Copolymer composition, foamed molded article, crosslinked molded article, and method for producing the same.

Abstract

The present invention provides a copolymer composition which is characterized by containing: a copolymer (S) which comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a specific non-conjugated polyene (C), and satisfies the requirement (i) and the requirement (ii) shown below; a hydrosilyl group-containing compound (Y) which is an organohydrogen polysiloxane that has at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in each molecule; and a platinum-based catalyst for hydrosilylation crosslinking. (i) (A) / (B) is 40 / 60 to 99.9 / 0.1. (ii) The mass percent concentration of the constituent unit derived from a non-conjugated polyene (C) is 0.07 to 10% by mass.

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin-nonconjugated polyene copolymer composition and a method for producing the same, a foamed molded article obtained from this copolymer composition and a method for producing the same, and a crosslinked molded article and a method for producing the same. This application claims priority based on Japanese Patent Application No. 2022-003316, filed in Japan on January 12, 2022, and Japanese Patent Application No. 2022-142879, filed in Japan on September 8, 2022, and the contents thereof are incorporated herein by reference. [Background technology]

[0002] A copolymer composition obtained by hydrosilyl crosslinking of an ethylene-α-olefin-non-conjugated polyene random copolymer (Patent Document 1) has advantages over sulfur vulcanization and peroxide crosslinking in terms of mechanical strength, heat aging resistance, compression set, and bloom, and is capable of continuous crosslinking, making it promising for application in sealing components such as packings and gaskets.

[0003] Patent Document 1 proposes a copolymer composition in which, at relatively low temperatures of 50 to 130°C during kneading and molding, the scorching time is long to prevent crosslinking during kneading, while at the crosslinking temperature of 150 to 200°C, crosslinking can occur in a short time. Patent Document 2 proposes crosslinking using a hydrosilyl-containing compound in combination with an organic peroxide that is relatively inexpensive and readily available. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-131527 [Patent Document 1] Japanese Patent Publication No. 2019-156950 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, Patent Documents 1 and 2 do not adequately examine the hydrosilyl group-containing compounds used for crosslinking. In view of the above circumstances, the present invention aims to provide a copolymer composition containing an ethylene-α-olefin-non-conjugated polyene copolymer that is excellent in terms of the physical properties and processability of the resulting molded article, a method for producing the same, a foamed molded article obtained from this copolymer composition, a method for producing the same, and a crosslinked molded article and a method for producing the same. [Means for solving the problem]

