Compositions, crosslinked materials, gaskets, packings, and molded articles

Abstract

The present invention provides a composition containing an ethylene-α-olefin-nonconjugated polyene copolymer, a hydrosilyl group-containing compound, a platinum-based catalyst, and a zeolite, which has a high crosslinking rate. [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, and a zeolite.

Description

[Technical Field]

[0001] This disclosure relates to compositions, crosslinked materials, gaskets, packings and molded articles. [Background technology]

[0002] Ethylene-α-olefin copolymer elastomers, such as ethylene-propylene copolymers (EPM, EPR) and ethylene-propylene-diene copolymers (EPDM), do not have unsaturated bonds in the main chain of their molecular structure. As a result, they offer superior heat aging resistance, weather resistance, and ozone resistance compared to general-purpose conjugated diene rubbers, and are widely used in applications such as automotive parts, wire materials, electronic and electrical components, construction and civil engineering materials, and industrial parts.

[0003] Among ethylene-α-olefin copolymer elastomers, EPDM-based rubber molded articles for sealing are known (for example, Patent Document 1). Packings and gaskets, which are rubber molded articles for sealing, are used in a variety of applications such as automobiles, industrial machinery, and electronic components.

[0004] In molded articles using EPDM, it has been proposed to incorporate reinforcing agents such as carbon black to ensure strength (for example, Patent Document 2). Generally, methods for crosslinking EPDM include sulfur vulcanization and peroxide crosslinking, but crosslinked products obtained using sulfur tend to have a strong odor and insufficient heat aging resistance. Crosslinked products obtained using organic peroxides also tend to have a strong odor, and since peroxides cannot be handled in air, equipment for handling organic peroxides is required. In recent years, hydrosilicone crosslinking using hydrosilyl group-containing compounds (for example, Patent Document 3) has attracted attention because crosslinking is less likely to occur at relatively low temperatures of 50 to 130°C during kneading and molding, allowing for sufficient scorching time, while crosslinking can occur in a short time at the crosslinking temperature of 150 to 200°C. Crosslinked products obtained using hydrosilyl group-containing compounds tend to have less odor and excellent heat aging resistance, and can be handled in air. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2000 / 59962 [Patent Document 2] Japanese Patent Publication No. 2012-52032 [Patent Document 3] Japanese Patent Publication No. 2018-131527 [Overview of the project] [Problems that the invention aims to solve]

[0006] When performing hydrosilicone crosslinking using hydrosilyl group-containing compounds, a platinum-based catalyst is added. However, there was a problem in that the platinum-based catalyst could be poisoned by other additives or impurities in the system, leading to a decrease in the crosslinking rate. The object of this disclosure is to provide a composition containing an ethylene-α-olefin-nonconjugated polyene copolymer, a hydrosilyl group-containing compound, a platinum-based catalyst, and a zeolite, which has a high crosslinking rate. [Means for solving the problem]

[0007] 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.

[0008] [1] Ethylene-α-olefin-non-conjugated polyene copolymer (A), A hydrosilyl group-containing compound (Y), Platinum-based catalysts, Zeolite and, A composition containing, 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 a total of two or more of at least one partial structure selected from the group consisting of the following formula (I) and formula (II) in one molecule. The hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (Y1) and having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in one molecule. Composition. [Chemical formula] [In formula (Y1), 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, and a plurality of Rs 1 and Rs 2 are each independently a monovalent alkyl group, R a is an aralkyl group, two Rs are each independently R 1 , R 2 , a hydrogen atom, and R a selected from the group consisting of, and the structural units 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 Rs is a hydrogen atom, and when n = 0, both of the two Rs are hydrogen atoms.] [2] The composition according to item [1], wherein the zeolite is a synthetic zeolite. [3] The composition according to item [1] or [2], wherein the pore diameter of the zeolite is 1 to 30 Å. [4] The composition according to any one of items [1] to [3], containing 0.1 to 100 parts by mass of the zeolite with respect to 100 parts by mass of the copolymer (A). [5] The composition according to any one of items [1] to [4], wherein the copolymer (A) satisfies the following requirements (i) and (ii). Requirement (i): The ratio [(A1) / (A2)] of the mole fraction (A2) of the structural units derived from ethylene [A1] to the mole fraction (A2) of the structural units derived from α-olefins [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; Requirement (ii): The mass fraction of structural units derived from the non-conjugated polyene [A3] is 0.07 to 10% by mass of the copolymer (A) in 100% by mass. [6] The composition according to item [5], wherein the copolymer (A) satisfies 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 structural units derived from the non-conjugated polyene [A3] (mass fraction of [A3] (mass%)), 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 frequency ω = 0.1 rad / sec, obtained by linear viscoelastic measurement (190°C) using a rheometer. * (ω=0.1) (Pa·seconds) and complex viscosity η at frequency ω = 100 rad / second * (ω=100) The ratio P(η) of (Pa·seconds) * (ω=0.1) / η * (ω=100) The intrinsic viscosity [η] (dL / g) and the mass fraction of structural units derived from the non-conjugated polyene [A3] (mass fraction of [A3] (mass%)) satisfy the following equation (2); P / ([η] 2.9 ) ≤ [A3] Mass fraction × 6 ... (2) Requirement (v): Complex viscosity η at frequency ω = 0.01 rad / sec, obtained by linear viscoelastic 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 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 unconjugated polyene [A3]} + 1.42···(3) [7] The composition according to any one of claims [1] to [6], wherein the non-conjugated polyene [A3] comprises 5-vinyl-2-norbornene (VNB). [8] The composition according to any one of items [1] to [7], wherein the α-olefin [A2] having 3 to 20 carbon atoms is propylene. [9] A composition for gaskets, as described in any one of the items [1] to [8]. A crosslinked body obtained by crosslinking the gasket composition described in item

[10] [9]. A gasket obtained using the crosslinking material described in item

[11]

[10] .

