties, the non-conjugated polyene [A4] preferably contains ENB, and more preferably is ENB. The non-conjugated polyene [A4] may be used alone or in combination of two or more.

[0020] The copolymer (A) may contain at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived ethylene, biomass-derived α-olefins having 3 to 20 carbon atoms, and biomass-derived non-conjugated polyenes. Examples of the biomass-derived α-olefins include biomass-derived propylene. Examples of the 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 (A) may contain only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers. The biomass-derived monomers can be obtained by known methods. It is preferable that the copolymer (A) contain structural units derived from biomass-derived monomers from the viewpoint of reducing the environmental impact.

[0021] The copolymer (A) may contain at least one structural unit derived from a chemically recycled monomer. Examples of the chemically recycled monomer include ethylene derived from chemical recycling, an α-olefin having 3 to 20 carbon atoms derived from chemical recycling, and a non-conjugated polyene derived from chemical recycling. The monomers used as raw materials for the copolymer (A) may contain only chemically recycled monomers, only fossil fuel-derived monomers, or both chemically recycled monomers and fossil fuel-derived monomers. The chemically recycled monomers are obtained by known methods. It is preferable that the copolymer (A) contains a structural unit derived from a chemically recycled monomer from the viewpoint of reducing the environmental load (mainly reducing waste).

[0022] The copolymer (A) preferably satisfies the following requirements (i) and (ii). In addition to satisfying the following requirements (i) and (ii), copolymer (A) preferably satisfies one or more of the following requirements (iii) to (v), more preferably satisfies two or more of the following requirements (iii) to (v), and even more preferably satisfies all of the following requirements (iii) to (v).

[0023] Requirement (i): When all structural units contained in the copolymer (A) are taken as 100 mol %, the ratio [(A1) / (A2)] of the molar fraction (A1) of structural units derived from ethylene [A1] to the molar fraction (A2) of structural units derived from an α-olefin [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1. 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, still more preferably 55 / 45 to 78 / 22, and particularly preferably 60 / 40 to 75 / 25.

[0024] When the copolymer (A) satisfies the requirement (i), the crosslinked product obtained from the composition containing such a copolymer tends to be excellent in rubber elasticity, flexibility and mechanical strength.

[0025] When all structural units contained in the copolymer (A) are taken as 100 mol %, the molar fraction (A1) of structural units derived from ethylene [A1] is preferably 50 to 85 mol %, more preferably 55 to 80 mol %, and even more preferably 60 to 75 mol %.

[0026] Requirement (ii): The mass fraction of the structural unit derived from the non-conjugated polyene [A3] is 0.07 to 10 mass % in 100 mass % of the copolymer (A). The mass fraction of the structural unit derived from the non-conjugated polyene [A3] is preferably 0.1 to 8.0 mass%, more preferably 0.5 to 5.0 mass%, further preferably 0.5 to 3.0 mass%, particularly preferably 0.5 to 2.0 mass%.

[0027] When the copolymer (A) satisfies the requirement (ii), the crosslinked product obtained from the composition containing such a copolymer tends to have sufficient hardness and excellent mechanical properties. When the copolymer (A) satisfies the requirement (ii), the crosslinked product tends to have excellent crosslinkability and a high crosslinking rate.

[0028] When the copolymer (A) further contains a structural unit derived from the non-conjugated polyene [A4], the mass fraction of the structural unit is preferably 20 mass% or less, more preferably 8.0 mass% or less, and even more preferably 0.01 to 8.0 mass% in 100 mass% of the copolymer (A).

[0029] The molar fraction (A1) of the structural unit derived from ethylene [A1], the molar fraction (A2) of the structural unit derived from an α-olefin having 3 to 20 carbon atoms [A2], the ratio [(A1) / (A2)], the mass fraction of the structural unit derived from the non-conjugated polyene [A3], and the mass fraction of the structural unit derived from the non-conjugated polyene [A4] were measured using the apparatus and conditions described in the Examples section below. 13 It can be calculated by measuring the C-NMR spectrum.

[0030] Requirement (iii): The weight average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), and the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]) satisfy the following formula (1): 4.5≦Mw×[A3] mass fraction / 100 / [A3] molecular weight≦80 (1)

[0031] The formula (1) in the requirement (iii) is preferably the following formula (1a). 4.5≦Mw×mass fraction of [A3] / 100 / molecular weight of [A3]≦75 (1a) Formula (1) in requirement (iii) is preferably the following formula (1b). 4.5≦Mw×mass fraction of [A3] / 100 / molecular weight of [A3]≦70 (1b)

[0032] Requirement (iii) represents the content of structural units derived from the non-conjugated polyene [A3] per weight-average molecular weight (Mw) in the copolymer (A). When the copolymer (A) satisfies requirement (iii), the content of structural units derived from the non-conjugated polyene [A3] in such a copolymer is more appropriate. Therefore, the composition tends to exhibit sufficient crosslinkability and a high crosslinking rate. Furthermore, the crosslinked body formed from the composition tends to have a good balance of mechanical properties and heat aging resistance.

[0033] The weight average molecular weight (Mw) of the copolymer (A) can be determined as a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the conditions described in the Examples section below.

[0034] Requirement (iv): Complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at a frequency of ω=100 rad / sec * (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η *(ω=100) ), the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) satisfy the following formula (2): P / ([η] 2.9 ) ≦ [A3] mass fraction × 6 (2)

[0035] Formula (2) in requirement (iv) is preferably the following formula (2a). P / ([η] 2.9 ) ≦ [A3] mass fraction × 5.7 (2a)

[0036] 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] 2.9 ) tends to show a high value when there is a lot of long-chain branching, although it is affected by factors such as short-chain branching and molecular weight. Generally, the more structural units derived from non-conjugated polyene an ethylene-α-olefin-non-conjugated polyene copolymer contains, the more long-chain branching it tends to have. However, copolymer (A) has less long-chain branching than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, and is therefore thought to be able to satisfy formula (2) or (2a).

[0037] The P value is the ratio of the complex viscosity measured at 190°C, 1.0% strain, and 0.1 rad / sec using a viscoelasticity measuring device (e.g., Ares (Rheometric Scientific)) to the complex viscosity measured at 100 rad / sec, with only the measurement frequency changed. The intrinsic viscosity [η] means the value measured in decalin at 135°C.

[0038] Requirement (v): Complex viscosity η at a frequency ω = 0.01 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.01) (Pa·sec) and the complex viscosity η at a frequency of ω=10 rad / sec* (ω=10) (Pa·sec) and the apparent iodine value derived from the non-conjugated polyene [A3] satisfy the following formula (3): Log[η * (ω=0.01) ] / Log[η * (ω=10) ] ≦ 0.0753 × {apparent iodine value derived from non-conjugated polyene [A3]} + 1.42 (3)

[0039] In formula (3), the left side represents the shear rate dependency, which is an index of the content of long chain branches, and the right side represents an index of the content of non-conjugated polyene [A3] that is not consumed as long chain branches during polymerization. If the copolymer (A) satisfies formula (3), the degree of long chain branching is not too high, which is preferable.