[12] A composition for packing, as described in any one of items [1] to [8].

[13] A crosslinked body obtained by crosslinking the packing composition described in item

[12] . A packing obtained using the crosslinking material described in item

[14]

[13] . A molded article formed using a copolymer composition described in any one of the items [1] to [8] of section

[15] . [Effects of the Invention]

[0009] The present invention makes it possible to provide a composition with a high crosslinking rate. [Modes for carrying out the invention]

[0010] In this specification, when the numerical range n1~n2 is mentioned, 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 lower limit value and an upper limit value are each described more than once in the description of an element, a numerical range formed by combining a value arbitrarily selected from the described lower limit values and a value arbitrarily selected from the described upper limit values is also considered to be described.

[0011] 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%".

[0012] 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.

[0013] In this specification, unless otherwise limited, 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 a homopolymer and a copolymer. That is, the term "polymer" is used in a meaning that it may be a homopolymer or a copolymer. Hereinafter, the present invention will be described in detail.

[0014] [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, and a zeolite. Hereinafter, each component will be described separately.

[0015] <Ethylene·α-olefin·non-conjugated polyene copolymer (A)> 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 α-olefin [A2] having 3 to 20 carbon atoms, and structural units derived from non-conjugated polyene [A3]. Non-conjugated polyene [A3] is a non-conjugated polyene that contains a total of two or more substructures selected from the group consisting of the following formulas (I) and (II) in one molecule.

[0016] [ka]

[0017] Examples of α-olefins [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 their raw material costs are relatively low, the resulting copolymers exhibit excellent mechanical properties, and crosslinked bodies with rubber elasticity can be obtained. The above α-olefin [A2] may be used alone or in combination of two or more types.

[0018] Examples of non-conjugated polyenes [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 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. Non-conjugated polyene [A3] is preferably VNB, and more preferably VNB, because it is readily available, the resulting copolymer has good crosslinkability, and the heat resistance of the above composition is easily improved. Non-conjugated polyenes [A3] may be used individually or in combination of two or more types.

[0019] The copolymer (A) may further contain structural units derived from the non-conjugated polyene [A4]. The non-conjugated polyene [A4] is a non-conjugated polyene that contains exactly one substructure selected from the group consisting of formulas (I) and (II) in each molecule.

[0020] Examples of non-conjugated polyenes [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. Non-conjugated polyenes [A4] preferably contain ENB, and more preferably ENB, because they are readily available, the crosslinking rate of the resulting copolymer is easy to control, and good mechanical properties can be easily obtained. Non-conjugated polyenes [A4] may be used individually or in combination of two or more types.

[0021] Copolymer (A) may contain at least one structural 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 copolymer (A) 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 copolymer (A) to contain structural units derived from biomass-derived monomers from the viewpoint of reducing environmental impact.

[0022] Copolymer (A) may contain at least one structural unit derived from chemically recycled monomers. Examples of chemically recycled monomers include chemically recycled ethylene, chemically recycled α-olefins having 3 to 20 carbon atoms, and chemically recycled non-conjugated polyenes. The monomers used as raw materials for copolymer (A) may consist solely of chemically recycled monomers, solely of fossil fuel-derived monomers, or both. Chemically recycled monomers can be obtained by known methods. It is preferable for copolymer (A) to contain structural units derived from chemically recycled monomers from the viewpoint of reducing environmental impact (mainly waste reduction).

[0023] The copolymer (A) preferably satisfies the following requirements (i) and (ii). In addition to satisfying the following requirements (i) and (ii), the 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).

[0024] The copolymer (A) preferably contains an ethylene-propylene-VNB copolymer, and more preferably consists solely of an ethylene-propylene-VNB copolymer. When copolymer (A) contains an ethylene-α-olefin-non-conjugated polyene copolymer other than ethylene-propylene-VNB copolymer, the content of ethylene-propylene-VNB copolymer in copolymer (A) 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.

[0025] Requirement (i): When the total structural units contained in copolymer (A) are 100 mol%, the ratio [(A1) / (A2)] of the mole fraction (A1) of structural units derived from ethylene [A1] to the mole fraction (A2) of structural units derived from 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, even more preferably 55 / 45 to 78 / 22, and particularly preferably 60 / 40 to 75 / 25.

[0026] If copolymer (A) satisfies requirement (i), the crosslinked material obtained from the above composition containing such copolymer tends to have excellent rubber elasticity, flexibility, and mechanical strength.

[0027] When the total structural units contained in copolymer (A) are considered to be 100 mol%, the mole 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%.

[0028] Requirement (ii): The mass fraction of structural units derived from non-conjugated polyene [A3] is 0.07 to 10% by mass of copolymer (A) per 100% by mass. The mass fraction of structural units derived from non-conjugated polyene [A3] is preferably 0.1 to 8.0 mass%, more preferably 0.3 to 5.0 mass%, even more preferably 0.5 to 3.0 mass%, and particularly preferably 1.0 to 2.0 mass%.

[0029] When copolymer (A) satisfies requirement (ii), the crosslinked material obtained from the above composition containing such copolymer tends to have sufficient hardness and excellent mechanical properties. When copolymer (A) satisfies requirement (ii), it tends to have excellent crosslinking properties and exhibit a large crosslinking rate.

[0030] If the copolymer (A) further contains structural units derived from a non-conjugated polyene [A4], the mass fraction of the structural 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 (A).

[0031] The mole fraction (A1) of structural units derived from ethylene [A1], the mole fraction (A2) of structural units derived from α-olefins having 3 to 20 carbon atoms, the ratio [(A1) / (A2)], the mass fraction of structural units derived from non-conjugated polyenes [A3], and the mass fraction of structural units derived from non-conjugated polyenes [A4] were determined using the apparatus and conditions described in the Examples section below. 13 It can be calculated by measuring the 1C-NMR spectrum.