[0040] Complex viscosity η * (ω=0.01) and complex viscosity η * (ω=10) is the complex viscosity η in requirement (iv) * (ω=0.1) and complex viscosity η * (ω=100) Measurements can be performed in the same way except for the measurement frequency. The apparent iodine value derived from the non-conjugated polyene [A3] is calculated by the formula (4). Apparent iodine value derived from [A3] = mass fraction of [A3] × 253.81 / molecular weight of [A3] (4)

[0041] In the copolymer (A), as described above, the non-conjugated polyene [A3] preferably contains VNB, and more preferably is VNB. That is, in the formulas (1) and (2), the "mass fraction of [A3]" is preferably the "mass fraction of structural units derived from VNB."

[0042] As described above, when the copolymer (A) contains structural units derived from ethylene [A1], an α-olefin [A2] having 3 to 20 carbon atoms, a non-conjugated polyene [A3], and a non-conjugated polyene [A4], the mass fraction of the structural units derived from the non-conjugated polyene [A4] is preferably 20 mass% or less (where the total mass fraction of the structural units derived from ethylene [A1], an α-olefin [A2] having 3 to 20 carbon atoms, a non-conjugated polyene [A3], and a non-conjugated polyene [A4] is taken as 100 mass%). In this case, the copolymer (A) preferably satisfies the following requirement (vi).

[0043] Requirement (vi): The weight average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), the mass fraction of the structural unit derived from the non-conjugated polyene [A4] (mass fraction (mass%) of [A4]), the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]), and the molecular weight of the non-conjugated polyene [A4] (molecular weight of [A4]) satisfy the following formula (5) (where the total of the mass fractions of the structural units derived from ethylene [A1], the α-olefin [A2] having 3 to 20 carbon atoms, the non-conjugated polyene [A3], and the non-conjugated polyene [A4] is 100% by mass). 4.5≦Mw×{(mass fraction of [A3] / 100 / molecular weight of [A3])+(mass fraction of [A4] / 100 / molecular weight of [A4])}≦80 (5) Formula (5) specifies the total content of structural units derived from non-conjugated polyenes ([A3] and [A4]) per weight average molecular weight (Mw) in the copolymer (A).

[0044] Formula (5) in requirement (vi) is preferably the following formula (5a): 4.5≦Mw×{(mass fraction of [A3] / 100 / molecular weight of [A3])+(mass fraction of [A4] / 100 / molecular weight of [A4])}≦75 (5a)

[0045] When the copolymer (A) containing structural units derived from the non-conjugated polyene [A4] satisfies the requirement (vi), a crosslinked product having excellent mechanical properties and heat aging resistance can be obtained.

[0046] The copolymer (A) preferably satisfies the following requirement (vii). Requirement (vii): The mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) and the natural logarithm [Ln(Mw)] of the weight average molecular weight (Mw) of the copolymer (A) satisfy the following formula (6): 6-0.45×Ln(Mw)≦[A3] mass fraction≦10 (6) When the copolymer (A) satisfies the requirement (vii), such a copolymer is preferred because it contains a sufficient amount of structural units derived from the non-conjugated polyene [A3].

[0047] The copolymer (A) preferably satisfies the following requirement (viii). Requirement (viii): The B value represented by the following formula (7) is 1.00 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(7) In formula (7), [E], [X], and [Y] represent the molar fraction of structural units derived from ethylene [A1], the molar fraction of structural units derived from an α-olefin having 3 to 20 carbon atoms [A2], and the molar fraction of structural units derived from a non-conjugated polyene [A3], respectively, and [EX] represents the ethylene-α-olefin having 3 to 20 carbon atoms dyad chain fraction. The B value is preferably 1.00 to 1.80, and more preferably 1.10 to 1.40.

[0048] When the copolymer (A) satisfies the requirement (viii), it tends to have an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature. The B value is an index showing the randomness of the copolymerization monomer sequence distribution in the copolymer (A), and [E], [X], [Y] and [EX] in the formula (7) are 13 The C-NMR spectrum can be measured and determined based on the reports of J. C. Randal [Macromolecules, 15, 353 (1982)] and J. Ray [Macromolecules, 10, 773 (1977)].

[0049] The intrinsic viscosity [η] of the copolymer (A) 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, still more preferably 1.5 to 3.5 dL / g, and particularly preferably 2.0 to 3.0 dL / g.

[0050] The weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 900,000, more preferably 30,000 to 550,000, even more preferably 50,000 to 530,000, still more preferably 100,000 to 500,000, and particularly preferably 200,000 to 490,000.

[0051] The intrinsic viscosity [η] and weight average molecular weight (Mw) of the copolymer (A) are preferably both within the above ranges. The intrinsic viscosity [η] of the copolymer (A) can be measured using the apparatus and conditions described in the Examples section. The weight average molecular weight (Mw) of the copolymer (A) can be measured by gel permeation chromatography (GPC) using the apparatus and conditions described in the Examples section.

[0052] The Mooney viscosity ML(1+4)125°C of copolymer (A) is preferably 10 to 90, more preferably 40 to 80, even more preferably 50 to 75, and particularly preferably 60 to 75. The composition containing copolymer (A) having a Mooney viscosity ML(1+4)125°C within the above range tends to have excellent roll processability even in high-hardness oil-less formulations, and also exhibits good post-treatment (ribbon handling properties) and excellent rubber physical properties. Details of the Mooney viscosity measurement conditions are described in the Examples section.

[0053] The glass transition temperature (Tg) of the copolymer (A) is preferably in the range of -80 to -40°C, more preferably -70 to -50°C, and even more preferably -60 to -40°C. When the glass transition temperature (Tg) of the copolymer (A) is in the above range, the obtained crosslinked product tends to have excellent low-temperature properties. Details of the measurement conditions for Tg are described in the Examples section.

[0054] The copolymer (A) can be obtained, for example, by copolymerizing ethylene [A1], an α-olefin [A2] having 3 to 20 carbon atoms, a non-conjugated polyene [A3], and, if necessary, a non-conjugated polyene [A4]. The copolymer (A) is preferably obtained by copolymerizing the above monomers in the presence of a metallocene compound, and more preferably by copolymerizing the above monomers in the presence of a catalyst system containing a metallocene compound. The copolymer (A) can be produced, for example, by the production method using a metallocene catalyst described in JP 2018-119096 A and WO 2015 / 122495 A.

[0055] The copolymer (A) may be used alone or in combination of two or more. The content of copolymer (A) 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, relative to 100% by mass of the composition.

[0056] <Hydrosilyl Group-Containing Compound (Y)> The hydrosilyl group-containing compound (Y) (hereinafter also referred to as "compound (Y)") is an organohydrogenpolysiloxane represented by the following formula (Y1): Compound (Y) has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in one molecule.

[0057] [ka]

[0058] The meanings of the symbols in formula (Y1) are as follows: n and p are each independently 0 or a positive number. m is 1 to 20. The sum of n, m, and p is 5 to 50. Multiple R 1 and R 2 are each independently a monovalent alkyl group. 1are each independently an alkyl group. 2 are each independently an alkyl group. 1 is R 2 In the alkyl group, some of the carbon atom-bonded hydrogen atoms may be substituted with halogen atoms. R a is an aralkyl group. The two R are independently R 1 , R 2 , hydrogen atoms, and R a When n=1, at least one of the two R is a hydrogen atom, and when n=0, both of the two R are hydrogen atoms. R is selected from the group consisting of R 1 or R 2 It is preferable that:

[0059] The crosslinked product obtained by crosslinking a composition containing the copolymer (A) and the compound (Y) as a crosslinking agent tends to have little odor and excellent heat aging resistance. In addition, the composition can be handled in air.

[0060] Compound (Y) is an organohydrogenpolysiloxane with a linear structure that has a relatively low degree of siloxane polymerization and has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule.

[0061] In formula (Y1), m is the number of diorganosiloxy units having silicon-bonded aralkyl groups, and is 1 to 20, preferably 2 to 10, more preferably 2 to 8, and even more preferably 3 to 6.

[0062] In formula (Y1), n ​​is the number of organohydrogensiloxy units having silicon-bonded hydrogen atoms. n can be 0 or 1, but when n=1, at least one of the two Rs is a hydrogen atom, and when n=0, both Rs are hydrogen atoms. In other words, the organohydrogenpolysiloxane represented by formula (Y1) has a structure containing at least two silicon-bonded hydrogen atoms per molecule. Note that even if n is a number other than 0 or 1, one or both of the Rs at both ends of the molecular chain can be silicon-bonded hydrogen atoms.

[0063] n is preferably a number other than 0 or 1, and more preferably a number satisfying n≧m. n is preferably 3-10, more preferably 3-9, and even more preferably 5-9.

[0064] In formula (Y1), p is the number of diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms. p may be 0, or may be the number obtained by subtracting the values ​​of n and m from the total degree of polymerization of siloxy units, which is represented by the sum of n, m, and p, as described below. p is preferably 0 to 12, more preferably 0 to 10, even more preferably 0 to 5, and particularly preferably 0 to 2.

[0065] In the organohydrogenpolysiloxane represented by formula (Y1), the diorganosiloxy unit (-[O-Si(R 1 )(R a )]-), organohydrogensiloxy units having silicon-bonded hydrogen atoms (-[O-Si(R 1 )H]-), and diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms (-[O-Si(R 1 )(R 2 The siloxy units such as (Y1)-) may be arranged in blocks or randomly. That is, the order of arrangement of the siloxy units in formula (Y1) is not particularly limited.

[0066] The compound (Y) has a relatively low degree of siloxane polymerization. In formula (Y1), 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 (Y1), it is preferable that m is 3 to 6, n is 5 to 9, and p is 0 to 2.

[0067] In formula (Y1), R 1 and R 2 The number of carbon atoms in the alkyl group 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, with a methyl group being particularly preferred.

[0068] In formula (Y1), R a The number of carbon atoms in the aralkyl group in R is preferably 7 to 20, more preferably 7 to 15. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. a As R, an aralkyl group containing at least one branching unit represented by -CH(CH3)- in the alkanediyl group between the aryl group such as a phenyl group and the silicon atom is preferred. a As the alkyl group, an aralkyl group represented by —CH2—CH(CH3)—C6H5 is particularly preferred.

[0069] The aralkyl group is a characteristic functional group that confers usefulness as a crosslinking agent to the hydrosilyl group-containing compound (Y). In particular, the presence of an aralkyl group together with a silicon-bonded hydrogen atom in the compound (Y) having n, m, and p within the above ranges tends to significantly improve the physical properties of the resulting crosslinked product. By using the compound (Y) in combination with the copolymer (A), a crosslinked product can be obtained that is particularly excellent in physical properties such as moldability, elongation at break, and compression molding strain.

[0070] The compound (Y) may be used alone or in combination of two or more. In the composition 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, still more preferably 0.8 to 30 parts by mass, particularly preferably 1 to 20 parts by mass, particularly preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass, relative to 100 parts by mass of copolymer (A).

[0071] <Platinum-based catalyst> Platinum catalysts for hydrosilyl crosslinking are widely used in hydrosilylation crosslinking reactions involving the addition of silicon-bonded hydrogen atoms to carbon-carbon double bonds. Platinum catalysts for hydrosilyl crosslinking are addition reaction catalysts, and any catalyst can be used without particular limitation as long as it promotes the addition reaction (hydrosilylation reaction of an alkene) between, for example, an alkenyl group contained in the copolymer (A) and a hydrosilyl group contained in the hydrosilyl group-containing compound (Y).

[0072] Examples of platinum-based catalysts include the fine powder metal platinum catalysts described in U.S. Pat. No. 2,970,150 and the like, the chloroplatinic acid catalysts described in U.S. Pat. No. 2,823,218 and the like, the complex compounds of platinum and hydrocarbons described in U.S. Pat. Nos. 3,159,601 and 159,662 and the like, the complex compounds of chloroplatinic acid and olefins described in U.S. Pat. No. 3,516,946 and the like, and the complex compounds of platinum and vinylsiloxanes described in U.S. Pat. Nos. 3,775,452 and 3,814,780 and the like.

[0073] Specific examples of platinum catalysts include platinum itself (platinum black); platinum complexes such as chloroplatinic acid, platinum-hydrocarbon complexes, platinum-vinylsiloxane complexes, platinum-alcohol complexes, chloroplatinic acid-olefin complexes, and chloroplatinic acid-vinylsiloxane complexes. Among these, platinum-vinylsiloxane complexes are preferred due to their high catalytic activity. Examples of platinum-vinylsiloxane complexes include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complexes. The platinum-based catalyst may be supported on a carrier such as alumina or silica.

[0074] The platinum catalyst may be used alone or in combination of two or more. In the composition of the present disclosure, the content of the platinum catalyst (e.g., platinum complex) is preferably 0.00001 to 0.3 parts by mass, more preferably 0.00005 to 0.15 parts by mass, even more preferably 0.0001 to 0.09 parts by mass, still more preferably 0.0002 to 0.03 parts by mass, particularly preferably 0.0003 to 0.021 parts by mass, particularly preferably 0.0005 to 0.018 parts by mass, and most preferably 0.001 to 0.015 parts by mass, relative to 100 parts by mass of copolymer (A).

[0075] <Heavy calcium carbonate and light calcium carbonate> In addition to the above-mentioned components, the composition of the present disclosure further contains ground calcium carbonate and light calcium carbonate.

[0076] Calcium carbonate is classified into heavy calcium carbonate, which is produced by mechanically crushing and processing limestone, marble, chalk, etc., and light calcium carbonate, which is produced by a chemical reaction using raw materials such as limestone. Light calcium carbonate usually has a more uniform particle size and shape than, for example, heavy calcium carbonate.

[0077] The composition of the present disclosure has excellent scorch resistance. In addition, the composition of the present disclosure can form a crosslinked body with high electrical resistance. Although the reasons for these effects are unclear, it is speculated that the fact that the composition of the present disclosure contains both heavy calcium carbonate and light calcium carbonate in a hydrosilyl crosslinking system of copolymer (A) / compound (Y) contributes to the manifestation of the above effects. Specifically, it is speculated that the mixture of heavy calcium carbonate with light calcium carbonate, which has a more uniform particle size and shape, allows the gaps in the heavy calcium carbonate to be filled with the light calcium carbonate, thereby contributing to the manifestation of the above effects.