[0032] Requirement (iii): The weight-average molecular weight (Mw) of copolymer (A), the mass fraction of structural units derived from non-conjugated polyene [A3] (mass fraction of [A3] (mass%)), and the molecular weight of 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)

[0033] The equation (1) of requirement (iii) is preferably the following equation (1a). 4.5 ≤ Mw × mass fraction of [A3] / 100 / molecular weight of [A3] ≤ 75 ···(1a) The equation (1) of requirement (iii) is preferably the following equation (1b). 4.5 ≤ Mw × mass fraction of [A3] / 100 / molecular weight of [A3] ≤ 70 ···(1b)

[0034] Requirement (iii) represents the content of structural units derived from non-conjugated polyene [A3] per weight-average molecular weight (Mw) in copolymer (A). When copolymer (A) satisfies requirement (iii), the composition exhibits sufficient crosslinkability and tends to have a high crosslinking rate. Furthermore, the crosslinked material formed from the composition tends to have a good balance of mechanical properties and heat aging resistance.

[0035] The weight-average molecular weight (Mw) of copolymer (A) can be determined as a polystyrene-equivalent value measured by 3D-GPC under the conditions described in the Examples section below.

[0036] Requirement (iv): Complex viscosity η at frequency ω = 0.1 rad / sec, obtained by linear viscoelastic measurement (190°C) using a rheometer. * (ω=0.1) (Pa·seconds) and complex viscosity η at frequency ω = 100 rad / second * (ω=100) The ratio P(η) of (Pa·seconds) * (ω=0.1) / η * (ω=100) The intrinsic viscosity [η] (dL / g) and the mass fraction of structural units derived from the non-conjugated polyene [A3] (mass fraction of [A3] (mass%)) satisfy the following equation (2). P / ([η] 2.9 ) ≤ [A3] Mass fraction × 6 ... (2)

[0037] The equation (2) of requirement (iv) is preferably the following equation (2a). P / ([η] 2.9 ) ≤ Mass fraction of [A3] × 5.7···(2a)

[0038] ratio P(η * (ω=0.1) / η * (ω=100) ) (hereinafter also referred to as the "P value") represents the frequency dependence of viscosity. Therefore, P / ([η], which is the left-hand side of equations (2) and (2a), 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 structural units derived from non-conjugated polyenes they contain. However, copolymer (A) has fewer long-chain branches than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, which is thought to allow it to satisfy equation (2) or (2a).

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

[0040] Requirement (v): Complex viscosity η at frequency ω = 0.01 rad / sec, obtained by linear viscoelastic 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 [A3] satisfy the following equation (3). Log[η * (ω=0.01) ] / Log[η * (ω=10) ]≦0.0753 × {Apparent iodine value derived from unconjugated polyene [A3]} + 1.42···(3)

[0041] In equation (3), 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 polyene [A3] that is not consumed as long-chain branching during polymerization. It is preferable that copolymer (A) satisfies equation (3) because the degree of long-chain branching is not too high.

[0042] complex viscosity η * (ω=0.01) and complex viscosity η * (ω=10) The complex viscosity η in requirement (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 the unconjugated polyene [A3] can be calculated using formula (4). Apparent iodine value derived from [A3] = Mass fraction of [A3] × 253.81 / Molecular weight of [A3] ... (4)

[0043] In copolymer (A), as described above, it is preferable that the non-conjugated polyene [A3] contains VNB, and more preferably that the non-conjugated polyene [A3] is VNB. That is, in formulas (1) and (2), etc., it is preferable that the "mass fraction of [A3]" is the "mass fraction of structural units derived from VNB".

[0044] As described above, when copolymer (A) contains structural units derived from ethylene [A1], α-olefins having 3 to 20 carbon atoms [A2], non-conjugated polyenes [A3], and non-conjugated polyenes [A4], the mass fraction of structural units derived from non-conjugated polyenes [A4] is preferably 20% by mass or less (provided that the sum of the mass fractions of structural units derived from ethylene [A1], α-olefins having 3 to 20 carbon atoms [A2], non-conjugated polyenes [A3], and non-conjugated polyenes [A4] is 100% by mass).

[0045] The copolymer (A) preferably satisfies the following requirement (vi). Requirement (vi): The mass fraction of structural units derived from the non-conjugated polyene [A3] (mass fraction of [A3] (mass%)) and the natural logarithm of the weight-average molecular weight (Mw) of the copolymer (A) [Ln(Mw)] satisfy the following equation (6). 6 - 0.45 × Ln(Mw) ≤ Mass fraction of [A3] ≤ 10···(6) When copolymer (A) satisfies requirement (vi), such copolymer is preferable because it suppresses the formation of branched structures and yields a crosslinked body with sufficient crosslink density.

[0046] The copolymer (A) preferably satisfies the following requirement (vii). Requirement (vii): The B value, expressed by the following formula (7), is 1.00 or greater. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(7) In equation (7), [E], [X], and [Y] represent the mole fractions of structural units derived from ethylene [A1], α-olefins with 3 to 20 carbon atoms [A2], and non-conjugated polyenes [A3], respectively, while [EX] represents the ethylene-α-olefin dyad chain fraction with 3 to 20 carbon atoms. The B value is preferably 1.00 to 1.80, and more preferably 1.10 to 1.40.

[0047] Copolymer (A), when meeting requirement (vii), 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 (A), where [E], [X], [Y], and [EX] 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.

[0048] The intrinsic viscosity [η] of copolymer (A) 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 copolymer (A) is above the lower limit, it is easier to obtain a molded article with superior physical properties. If the intrinsic viscosity [η] of copolymer (A) is below the upper limit, it is easier to obtain a copolymer composition with superior processability. The intrinsic viscosity [η] of copolymer (A) can be adjusted by the amount of hydrogen feed during polymerization. The intrinsic viscosity [η] of copolymer (A) is the value measured in decalin at 135°C.