[0078] Scorch resistance refers to the property of a long induction time required for the crosslinking reaction to begin after an uncrosslinked rubber composition is heated. In the production of rubber products, a molding step is usually required before or during the crosslinking treatment of an uncrosslinked rubber composition, and the uncrosslinked rubber composition is exposed to heat during this process. If crosslinking progresses significantly during molding, molding becomes difficult, so an induction time appropriate for molding is required. A long induction time can be said to have good scorch resistance.

[0079] The composition of the present disclosure has excellent scorch resistance because the crosslinking reaction is suppressed, for example, at a relatively low temperature (e.g., 50 to 140°C) during molding. Furthermore, the composition of the present disclosure can crosslink in a short time at a relatively high temperature (e.g., 150 to 220°C) during crosslinking treatment.

[0080] Examples of grinding methods for producing heavy calcium carbonate include a dry method and a wet method. Among these, from the viewpoint of the storage stability of the composition of the present disclosure, heavy calcium carbonate obtained by a dry method is preferred. A wet method is preferred as a method for producing light calcium carbonate.

[0081] The calcium carbonate may be surface-treated with a surface treatment agent from the viewpoint of improving the workability of the composition, etc. The amount of the surface treatment agent used is preferably 0.1 to 20 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of calcium carbonate.

[0082] Surface treatment agents include, for example, organic substances or surfactants such as fatty acids, fatty acid soaps, and fatty acid esters, as well as coupling agents such as silane coupling agents and titanate coupling agents. Fatty acids include, for example, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. Fatty acid soaps include, for example, salts of the above fatty acids, such as sodium salts or potassium salts. Fatty acid esters include, for example, alkyl esters of the above fatty acids. Surfactants include, for example, sulfate ester-type anionic surfactants and sulfonic acid-type anionic surfactants. Sulfate ester-type anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate esters and long-chain alcohol sulfate esters, as well as their salts, such as sodium salts or potassium salts. Examples of sulfonic acid type anionic surfactants include alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acids, paraffin sulfonic acids, α-olefinsulfonic acids, and alkylsulfosuccinic acids, as well as salts thereof such as sodium salts or potassium salts.

[0083] The particle size D50 of the heavy calcium carbonate is preferably 0.1 to 10.0 μm, more preferably 1.0 to 5.0 μm, and even more preferably 1.5 to 2.5 μm. The particle size D50 of the precipitated calcium carbonate is preferably 0.0005 to 30.0 μm, more preferably 0.001 to 10.0 μm, and even more preferably 0.01 to 3.0 μm. The particle diameter D50 means the particle diameter at 50% accumulation of particles when particle size distribution of particles is measured on a volume basis by a laser diffraction particle size distribution measurement method.

[0084] The heavy calcium carbonate may be used alone or in combination of two or more. The precipitated calcium carbonate may be used alone or in combination of two or more.

[0085] In the composition of the present disclosure, the total content of the heavy calcium carbonate and the light calcium carbonate is preferably 5 to 500 parts by mass, more preferably 10 to 350 parts by mass, even more preferably 20 to 200 parts by mass, still more preferably 30 to 150 parts by mass, and particularly preferably 50 to 120 parts by mass, relative to 100 parts by mass of the copolymer (A).

[0086] In the composition of the present disclosure, the proportion of the content of light calcium carbonate relative to the total content of heavy calcium carbonate and light calcium carbonate is preferably 10 to 90 mass%, more preferably 30 to 85 mass%, even more preferably 50 to 80 mass%, and particularly preferably 55 to 75 mass%.

[0087] <Other ingredients> The composition of the present disclosure may further contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include antioxidants, reinforcing agents, softeners, moisture absorbents, reaction inhibitors, organic peroxides, crosslinking aids, crosslinking accelerators, foaming agents, activators, processing aids, plasticizers, tackifiers, colorants, and polymers other than the copolymer (A). The other components may be used alone or in combination of two or more.

[0088] (anti-aging agent) The compositions of the present disclosure may further contain an anti-aging agent. As the antiaging agent, known antiaging agents that can be compounded in general rubber compositions can be used. Examples of antiaging agents include phenolic antiaging agents, amine antiaging agents, and sulfur antiaging agents. Among these, phenolic antiaging agents are preferred.

[0089] The phenolic antioxidant is preferably a hindered phenolic compound, such as 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4'-butylidenebis(6-tert-butyl-m-cresol), N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], dibutylhydroxytoluene, and 2,5-di-tert-butylhydroquinone.

[0090] Examples of the amine-based antioxidant include aromatic secondary amine-based antioxidants such as phenylbutylamine, N,N-di-2-naphthyl-p-phenylenediamine, and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

[0091] Examples of sulfur-based antioxidants include thioether-based antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0092] The antioxidant may be used alone or in combination of two or more. The case where the composition of the present disclosure contains an antioxidant will be described below: The content of the antioxidant 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 0.5 to 8 parts by mass, relative to 100 parts by mass of copolymer (A).

[0093] (reinforcing agent) The composition of the present disclosure may further contain a reinforcing agent other than the calcium carbonate described above in order to improve physical properties such as tensile stress at break and tensile elongation at break. As the reinforcing agent, any known reinforcing agent that can be compounded in a general rubber composition can be used. Examples of reinforcing agents other than calcium carbonate include carbon black, talc, clay, kaolin, silica, and differential silicic acid.

[0094] Among the reinforcing agents, carbon black is preferred. The composition containing carbon black tends to have better processability and also tends to form a crosslinked product having better mechanical properties such as tensile strength, tear strength, and abrasion resistance. The carbon black may be surface-treated with a silane coupling agent or the like.

[0095] The reinforcing agent may be used alone or in combination of two or more. The case where the composition of the present disclosure contains a reinforcing agent will be described below. The content of the reinforcing agent is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 30 to 100 parts by mass, per 100 parts by mass of copolymer (A). The content of carbon black is preferably within the above range.

[0096] (softener) The compositions of the present disclosure may further contain an emollient. The softener may be any known softener that can be incorporated into a typical rubber composition. Examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic polymers such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub(factice). Among these, petroleum-based softeners are preferred, process oils are more preferred, and paraffin-based process oils are particularly preferred.

[0097] The softener may be used alone or in combination of two or more kinds. The case where the composition of the present disclosure contains a softener will be described below. The content of the softener is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 10 to 120 parts by mass, per 100 parts by mass of copolymer (A). When the content of the softener is within the above range, a composition can be obtained that has little tack and is excellent in processability, heat aging resistance, mechanical properties, etc.

[0098] (moisture absorbent) The compositions of the present disclosure may further contain a moisture absorbent. Examples of moisture absorbents include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. Of these, calcium oxide is preferred.

[0099] The moisture absorbent may be used alone or in combination of two or more kinds. The case where the composition of the present disclosure contains a moisture absorbent will be described below: The content of the moisture absorbent is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of copolymer (A).

[0100] (Reaction inhibitor) The composition of the present disclosure preferably further contains a reaction inhibitor. The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation reaction of an alkene) between, for example, an alkenyl group contained in the copolymer (A) and a hydrosilyl group contained in the hydrosilyl group-containing compound (Y). The composition containing the reaction inhibitor tends to have stable processability during kneading and molding.