[0049] The weight-average molecular weight (Mw) of copolymer (A) is preferably 10,000 to 900,000, more preferably 150,000 to 550,000, even more preferably 300,000 to 520,000, even more preferably 400,000 to 500,000, and particularly preferably 450,000 to 490,000. The weight-average molecular weight (Mw) of copolymer (A) can be measured by 3D-GPC using the apparatus and conditions described in the Examples section.

[0050] It is preferable that the intrinsic viscosity [η] and weight-average molecular weight (Mw) of the copolymer (A) are both within the aforementioned range.

[0051] The Mooney viscosity ML(1+4)125℃ 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 above composition containing copolymer (A) having a Mooney viscosity ML(1+4)125℃ within the above range tends to exhibit excellent roll processability even in high-hardness oil-free formulations, as well as good post-treatment (ribbon handling properties) and excellent rubber properties. Details of the Mooney viscosity measurement conditions are described in the Examples section.

[0052] The glass transition temperature (Tg) of copolymer (A) 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 copolymer (A) is, for example, -80°C. When the glass transition temperature (Tg) of copolymer (A) is within the above range, the resulting crosslinked material tends to have excellent low-temperature properties. Details of the Tg measurement conditions are described in the Examples section.

[0053] Copolymer (A) can be obtained, for example, by copolymerizing ethylene [A1], a carbon-3 to carbon-20 α-olefin [A2], a non-conjugated polyene [A3], and optionally a non-conjugated polyene [A4]. 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. Copolymer (A) 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.

[0054] The copolymer (A) may be used alone or in combination of two or more types. 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, based on 100% by mass of the composition.

[0055] <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 atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in one molecule.

[0056] [ka]

[0057] The meanings of each symbol in equation (Y1) 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 1Each 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.

[0058] Crosslinked materials obtained by crosslinking a composition containing copolymer (A) and a compound (Y) as a crosslinking agent tend to have low odor and excellent heat aging resistance. In addition, the above composition can be handled in air.

[0059] 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.

[0060] In formula (Y1), 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.

[0061] In equation (Y1), n ​​is the number of organohydrogensiloxy units that have silicon-bonded hydrogen atoms. n can 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 (Y1) has a structure that contains at least two silicon-bonded hydrogen atoms in one molecule. Note that even if n is a number other than 0 or 1, it does not prevent one or both of the R atoms at the ends of the molecular chain from being silicon-bonded hydrogen atoms.

[0062] 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.

[0063] 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 it may be the number obtained by subtracting the values ​​of n and m from the total degree of polymerization of siloxy units, which is expressed as the sum of n, m, and p described later. p is preferably 0 to 12, more preferably 0 to 10, even more preferably 0 to 5, and particularly preferably 0 to 2.

[0064] In the organohydrogenpolysiloxane represented by formula (Y1), a diorganosiloxy unit (-[O-Si(R 1 )(R a )]-), an organohydrogensiloxy unit having a silicon atom bonded to a hydrogen atom (-[O-Si(R 1 )H]-), and diorganosiloxy units (-[O-Si(R) that do not contain aralkyl groups or silicon atom-bonded hydrogen atoms. 1 )(R 2 Siloxy units such as )-) may be arranged in a block-like manner or randomly. In other words, the order of arrangement of the siloxy units in formula (Y1) is not particularly limited.

[0065] 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.

[0066] In equation (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, even more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, propyl, and butyl groups, with methyl being particularly preferred.

[0067] In equation (Y1), R a The 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.

[0068] 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 above ranges, the physical properties of the resulting crosslinked material tend to be significantly improved. By using compound (Y) in combination with copolymer (A), it is possible to obtain crosslinked materials that are particularly excellent in physical properties such as moldability, elongation at fracture, and compression molding strain.

[0069] 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 10 parts by mass, and most preferably 3 to 8 parts by mass, per 100 parts by mass of copolymer (A).

[0070] <Platinum-based catalyst> In hydrosilylation crosslinking reactions involving the addition of silicon-bonded hydrogen atoms to carbon-carbon double bonds, platinum-based catalysts for hydrosilyl crosslinking are widely used. Platinum-based catalysts for hydrosilyl crosslinking are addition reaction catalysts and can be used without particular limitations as long as they promote the addition reaction (hydrosilylation reaction of alkenes) between, for example, an alkenyl group contained in copolymer (A) and a hydrosilyl group contained in a hydrosilyl group-containing compound (Y).

[0071] Examples of platinum-based catalysts include finely powdered metal platinum catalysts described in U.S. Patent No. 2,970,150, chloroplatinic acid catalysts described in U.S. Patent No. 2,823,218, complex compounds of platinum and hydrocarbons described in U.S. Patent No. 3,159,601 and U.S. Patent No. 159,662, complex compounds of chloroplatinic acid and olefins described in U.S. Patent No. 3,516,946, complex compounds of platinum and vinylsiloxanes described in U.S. Patent No. 3,775,452 and U.S. Patent No. 3,814,780.

[0072] Examples of platinum-based catalysts include elemental platinum (platinum black); chloroplatinic acid, platinum-hydrocarbon complexes, platinum-vinylsiloxane complexes, platinum-alcohol complexes, chloroplatinic acid-olefin complexes, and platinum complexes such as chloroplatinic acid-vinylsiloxane complexes. Among these, platinum-vinylsiloxane complexes are preferred due to their high catalytic activity. An example of a platinum-vinylsiloxane complex is 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complex. The platinum-based catalyst may be supported on a carrier such as alumina or silica.

[0073] Platinum-based catalysts may be used individually or in combination of two or more types. In the compositions of this disclosure, the content of the platinum-based 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, even more preferably 0.0002 to 0.03 parts by mass, particularly preferably 0.0003 to 0.021 parts by mass, especially preferably 0.0005 to 0.018 parts by mass, and most preferably 0.001 to 0.015 parts by mass, per 100 parts by mass of copolymer (A).

[0074] <Zeolite> Zeolites are hydrated aluminosilicates with a three-dimensional skeletal structure, and their general formula is XM 2 / n It is represented as O·Al2O2·YSiO2·ZH2O. Here, M represents the ion-exchangeable ion, usually a monovalent or divalent metal ion, n is the valence of the metal ion, X is the metal oxide, Y is the silica coefficient, and Z is the number of water molecules in crystallization. Zeolites are broadly classified into synthetic zeolites and natural zeolites, with synthetic zeolites being preferred. Synthetic zeolites are preferred because they have high purity and excellent reactivity even in small amounts. Examples of zeolites include A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high-silica zeolite, sodalite, mordenite, analcime, clinoptilolite, chabasite, and irionite.

[0075] The pore size of the zeolite is preferably 1 to 30 Å, more preferably 3 to 25 Å, even more preferably 5 to 20 Å, and particularly preferably 5 to 15 Å. Having the pore size of the zeolite within the above range is preferable because it suppresses poisoning of the platinum-based catalyst and increases the crosslinking rate.

[0076] Zeolite may be used individually or in combination of two or more types. In the compositions of this disclosure, the content of zeolite (e.g., synthetic zeolite) is preferably 0.1 to 100 parts by mass, more preferably 1 to 75 parts by mass, even more preferably 5 to 50 parts by mass, and particularly preferably 5 to 25 parts by mass, per 100 parts by mass of copolymer (A).

[0077] <Other ingredients> The compositions of this 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, hygroscopic agents, reaction inhibitors, organic peroxides, crosslinking aids, crosslinking accelerators, foaming agents, surfactants, processing aids, plasticizers, tackifiers, colorants, and polymers other than copolymer (A). Other ingredients may be used individually or in combination of two or more.

[0078] (Anti-aging agent) The compositions of this disclosure may further contain an anti-aging agent. As the antioxidant, known antioxidants that can be incorporated into general rubber compositions can be used. Examples of antioxidants include phenolic antioxidants, amine-based antioxidants, and sulfur-based antioxidants. Among these, phenolic antioxidants are preferred.

[0079] Hindered phenol compounds are preferred as phenolic antioxidants. Examples of hindered phenol compounds include 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.

[0080] Examples of amine-based antioxidants include aromatic second amine-based antioxidants such as phenylbutylamine, N,N-di-2-naphthyl-p-phenylenediamine, and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

[0081] 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 dibutyldithiocarbamate nickel; and 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salts of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0082] Anti-aging agents may be used individually or in combination of two or more types. The case in which the composition of this disclosure contains an antioxidant is described below. The amount of the antioxidant is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 10 parts by mass, even more preferably 0.01 to 10 parts by mass, and particularly preferably 0.03 to 8 parts by mass, per 100 parts by mass of copolymer (A).

[0083] (Reinforcement agent) The compositions of this disclosure may further contain reinforcing agents to improve physical properties such as tensile stress at fracture and tensile elongation at fracture. As reinforcing agents, known reinforcing agents that can be incorporated into general rubber compositions can be used. Examples of reinforcing agents other than calcium carbonate include carbon black, talc, clay, kaolin, silica, heavy calcium carbonate, light calcium carbonate, and differential silicic acid.

[0084] Among reinforcing agents, carbon black is preferred. The above composition containing carbon black tends to have superior processability and tends to form crosslinked bodies with superior 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.

[0085] Examples of carbon black include SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. The surface of the carbon black may be treated with a silane coupling agent. Examples of commercially available carbon black include the product names "Asahi #55G", "Asahi #50HG", "Asahi #60G", "Asahi #60UG", and "Asahi #70" (manufactured by Asahi Carbon Co., Ltd.), and the product names "Seas SVH", "Seas V", and "Seas G-SO" (manufactured by Tokai Carbon Co., Ltd.).

[0086] The reinforcing agent may be used alone or in combination of two or more types. The case in which the composition of this disclosure contains a reinforcing agent is described below. The reinforcing agent content is preferably 5 to 200 parts by mass, more preferably 30 to 150 parts by mass, even more preferably 50 to 140 parts by mass, and particularly preferably 80 to 120 parts by mass, per 100 parts by mass of copolymer (A). When the reinforcing agent content is within the above range, a composition with excellent dynamic modulus (dynamic modulus / static modulus), processability, mechanical properties (especially tensile breaking strength), etc. can be obtained.

[0087] (Softener) The compositions of this disclosure may further contain a softening agent. As a softening agent, known softening agents that can be incorporated into general rubber compositions can be used. Examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymers 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). Among these, petroleum-based softening agents are preferred, process oils are more preferred, and paraffin-based process oils are particularly preferred.

[0088] The softening agent may be used alone or in combination of two or more types. The case in which the composition of this disclosure contains a softening agent will be described below. The content of the softening agent is preferably 1 to 200 parts by mass, more preferably 10 to 160 parts by mass, even more preferably 50 to 140 parts by mass, and particularly preferably 80 to 120 parts by mass, per 100 parts by mass of copolymer (A). When the content of the softening agent is within the above range, a composition with low tack and excellent processability, heat aging resistance, and mechanical properties can be obtained.

[0089] (Desiccant) The compositions of this disclosure may further contain a desiccant. Examples of desiccants include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolites, and white carbon. Among these, calcium oxide is preferred.

[0090] Desiccant may be used individually or in combination of two or more types. The case in which the composition of this disclosure contains a desiccant is described below. The content of the desiccant 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).

[0091] (Reaction inhibitor) The compositions of this disclosure preferably further contain a reaction inhibitor. The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation reaction of alkenes) between, for example, an alkenyl group contained in copolymer (A) and a hydrosilyl group contained in hydrosilyl group-containing compound (Y). The above composition containing the reaction inhibitor tends to have stable processability during kneading and molding.