[0101] Examples of the reaction inhibitor include benzotriazole; acrylonitrile; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1-ethynyl-1-cyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; N,N-diallylacetate; amide compounds such as N,N-diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalic acid diamide, N,N,N',N'-tetraallyl-m-phthalic acid diamide, and N,N,N',N'-tetraallyl-p-phthalic acid diamide; and others, sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, and tetramethyltetravinylcyclotetrasiloxane. Among these compounds, acetylene alcohols such as 1-ethynyl-1-cyclohexanol are preferred.

[0102] The reaction inhibitor may be used alone or in combination of two or more. The case where the composition of the present disclosure contains a reaction inhibitor will be described below: The content of the reaction inhibitor is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.005 to 0.8 parts by mass, per 100 parts by mass of copolymer (A).

[0103] <Preparation of Composition> The composition of the present disclosure can be prepared, for example, by mixing the copolymer (A), the hydrosilyl group-containing compound (Y), a platinum-based catalyst, heavy calcium carbonate, and light calcium carbonate, and, if necessary, other components.

[0104] The composition can be prepared, for example, by a method comprising: a first step of kneading the copolymer (A), the hydrosilyl group-containing compound (Y), and, if necessary, the other components; and a second step of adding a platinum catalyst and, if necessary, the other components to the kneaded mixture obtained in the first step, and kneading the mixture. The heavy calcium carbonate may be added in the first step, the second step, or both steps separately, but is preferably added in the first step. The light calcium carbonate may be added in the first step, the second step, or both steps separately, but is preferably added in the first step.

[0105] When at least one selected from the group consisting of an antioxidant, a reinforcing agent, a softener, an activator, a processing aid, a plasticizer, a tackifier, a colorant, and a polymer other than the copolymer (A) is added as another component, it is preferable to add it in the first step, and when at least one selected from the group consisting of a moisture absorbent, a reaction inhibitor, an organic peroxide, a crosslinking aid, a crosslinking accelerator, and a foaming agent is added, it is preferable to add it in the second step. For example, the case where an antioxidant, a reinforcing agent, a softener, a moisture absorbent, and a reaction inhibitor are blended as other components will be described. In one embodiment, it is preferable to blend the antioxidant, the reinforcing agent, and the softener in the first step, and it is preferable to blend the moisture absorbent and the reaction inhibitor in the second step.

[0106] In the first step, the components may be kneaded using a kneading device such as a Banbury mixer, a kneader, or an internal mixer. The kneading temperature in the first step is preferably 80 to 170° C., more preferably 110 to 170° C., and even more preferably 130 to 170° C. The kneading time in the first step is preferably 1 to 10 minutes, and more preferably 2 to 8 minutes.

[0107] In the second step, the above components may be added to the kneaded product obtained in the first step and kneaded using a kneading device such as a roll, kneader, or extruder. The kneading temperature in the second step is preferably 10 to 100° C., more preferably 20 to 80° C., and even more preferably 40 to 80° C. The kneading time in the second step is preferably 1 to 30 minutes, and more preferably 5 to 20 minutes.

[0108] The Mooney viscosity ML(1+4)125°C of the composition before blending with the platinum catalyst (for example, the composition obtained in the first step) is preferably 10 to 250, more preferably 20 to 100, even more preferably 30 to 70, and particularly preferably 40 to 55. The composition having such a Mooney viscosity exhibits good post-treatment quality and has excellent rubber physical properties. The Mooney viscosity is measured in accordance with JIS K6300-1:2013.

[0109] The composition of the present disclosure has excellent scorch resistance. Specifically, when the torque of the composition is measured using a vulcanization measuring device at a temperature of 125°C, the time (TS1) from the start of measurement until the torque reaches a minimum value (S'min) and then increases by 1 [dNm] is preferably 30 minutes or more, more preferably 40 minutes or more, even more preferably 50 minutes or more, and particularly preferably 60 minutes or more. There is no particular upper limit for TS1, but it is, for example, 480 minutes or less. Details of the measurement conditions for TS1 are described in the Examples section.

[0110] By using the composition of the present disclosure, a crosslinked body having high electrical resistance can be formed. Specifically, the volume resistivity of a sheet having a thickness of 1 mm obtained by press-molding the composition at 180° C. for 10 minutes is preferably 1.0×10 5 Ω·cm or more, preferably 5.0×10 5 ~1.0×10 14 Ω·cm, more preferably 1.0×10 6 ~1.0×10 14 The volume resistivity is measured by a volume resistivity test at an applied voltage of 100 V in accordance with JIS K6911:1995.

[0111] [Crosslinked product and its uses] The crosslinked body of the present disclosure can be obtained by subjecting the composition of the present disclosure to a crosslinking treatment. The crosslinked body of the present disclosure can be obtained, for example, by molding the composition of the present disclosure into a desired shape by various molding methods, and then introducing the molded body into a crosslinking tank and heating it to crosslink it, either simultaneously with molding. When the composition of the present disclosure contains a foaming agent, foaming proceeds along with crosslinking, resulting in a foamed crosslinked body. Examples of molding methods include methods using an extruder, a calendar roll, a press molding machine, an injection molding machine, or a transfer molding machine. Molding and crosslinking may or may not require the use of a mold. When a mold is not used, the composition is usually molded and crosslinked continuously.

[0112] The heating temperature during crosslinking of the composition or the molded article is preferably 140°C or higher, more preferably 150 to 220°C, and even more preferably 160 to 200°C. The heating time during the crosslinking treatment is preferably 1 to 30 minutes, more preferably 5 to 20 minutes. The crosslinking treatment may be performed using a heating bath such as a hot air vulcanization bath (HAV), a steam vulcanization bath, a glass bead fluidized bed, a far-infrared heating furnace, a microwave vulcanization bath (UHF), or a molten salt bath (LCM).

[0113] The composition may be press-molded to effect primary crosslinking, followed by removal from the mold to obtain a primary molded article, which may then be subjected to secondary crosslinking in a heat medium. Specifically, the composition may be press-molded, preferably at 120 to 200°C for 1 to 20 minutes, more preferably at 150 to 200°C for 10 to 18 minutes, to effect primary crosslinking, and then removed from the mold to obtain a primary molded article. The resulting primary molded article may then be subjected to secondary crosslinking in a heat medium, preferably at 120 to 160°C for 10 to 24 hours, more preferably at 140 to 160°C for 15 to 20 minutes. Examples of heat mediums used for secondary crosslinking include air, steam, paraffin-based process oil, and molten salt.

[0114] The article of the present disclosure includes the crosslinked body of the present disclosure. The above-mentioned articles can be used for various purposes, and are preferably used for, for example, hose products, vibration-proof rubber, vibration-insulating or vibration-damping materials (e.g., engine mounts and motor mounts), muffler hangers, sponges (e.g., weatherstrip sponges, heat-insulating sponges, protect sponges, and micro-foam sponges), cables (e.g., ignition cables, cab tire cables, and high-tension cables), wire coating materials (e.g., high-voltage wire coating materials, low-voltage wire coating materials, and marine wire coating materials), glass run channels, tire rubber, O-rings, packings (e.g., condenser packing), gaskets, industrial rolls, belts (e.g., heat-insulating belts, copier belts, and conveyor belts), golf club grips, cane grips, toothbrush grips, tableware (e.g., spoons, forks, and chopsticks) grips, broom grips, teacup and rice bowl grips, colored skin materials, paper feed rolls, roofing sheets, highly foamed sealants, automotive sealants, civil engineering or construction sealants, and industrial sealants.