[0092] Examples of reaction inhibitors include benzotriazole; acrylonitrile; 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; and N,N-diallylacetate. Examples of amide compounds include mid, 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 other compounds such as 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.

[0093] The reaction inhibitor may be used alone or in combination of two or more types. The case in which the composition of this 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 0.01 to 1 part by mass, even more preferably 0.05 to 0.8 parts by mass, and particularly preferably 0.10 to 0.50 parts by mass, per 100 parts by mass of copolymer (A).

[0094] <Preparation of Composition> The compositions of this disclosure can be prepared, for example, by mixing a copolymer (A), a hydrosilyl group-containing compound (Y), a platinum-based catalyst, a zeolite, and other components as needed.

[0095] The above composition can be prepared, for example, by a method comprising: a first step of kneading a copolymer (A), a hydrosilyl group-containing compound (Y), a zeolite, and optionally the above-mentioned other components; and a second step of adding a platinum-based catalyst and optionally the above-mentioned other components to the kneaded product obtained in the first step and kneading it.

[0096] If, for example, at least one selected from the group consisting of reinforcing agents, softening agents, activators, processing aids, plasticizers, tackifiers, colorants, and polymers other than copolymer (A) is added, it is preferable to add it in the first step. If, if at least one selected from the group consisting of antioxidants, hygroscopic agents, reaction inhibitors, organic peroxides, crosslinking aids, crosslinking accelerators, and foaming agents is added, it is preferable to add it in the second step. For example, we will describe cases in which other components such as antioxidants, reinforcing agents, softeners, hygroscopic agents, and reaction inhibitors are included. In one embodiment, it is preferable to include reinforcing agents and softeners in the first step, and it is preferable to include antioxidants, hygroscopic agents, and reaction inhibitors in the second step.

[0097] In the first step, the above components may be kneaded using a kneading device such as a Banbury mixer, kneader, or 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 0.1 to 10 minutes, more preferably 1 to 8 minutes.

[0098] In the second step, the above components may be added to the mixture obtained in the first step and mixed using a mixing device such as a roll, kneader, or extruder. The mixing 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 mixing time in the second step is preferably 1 to 30 minutes, more preferably 5 to 20 minutes.

[0099] [Crosslinked body] The crosslinked material of this disclosure is obtained by crosslinking the composition of this disclosure. The crosslinked body of the present disclosure can be obtained, for example, by introducing the molded body into a crosslinking tank and heating it after or simultaneously with molding the composition of the present disclosure into a desired shape using various molding methods, and crosslinking it. If the composition of the present disclosure contains a foaming agent, foaming will also proceed along with crosslinking, and a foamed crosslinked body will be obtained. Examples of molding methods include using an extrusion molding machine, calender roll, press molding machine, injection molding machine, or transfer molding machine. A mold may or may not be used during molding and crosslinking. If a mold is not used, the composition is usually molded and crosslinked continuously.

[0100] The heating temperature when crosslinking the above composition or 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 25 minutes. For the crosslinking treatment, a heating tank of any type, such as a hot air vulcanizing tank (HAV), a steam vulcanizing tank, a glass bead fluidized bed, a far-infrared heating furnace, a microwave vulcanizing tank (UHF), or a molten salt tank (LCM), may be used.

[0101] The above composition may be press-molded to perform primary crosslinking, and after obtaining a primary molded body by removing it from the mold, the obtained primary molded body may be secondary crosslinked in a heat transfer medium. Specifically, the above composition is press-molded to perform primary crosslinking, preferably at 120-200°C for 1-30 minutes, more preferably at 150-200°C for 10-25 minutes, and then removed from the mold to obtain a primary molded body. Next, the obtained primary molded body is secondary crosslinked in a heat transfer medium, preferably at 120-160°C for 10-24 hours, more preferably at 140-160°C for 15-20 minutes. Examples of heat transfer mediums used for secondary crosslinking include air, steam, paraffin-based process oil, and molten salt.

[0102] [Uses of the composition] The articles of this disclosure include the crosslinked materials of this disclosure. This composition is suitable for rubber molded articles for sealing, such as gaskets or packings. That is, this composition is suitable as a gasket composition. This composition is also suitable as a packing composition. By using this composition, it is possible to obtain gaskets and packings with a higher crosslinking rate and superior productivity compared to those obtained using conventional rubber compositions.

[0103] [gasket] Examples of gaskets include fuel cell gaskets, automotive gaskets, industrial gaskets, and building gaskets, and are preferably used as fuel cell gaskets, and more preferably as fuel cell gaskets used in hydrogen lines.

[0104] [rubber seal] The articles disclosed herein are suitably used in automotive packing parts, machine sealing parts, electronic and electrical component packing parts, civil engineering and construction material packing parts, and the like.

[0105] Specific examples of packings of this disclosure include brake master cylinder cups, brake wheel cylinder cups, brake fluid pressure control seal packings, and brake O-rings, as well as clutch cylinder cups, condenser packings, and hydrogen seal packings in hydraulic brakes.

[0106] [Molded body] The molded articles of this disclosure include the composition. The copolymer (A) of the composition may be uncrosslinked or crosslinked, and a combination of uncrosslinked copolymer (A) and crosslinked copolymer (A) may be used. The composition has a high crosslinking rate, excellent productivity and processability, and the molded articles obtained from the composition (e.g., crosslinked molded articles and crosslinked foams) have excellent physical properties and can be used in a variety of applications.

[0107] The above-mentioned molded products are suitably used in, for example, hose products, vibration-damping rubber, vibration-damping or vibration-reducing materials (e.g., engine mounts, motor mounts), muffler hangers, sponges (e.g., weatherstrip sponges, heat-insulating sponges, protective sponges, micro-foamed sponges), cables (e.g., ignition cables, cabtyre cables, high-tension cables), wire covering materials (e.g., high-voltage wire covering materials, low-voltage wire covering materials, marine wire covering materials), glass run channels, tire rubber, O-rings, industrial rolls, belts (e.g., heat-insulating belts, photocopier belts, conveyor belts), golf club grips, cane grips, toothbrush grips, tableware (e.g., spoons, forks, chopsticks) grips, broom grips, teacup grips, colored surface materials, paper feed rolls, roofing sheets, high-foamed sealing materials, automotive sealing materials, civil engineering or construction sealing materials, industrial sealing materials, and the like. [Examples]

[0108] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0109] [Physical properties of copolymer (A)] The physical properties of the copolymer (A) were measured as follows.

[0110] <Composition of copolymer (A)> The content of each structural unit in the copolymer (A) was 13 calculated from the C-NMR spectrum. Using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.), at a measurement temperature of 120 °C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an integration number of 8000 times, the 13 C-NMR spectrum of the copolymer (A) was measured.

[0111] <Mooney viscosity> The Mooney viscosity ML(1+4) 125 °C of the copolymer (A) was measured using a Mooney viscometer (SMV-301 type manufactured by Shimadzu Corporation) in accordance with JIS K6300-1:2013.

[0112] The B value of the copolymer (A) 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 The 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.

[0113] <Limiting viscosity> The limiting viscosity [η] of the copolymer (A) was measured using an automatic limiting viscometer (manufactured by Rika Corporation) under the conditions of a temperature of 135 °C and a measurement solvent of decalin.

[0114] <Weight-average molecular weight (Mw)> The weight average molecular weight (Mw) of the copolymer (A) is a value in terms of polystyrene measured by 3D-GPC. The measuring apparatus and conditions are as follows. The dn / dc value (differential value of refractive index n with respect to concentration c, dn / dc value) required for the determination of absolute molecular weight was determined for each sample from the dn / dc value of standard polystyrene (molecular weight 190,000) of 0.053 and the response intensity of the differential refractometer per unit injection mass. Apparatus: 3D-high temperature GPC apparatus PL-GPC\(220\) type (manufactured by Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT × 2 pieces + TSKgel GMH HR -M(S) × 1 piece (All have an inner diameter of \(7.8\) mmφ and a length of \(300\) mm per piece) Column temperature: \(140\) °C Mobile phase: 1,2,4-trichlorobenzene (containing \(0.025\%\) BHT) Detector: Differential refractometer (RI) / built-in GPC apparatus Two-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Injection volume: \(0.5\) mL Sample concentration: ca \(1.0\) mg / mL Sample filtration: Filtered through a sintered filter with a pore size of \(1.0\) μm

[0115] <Complex viscosity η * > Using a viscoelastic measuring apparatus Ares (manufactured by Rheometric Scientific) as a rheometer, the complex viscosity η at a frequency ω = \(0.01\) rad / s, a temperature of \(190\) °C, and a strain of \(1.0\%\) * (ω=0.01) and the complex viscosity η at a frequency ω = \(0.1\) rad / s * (ω=0.1) and the complex viscosity η at a frequency ω = \(10\) rad / s * (ω=10) and the complex viscosity η at a frequency ω = \(100\) rad / s * (ω=100) were 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.

[0116] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of copolymer (A) was determined by measurement using a differential scanning calorimeter (DSC) under the following conditions. Using a differential scanning calorimeter (RDC220, SII Corporation), approximately 10 mg of the sample was heated from 30°C to 200°C at a heating rate of 50°C / min under a nitrogen atmosphere and held at 200°C for 10 minutes. It was then cooled to -100°C at a heating rate of 10°C / min and held at -100°C for 5 minutes, after which it was heated to 200°C at a heating rate of 10°C / min. The temperature based on the glass transition at this time was defined as the glass transition temperature (Tg).

[0117] [Manufacturing Example 1: Manufacturing of Copolymer (A-1)] Using a continuous polymerization apparatus, ethylene-propylene-5-vinyl-2-norbornene (VNB) copolymer (A-1) was produced as follows.

[0118] A 300 L polymerization reactor was continuously supplied with 58.3 L / hr of dehydrated and purified hexane solvent from line 1, 4.5 mmol / hr of triisobutylaluminum (TIBAL) from line 2, 0.150 mmol / hr of (C6H5)3CB(C6F5)4, and 0.030 mmol / hr of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride from line 2. Simultaneously, 6.6 kg / hr of ethylene, 9.3 kg / hr of propylene, 18 L / hr of hydrogen, and 340 g / hr of VNB were continuously supplied to the polymerization reactor from separate lines. Copolymerization was carried out under conditions of a polymerization temperature of 87°C, a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

[0119] 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 supplied to the phase separator. At this time, ethanol, a polymerization inhibitor, was continuously introduced into the discharge line at an amount equal to 0.1 mol relative to the TIBAL in the liquid component withdrawn from the polymerization reactor.

[0120] In the phase separator described above, the ethylene-propylene-VNB copolymer solution was separated into a concentrated phase (lower phase) containing most of the ethylene-propylene-VNB copolymer and a dilute phase (upper phase) containing a small amount of polymer. The separated concentrated phase was led to heat exchanger K at 85.4 L / hr, and then to a hopper where the solvent was evaporated and separated to obtain ethylene-propylene-VNB copolymer (A-1) at a rate of 7.8 kg / hr. The physical properties of the obtained ethylene-propylene-VNB copolymer (A-1) were evaluated as described above. The results are shown in Table 1.

[0121] [Table 1]

[0122] [Manufacturing Example 2: Manufacturing of Compound (Y-1)] 536 g of methylhydrogenpolysiloxane represented by the following formula (Y1b) 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.

[0123] 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).

[0124] The resulting compound (Y-1) is, 29 Si-NMR confirmed that the compound was represented by the formula (Y1a) 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.