[0115] A preferred article of the present disclosure is a hose product. The hose product includes a crosslinked body formed from the composition of the present disclosure, and has, for example, a layer (crosslinked body layer) formed from the composition of the present disclosure. The hose product may be a single-layer hose product consisting solely of a layer formed from the composition of the present disclosure, or a hose product having two or more layers. In the case of a hose product having two or more layers, the hose product may further have at least one layer selected from the group consisting of, for example, a layer made of natural rubber, a fabric layer, a thermoplastic resin layer, and a thermosetting resin layer.

[0116] A method for producing a hose product from the composition of the present disclosure includes, for example, molding the composition into a desired hose shape, followed by crosslinking the composition (molded product) simultaneously with molding. During molding, the composition is molded into a hose shape having a hollow portion using an extruder, calendar roll, press molding machine, injection molding machine, transfer molding machine, or the like.

[0117] Examples of hose products include hoses for vehicles (e.g., automobiles and motorbikes), industrial machinery, industrial machinery, and agricultural machinery. Specifically, the hose products can be suitably used as water hoses, oil hoses, or air hoses, and more specifically, can be suitably used as various hoses such as radiator hoses, heater hoses, air conditioner drain hoses, wiper water supply hoses, roof drain hoses, radiator overflow drain hoses, and brake reservoir hoses.

[0118] Among hose products, vehicle hoses are preferred, vehicle water system hoses are more preferred, and radiator hoses or heater hoses are even more preferred. In recent years, in order to realize a carbon-free society, there has been an active movement toward an EV shift, which aims to switch from gasoline or diesel vehicles to electric vehicles (EVs) powered by electric motors. From a safety perspective, hoses used in the coolant systems that cool the batteries or motors of EVs are desirably highly electrically insulating. Furthermore, it is known that minute currents flowing through the vehicle body can cause the hose itself to corrode and deteriorate, which can lead to water leakage in vehicle water system hoses. The crosslinked body of the present disclosure has a high electrical resistance value, and is therefore considered to have excellent electrical insulation and be able to suppress the water leakage, making it suitable for use in the above applications.

[0119] [Example of situation] The present disclosure relates to, for example, the following [1] to

[13] . [1] A composition containing an ethylene-α-olefin-non-conjugated polyene copolymer (A), a hydrosilyl group-containing compound (Y), a platinum catalyst, heavy calcium carbonate, and light calcium carbonate, The copolymer (A) comprises a structural unit derived from ethylene [A1], a structural unit derived from an α-olefin [A2] having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures in total, at least one of which is selected from the group consisting of the following formulas (I) and (II): The hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (Y1) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in one molecule: composition. [ka] [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and a plurality of R 1 and R 2are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 , R 2 , hydrogen atoms, and R a -[O-Si(R 1 )(R a )]-, -[O-Si(R 1 )H]- and -[O-Si(R 1 )(R 2 The structural units of n=1, n=2, and n=3 may be arranged in a block fashion or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms. [2] The composition according to [1], wherein the proportion of the content of the light calcium carbonate relative to the total content of the heavy calcium carbonate and the light calcium carbonate is 10 to 90 mass%. [3] The composition according to [1] or [2], wherein the copolymer (A) satisfies the following requirements (i) and (ii): Requirement (i): the ratio [(A1) / (A2)] of the molar fraction (A1) of the structural units derived from the ethylene [A1] to the molar fraction (A2) of the structural units derived from the α-olefin [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; Requirement (ii): The mass fraction of the structural units derived from the non-conjugated polyene [A3] is 0.07 to 10 mass % in 100 mass % of the copolymer (A). [4] The composition according to [3] above, wherein the copolymer (A) satisfies any one or more of the following requirements (iii) to (v): Requirement (iii): the weight-average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), and the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]) satisfy the following formula (1): 4.5≦Mw×[A3] mass fraction / 100 / [A3] molecular weight≦80 (1) Requirement (iv): Complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at a frequency of ω=100 rad / sec * (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) satisfy the following formula (2): P / ([η] 2.9 ) ≦ [A3] mass fraction × 6 (2) Requirement (v): Complex viscosity η at a frequency ω = 0.01 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.01) (Pa·sec) and the complex viscosity η at a frequency of ω=10 rad / sec * (ω=10) (Pa·sec) and the apparent iodine value derived from the non-conjugated polyene [A3] satisfy the following formula (3). Log[η * (ω=0.01) ] / Log[η * (ω=10) ] ≦ 0.0753 × {apparent iodine value derived from non-conjugated polyene [A3]} + 1.42 (3) [5] The composition according to any one of the above [1] to [4], wherein the non-conjugated polyene [A3] includes 5-vinyl-2-norbornene (VNB). [6] The composition according to any one of the above [1] to [5], wherein the α-olefin [A2] having 3 to 20 carbon atoms is propylene. [7] The composition according to any one of the above [1] to [6], further comprising 5 to 200 parts by mass of carbon black per 100 parts by mass of the copolymer (A). [8] The composition according to any one of the above [1] to [7], further comprising 1 to 200 parts by mass of a softener per 100 parts by mass of the copolymer (A). [9] The composition according to any one of [1] to [8], wherein, when the torque of the composition is measured using a vulcanization measuring device at a temperature of 125°C, the time (TS1) from the start of measurement until the torque reaches a minimum value (S'min) and then increases by 1 [dNm] is 30 minutes or longer.

[10] The composition is press-molded at 180°C for 10 minutes to obtain a sheet having a thickness of 1 mm, and the volume resistivity measured by a volume resistivity test at an applied voltage of 100 V in accordance with JIS K6911:1995 is 1.0 x 10 5 The composition according to any one of [1] to [9] above, which has a resistivity of Ω·cm or more.

[11] The composition according to any one of [1] to

[10] above, which is for use in a hose.

[12] A crosslinked product of the composition according to any one of [1] to

[11] above.

[13] A hose product comprising the crosslinked body according to

[12] above. [Example]

[0120] The composition of the present disclosure will be described in more detail below based on examples, but the composition of the present disclosure is not limited to these examples.

[0121] [Physical properties of copolymer (A)] The physical properties of the copolymer (A) were measured as follows.

[0122] <Composition of Copolymer (A)> The content of each structural unit in the copolymer (A) is: 13 The C-NMR spectrum of copolymer (A) was calculated using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.) under the conditions of a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an accumulation number of 8000. 13 C-NMR spectrum was measured.

[0123] <Mooney viscosity> The Mooney viscosity ML(1+4) at 125°C of the copolymer (A) was measured in accordance with JIS K6300-1:2013 using a Mooney viscometer (Model SMV-301 manufactured by Shimadzu Corporation).

[0124] The B value of the copolymer (A) was calculated based on the following formula by measuring the C-NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) 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 = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] The meanings of [E], [X], [Y], and [EX] are as described above.

[0125] <Limiting viscosity> The limiting viscosity [η] of the copolymer (A) was measured using an automatic limiting viscometer (manufactured by Reikai Co., Ltd.) under the conditions of a temperature of 135°C and a measurement solvent of decalin.