[0125] [ka]

[0126] The raw materials used in the examples are listed below. Carbon Black: Manufactured by Asahi Carbon Co., Ltd., Asahi #50HG Softener: Diana Process PS-430, manufactured by Idemitsu Kosan Co., Ltd., paraffin-based process oil Zeolite: Manufactured by Tosoh Corporation, Zeolam F-9 Reaction inhibitor: ETCH, 1-ethynyl-1-cyclohexanol, manufactured by Nisshin Chemical Industry Co., Ltd. Platinum-based catalyst: Toray Dow SRX212 Catalyst, product containing 1% to less than 3% by mass of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complex. Anti-aging agent: Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd., 2-mercaptobenzimidazole (MBI)

[0127] [Examples and Comparative Examples: Preparation of Uncrosslinked Compositions (Unvulcanized Rubber)] In the first step, the raw materials shown in Raw Materials 1 of Table 2 were kneaded at 140°C for 2 minutes using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.). After that, the ram was raised and cleaned, and kneaded for another minute, then discharged at approximately 150°C to obtain the first step mixture (mixture 1).

[0128] Next, in the second step, the mixture 1 obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C, a rear roll surface temperature of 50°C, a front roll rotation speed of 16 rpm, and a rear roll rotation speed of 18 rpm). The raw materials shown in Raw Materials 2 of Table 2 were added to this, and the mixture was kneaded for 10 minutes to obtain the mixture for the second step (mixture 2).

[0129] [Mooney Viscosity] The Mooney viscosity ML(1+4) at 125°C of the above formulation 1 was measured using a Mooney viscometer (Shimadzu Corporation, SMV-301 model) in accordance with JIS K6300-1:2013.

[0130] [Vulcanization rate test] Vulcanization measurement device: Using the MDR2000 (manufactured by Alpha Technologies), the vulcanization rates (tc10, tc50, tc90) of the above compound 2 were measured as follows under measurement conditions of 125°C and 60 minutes, and 180°C and 20 minutes.

[0131] The torque change obtained under constant temperature and 1.66 Hz conditions was measured, and a vulcanization curve was obtained. The difference between the maximum torque (S'max) and the minimum torque (S'min): S'max-S'min [dNm], the time when the torque of the measured sample increased by 0.1 [dNm] after reaching the minimum torque (S'min): TS0.1 [min], the time when the torque increased by 1.0 [dNm]: TS1.0 [min], the time when the torque increased by 2.0 [dNm]: TS2.0 [min], the time when the torque of the measured sample reached 10% [min]: tc10, the time when the torque of the measured sample reached 50% [min]: tc50, the time when the torque of the measured sample reached 90% [min]: tc90, with the minimum torque (S'min) set to 0% and the maximum torque (S'max) set to 100%, was determined.

[0132] [Table 2]

Claims

1. Ethylene-α-olefin-non-conjugated polyene copolymer (A), A hydrosilyl group-containing compound (Y), Platinum-based catalysts, Zeolite and, A composition containing, The copolymer (A) comprises structural units derived from ethylene [A1], structural units derived from α-olefin [A2] having 3 to 20 carbon atoms, and structural units derived from non-conjugated polyene [A3] containing a total of two or more substructures selected from the group consisting of the following formulas (I) and (II) in one molecule. The hydrosilyl group-containing compound (Y) is represented by the following formula (Y1) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in one molecule. composition. 【Chemistry 1】 [In formula (Y1), 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, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, R a is an aralkyl group, and two Rs are each independently R 1 , R 2 , a hydrogen atom, and R a selected from the group consisting of, and the structural units 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 arranged, provided that when n = 1, at least one of the two Rs is a hydrogen atom, and when n = 0, both of the two Rs are hydrogen atoms.]

2. The composition according to claim 1, wherein the zeolite is a synthetic zeolite.

3. The composition according to claim 1, wherein the pore size of the zeolite is 1 to 30 Å.

4. The composition according to claim 1, comprising 0.1 to 100 parts by mass of the zeolite per 100 parts by mass of the copolymer (A).

5. 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 mole fraction (A1) of structural units derived from ethylene [A1] to the mole fraction (A2) of structural units derived from α-olefins having 3 to 20 carbon atoms [A2] is 40 / 60 to 99.9 / 0.1; Requirement (ii): The mass fraction of structural units derived from the non-conjugated polyene [A3] is 0.07 to 10% by mass of the copolymer (A) in 100% by mass.

6. The composition according to claim 5, wherein the copolymer (A) satisfies 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 structural units derived from the non-conjugated polyene [A3] (mass fraction of [A3] (mass%)), 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 frequency ω = 0.1 rad / sec, obtained by linear viscoelastic measurement using a rheometer (190°C). * (ω=0.1) (Pa·seconds) and the complex viscosity η at frequency ω = 100 rad / second * (ω=100) The ratio P(η) to (Pa·seconds) * (ω=0.1) / η * (ω=100) The intrinsic viscosity [η] (dL / g) and the mass fraction of structural units derived from the non-conjugated polyene [A3] (mass fraction of [A3] (mass%)) satisfy the following formula (2): P / ([η] 2.9 ) ≤ Mass fraction of [A3] × 6 ... (2) Requirement (v): Complex viscosity η at frequency ω = 0.01 rad / sec, obtained by linear viscoelasticity measurement using a rheometer (190°C). * (ω=0.01) (Pa·seconds) and the complex viscosity η at frequency ω = 10 rad / second * (ω=10) The (Pa·second) 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 unconjugated polyene [A3]} + 1.42 ... (3)

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

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

9. A composition for gaskets, according to any one of claims 1 to 8.

10. A crosslinked body obtained by crosslinking the gasket composition described in claim 9.

11. A gasket obtained using the crosslinked material described in claim 10.

12. A composition for packing, according to any one of claims 1 to 8.

13. A crosslinked body obtained by crosslinking the packing composition described in claim 12.

14. A packing obtained using the crosslinked material described in claim 13.

15. A molded article formed using the composition described in any one of claims 1 to 8.

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