[0126] <Weight-average molecular weight (Mw)> The weight-average molecular weight (Mw) of the copolymer (A) is a value in terms of polystyrene measured by gel permeation chromatography (GPC). The measuring apparatus and conditions are as follows. The molecular weight was calculated based on the calibration curve prepared using commercially available monodisperse polystyrene and the conversion method. Apparatus: Gel permeation chromatograph Alliance GP2000 type (manufactured by Waters) Analytical apparatus: Empower2 (manufactured by Waters) Column: TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (7.5 mm I.D. × 30 cm, manufactured by Tosoh Corporation) Column temperature: 140°C Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Detector: Differential refractometer (RI) Flow rate: 1.0 mL / min Injection volume: 400 μL Sampling time interval: 1 second Column calibration: Monodisperse polystyrene (Tosoh Corporation) Molecular weight conversion: Old EPR conversion / calibration method taking viscosity into account

[0127] <Complex viscosity η * > The Ares rheometer (Rheometric Scientific) was used as a rheometer. The complex viscosity η was measured at 190°C, 1.0% strain, and a frequency of ω = 0.01 rad / s. * (ω=0.01) , complex viscosity η at frequency ω = 0.1 rad / s * (ω=0.1) , complex viscosity η at frequency ω=10 rad / s * (ω=10) , and the complex viscosity η at frequency ω = 100 rad / s * (ω=100) From the results obtained, η * (ω=0.1) and η * (ω=100) The P value (η * (ω=0.1) / η * (ω=100) ), and Log[η * (ω=0.01) ] / Log[η * (ω=10) ] was calculated.

[0128] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of copolymer (A) was measured by DSC (differential scanning calorimeter) under the following conditions. Using a differential scanning calorimeter (RDC220, manufactured by SII Corporation), approximately 10 mg of a 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. The sample was then cooled to -100°C at a heating rate of 10°C / min, held at -100°C for 5 minutes, and then heated to 200°C at a heating rate of 10°C / min. The temperature based on the glass transition at this time was taken as the glass transition temperature (Tg).

[0129] [Production Example 1: Production of Copolymer (A-1)] Ethylene-propylene-5-vinyl-2-norbornene (VNB) copolymer (A-1) was produced using a continuous polymerization apparatus as follows.

[0130] A 300-L polymerization reactor was continuously fed with 58.3 L / hr of dehydrated and purified hexane solvent through line 1, and 4.5 mmol / hr of triisobutylaluminum (TIBAL), 0.150 mmol / hr of (C6H5)3CB(C6F5)4, and 0.030 mmol / hr of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride through line 2. Ethylene, 6.6 kg / hr, 9.3 kg / hr of propylene, 18 L / hr of hydrogen, and 340 g / hr of VNB were simultaneously fed into the reactor through separate lines, and copolymerization was carried out under the conditions of a polymerization temperature of 87°C, a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

[0131] The ethylene-propylene-VNB copolymer solution produced in the polymerization reactor was continuously discharged at a flow rate of 88.0 L / hr, heated to 170°C (pressure increased to 4.1 MPaG), and fed to a phase separator. At this time, ethanol, a polymerization inhibitor, was continuously introduced into the discharge line in an amount of 0.1 mol relative to the TIBAL in the liquid component extracted from the polymerization reactor.

[0132] In the phase separator, the ethylene-propylene-VNB copolymer solution was separated into a dense phase (lower phase) containing the majority of the ethylene-propylene-VNB copolymer and a dilute phase (upper phase) containing a small amount of polymer. The separated dense phase was introduced into heat exchanger K at a flow rate of 85.4 L / hr and then into a hopper where the solvent was evaporated and separated, yielding ethylene-propylene-VNB copolymer (A-1) at a rate of 7.8 kg / hr. The physical properties of the resulting ethylene-propylene-VNB copolymer (A-1) were evaluated as described above. The results are shown in Table 1.

[0133] [Table 1]

[0134] [Production Example 2: Production of Compound (Y-1)] A reactor was charged with 536 g of methylhydrogenpolysiloxane represented by the following formula (Y1b) 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 to 90°C.

[0135] After the dropwise addition, stirring was continued for 2 hours at 85°C, and then 0.5 g of the reaction solution was sampled and confirmed to be about 36% by alkali decomposition gas generation method (remaining Si-H groups were decomposed with an ethanol / aqueous solution of KOH, and the reaction rate of Si-H groups was calculated from the volume of generated hydrogen gas). The reaction solution was then heated to 135°C under reduced pressure for 2 hours to distill off low boiling points, yielding 673 g of compound (Y-1).

[0136] The obtained compound (Y-1) is 29 The compound (Y-1) was confirmed to be a compound represented by the following formula (Y1a) by Si-NMR. The viscosity of the obtained compound (Y-1) was measured at 25°C using an Ubbelohde viscometer according to JIS Z8803:2011. 2 / s.

[0137] [ka]

[0138] The raw materials used in the examples are listed below. Anti-aging agent: Irganox 1010, manufactured by BASF Japan Ltd. Carbon black: Asahi #52, manufactured by Asahi Carbon Co., Ltd. Heavy calcium carbonate: Whiten SB, manufactured by Shiraishi Calcium Co., Ltd. Clay 1: Kaolin (hydrate), Vanderbilt Chemicals, Dixie Clay Clay 2: Kaolin clay, manufactured by Shiraishi Kogyo Co., Ltd., Burgess 30, average particle size 1.5 μm Clay 3: Calcined kaolin, manufactured by Burgess, Burgess KE Precipitated calcium carbonate 1: Shiraishi Calcium Co., Ltd., Silver W Precipitated calcium carbonate 2: Shiraishi Kogyo Co., Ltd., Hakuenka CC Softener: Idemitsu Kosan Co., Ltd., Diana Process PS-430 Paraffin-based process oil Moisture absorbent: Inoue Lime Industry Co., Ltd., Vesta PP, calcium oxide Reaction inhibitor: manufactured by Nissin Chemical Industry Co., Ltd. ETCH, 1-ethynyl-1-cyclohexanol Platinum catalyst: SRX212Catalyst manufactured by Toray Dow, a product containing 1% by mass or more but less than 3% by mass of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complex

[0139] [Examples and Comparative Examples: Preparation of Uncrosslinked Composition (Unvulcanized Rubber)] In the first step, the raw materials shown in Raw Material 1 in Table 2 were mixed for 2 minutes at 140°C using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.). After that, the ram was raised and cleaned, and the mixture was mixed for another minute and then discharged at approximately 150°C to obtain the compound for the first step (Compound 1).

[0140] Next, in the second step, Compound 1 obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; surface temperature of front roll: 50°C; surface temperature of rear roll: 50°C; rotation speed of front roll: 16 rpm; rotation speed of rear roll: 18 rpm), and the raw materials shown in Raw Material 2 in Table 2 were added thereto and kneaded for 10 minutes to obtain the compound for the second step (Compound 2).

[0141] [Mooney viscosity] The Mooney viscosity ML(1+4)125°C of the above-mentioned Blend 1 was measured using a Mooney viscometer (Model SMV-301 manufactured by Shimadzu Corporation) in accordance with JIS K6300-1:2013.

[0142] [Vulcanization speed test] Using a vulcanization measuring device: MDR2000 (manufactured by ALPHATECHNOLOGIES), TS1 of the above-mentioned Compound 2 was measured as follows under the measurement conditions of a temperature of 125°C, and the vulcanization rate (tc80, tc90) of the above-mentioned Compound 2 was measured as follows under the measurement conditions of a temperature of 180°C and a time of 20 minutes.

[0143] The torque change obtained under conditions of constant temperature and 1.66 Hz was measured. The difference between the maximum torque (S'max) and the minimum torque (S'min) was S'max - S'min [dNm]. The time when the torque of the measured sample increased by 1 [dNm] after reaching the minimum torque (S'min) was TS1 [min]. The time when the torque of the measured sample reached 80% (tc80) and the time when the torque of the measured sample reached 90% (tc90) were calculated, assuming the minimum torque (S'min) is 0% and the maximum torque (S'max) is 100%. A higher TS1 indicates better scorch resistance for the composition. A lower tc90 indicates a faster vulcanization rate (crosslinking rate).

[0144] [Hardness test: Hardness (Durometer-A)] The above-mentioned compound 2 was press-molded in a mold at 180°C for 10 minutes using a press molding machine to produce a sheet with a thickness of 2 mm. The hardness of the above-mentioned sheet was measured in accordance with the description of "Hardness test" in Section 7 of JIS K7312:1996 "Physical test methods for thermosetting polyurethane elastomer molded products" and the description of Test Type A in Section 6 of JIS K6253:2006 "Vulcanized rubber and thermoplastic rubber - Determination of hardness".

[0145] [Tensile test: modulus, tensile stress at break, tensile elongation at break] The above-mentioned sheet with a thickness of 2 mm was punched out to prepare a No. 3 dumbbell test piece as described in JIS K6251:1993. Using this test piece, a tensile test was carried out according to the method specified in JIS K6251, paragraph 3, at a measurement temperature of 25°C and a tensile speed of 500 mm / min, and the tensile stress at 100% and 300% elongation (100% modulus (M100) and 300% modulus (M300)), tensile stress at break (TB), and tensile elongation at break (EB) were measured.

[0146] [Effective network chain density (crosslink density)] The 2 mm thick sheet was cut into a size of 20 mm × 20 mm × 2 mm, and then immersed in toluene at 37°C for 72 hours to swell it in accordance with JIS K6258:1993. The effective network chain density (crosslink density) was calculated using the Flory-Rehner formula (B).

[0147]

number

[0148] In formula (B), ν(pieces / cm 3 ) is the effective network chain density (crosslink density), and 3 is the number of effective network chains in R is the volume fraction of pure rubber in the swollen crosslinked rubber, V0 is the molar volume of the solvent, μ is the rubber-solvent interaction constant = 0.49, and A is Avogadro's number.

[0149] [Compression set (CS)] Compound 2 was crosslinked by heating at 180°C for 15 minutes using a press molding machine equipped with a cylindrical mold, to prepare a right cylindrical test piece with a thickness of 12.7 mm and a diameter of 29 mm. These test pieces were held in a -25°C atmosphere at a compression ratio of 25% for 22 hours, or in a 120°C atmosphere at a compression ratio of 25% for 70 hours, in accordance with JIS K6262:1997, and the permanent set (%) after release from compression was determined.

[0150] [Electrical properties (volume resistivity)] The above-mentioned Compound 2 was press-molded in a mold at 180°C for 10 minutes using a press molding machine to produce a sheet with a thickness of 1 mm. A volume resistivity test was carried out in accordance with JIS K6911:1995 at an applied voltage of 100V to measure the specific volume resistivity of the above-mentioned 1 mm thick sheet. Table 2 shows the average values.

[0151] [Table 2]

Claims

1. an ethylene / α-olefin / non-conjugated polyene copolymer (A); a hydrosilyl group-containing compound (Y); A platinum-based catalyst; Heavy calcium carbonate, Light calcium carbonate, A composition comprising: The copolymer (A) comprises a structural unit derived from ethylene [A1], a structural unit derived from an α-olefin [A2] having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures in total, each of which is at least one type selected from the group consisting of the following formulas (I) and (II): The hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (Y1), which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule: composition. 【Chemistry 1】 [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 , R 2 , a hydrogen atom, and R a is selected from the group consisting of —[O—Si(R 1 ) (R a )]-,-[O-Si(R 1 )H]- and -[O-Si(R 1 ) (R 2 ) )]- may be arranged in a block form or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

2. 2. The composition according to claim 1, wherein a ratio of a content of the light calcium carbonate to a total content of the heavy calcium carbonate and the light calcium carbonate is 10 to 90 mass%.

3. The composition according to claim 1, wherein the copolymer (A) satisfies the following requirements (i) and (ii): Requirement (i): the ratio [(A1) / (A2)] of the molar fraction (A1) of the structural units derived from the ethylene [A1] to the molar fraction (A2) of the structural units derived from the α-olefin [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; Requirement (ii): The mass fraction of the structural units derived from the non-conjugated polyene [A3] is 0.07 to 10 mass % in 100 mass % of the copolymer (A).

4. The composition according to claim 3, wherein the copolymer (A) satisfies any one or more of the following requirements (iii) to (v): Requirement (iii): the weight average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), and the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]) satisfy the following formula (1): 4.5≦Mw×mass fraction of [A3] / 100 / molecular weight of [A3]≦80 (1) Requirement (iv): Complex viscosity η at a frequency ω = 0.1 rad / sec obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at a frequency ω = 100 rad / sec * (ω=100) (Pa sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) satisfy the following formula (2): P / ([η] 2.9 ) ≦ mass fraction of [A3] × 6 (2) Requirement (v): Complex viscosity η at a frequency ω = 0.01 rad / sec obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer * (ω=0.01) (Pa·sec) and the complex viscosity η at a frequency ω = 10 rad / sec * (ω=10) (Pa·sec) and the apparent iodine value derived from the non-conjugated polyene [A3] satisfy the following formula (3). Log [η * (ω=0.01) ] / Log[η * (ω=10) ] ≦ 0.0753 × {apparent iodine value derived from the non-conjugated polyene [A3]} + 1.42 (3)

5. The composition according to claim 1, wherein the non-conjugated polyene [A3] comprises 5-vinyl-2-norbornene (VNB).

6. The composition according to claim 1, wherein the α-olefin [A2] having 3 to 20 carbon atoms is propylene.

7. The composition according to claim 1, further comprising 5 to 200 parts by mass of carbon black per 100 parts by mass of the copolymer (A).

8. The composition according to claim 1, further comprising 1 to 200 parts by mass of a softener relative to 100 parts by mass of the copolymer (A).

9. 2. The composition according to claim 1, wherein, when the torque of the composition is measured using a vulcanization measuring device at a temperature of 125°C, the time (TS1) from the start of measurement until the torque reaches a minimum value (S'min) and then increases by 1 [dNm] is 30 minutes or longer.

10. The composition is press-molded at 180°C for 10 minutes to obtain a sheet having a thickness of 1 mm. The specific volume resistivity measured by a volume resistivity test at an applied voltage of 100 V in accordance with JIS K6911:1995 is 1.0 x 10 5 The composition of claim 1 , wherein the viscosity is Ω·cm or greater.

11. The composition according to any one of claims 1 to 10, which is for use in hoses.

12. A crosslinked product of the composition according to any one of claims 1 to 10.

13. A hose product comprising the crosslinked body according to claim 12.

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