[0006] To achieve the above objectives, the present invention has the following embodiments. [1] Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The above requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefins (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. The requirement (ii) is a copolymer composition in which the mass percentage concentration of constituent units derived from the non-conjugated polyene (C) is 0.07 to 10% by mass relative to all constituent units of the copolymer (S); [ka] [ka] In equation (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, and multiple R 1 and R 2 Each of these is independently a monovalent alkyl group, and R a It is an aralkyl group, and the two Rs are each independently R 1 ,R 2 , hydrogen atom, and R a The group is selected from the group consisting of the following, and these constituent units may be arranged in a block-like manner or randomly, however, 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. [2] Furthermore, it contains a baking soda-based foaming agent that meets the following requirement (b): The above requirement (b) is that the cumulative roughness at 10% of the cumulative distribution curve based on the number of irregularities is 0.9 or less, and the cumulative equivalent diameter at 90% of the cumulative distribution curve based on the number of equivalent diameters is 43 μm or more. The copolymer composition according to [1], wherein the degree of roughness is the ratio of the envelope perimeter to the perimeter measured by dynamic image analysis using methyl ethyl ketone as the dispersion solvent, and the equivalent circle diameter is the diameter of a circle having an area equal to the projected area of ​​the particle measured by dynamic image analysis using methyl ethyl ketone as the dispersion solvent. [3] The copolymer composition according to [2], comprising 0.1 to 100 parts by mass of the hydrosilyl group-containing compound (Y), 0.001 to 10 parts by mass of the platinum-based catalyst, and 1 to 30 parts by mass of the sodium bicarbonate-based blowing agent per 100 parts by mass of the copolymer (S). [4] The copolymer composition according to [2] or [3], further comprising 0 to 2 parts by mass of a reaction inhibitor per 100 parts by mass of the copolymer (S). [5] The copolymer composition according to any one of [2] to [4], further comprising 0.07 to 10 parts by mass of a hindered phenol antioxidant per 100 parts by mass of the copolymer (S). A foamed molded article comprising a foam obtained by crosslinking and foaming a copolymer composition according to any one of the items [6] [2] to [5]. [7] A method for producing a foamed molded article, comprising melt-extruding the copolymer composition according to any one of [2] to [5] and crosslinking it. [8] The copolymer (S) further satisfies the following requirements (iii) to (v) and has an intrinsic viscosity [η] of 2.0 to 4.0 dL / g, furthermore, based on 100 parts by mass of the copolymer (S), 0.1 to 200 parts by mass of carbon black, 0.1 to 200 parts by mass of paraffinic process oil, and optionally a reaction inhibitor are included, The Mooney viscosity "ML(1+4)100°C" determined by the method described in JIS K 6300-1:2013 of the composition obtained by mixing the components excluding the hydrosilyl group-containing compound (Y), the platinum-based catalyst, and the reaction inhibitor is 8 to 200, the requirement (iii) is that (n C ) obtained by the following formula (1) is 4.5 or more and 40 or less, (n C )=(Mw)×{(mass percentage concentration of (C)) / 100} / (molecular weight of (C)) ···(1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the structural unit derived from the non-conjugated polyene (C) with respect to the total mass of the structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). [[ID=,18]] The requirement (iv) is that the ratio P(η <00,00009> (ω=0.1) (Pa·sec) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω=100) (Pa·sec) at a frequency ω = 100 rad / s, and the intrinsic viscosity [η], and the mass percentage concentration of the structural unit derived from the non-conjugated polyene (C) (the content (mass%) of the structural unit derived from the non-conjugated polyene (C) with respect to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2),​​​​​​ P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. 1000C The copolymer composition described in [1], wherein the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3), LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3). A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in [9] [8].

[10] The copolymer (S) further satisfies the following requirements (iii) to (v) and has an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g, Furthermore, the copolymer (S) contains 10 to 100 parts by mass of paraffinic process oil per 100 parts by mass. The Mooney viscosity "ML(1+4)100℃" obtained by the method described in JIS K 6300-1:2013 is 0.1 to 8. The above requirement (iii) can be obtained by the following formula (1) (n C ) is between 4.5 and 40, (n C ) = (Mw) × {(Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and complex viscosity η at frequency ω = 100 rad / s * (ω=100) The ratio P(η) to (Pa·sec) * (ω=0.1) / η *(ω=100) The following equation (2) satisfies the intrinsic viscosity [η] and the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) (the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S)): P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. 1000C The copolymer composition described in [1], wherein the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3), LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3). A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in

[11]

[10] .

[12] The copolymer (S) further satisfies the following requirements (iii) to (v) and has an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g, Furthermore, the copolymer (S) contains 0.1 to 200 parts by mass of carbon black and 100 to 400 parts by mass of paraffinic process oil per 100 parts by mass. The Brookfield rotational viscosity at 25°C, as determined by the method described in JIS K 7117:1999, is 6000 Pa·s or less. The above requirement (iii) can be obtained by the following formula (1) (n C ) is between 4.5 and 40, (n C ) = (Mw) × {(Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and complex viscosity η at frequency ω = 100 rad / s * (ω=100) The ratio P(η) to (Pa·sec) * (ω=0.1) / η * (ω=100) The following equation (2) satisfies the intrinsic viscosity [η] and the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) (the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S)): P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. 1000C The copolymer composition described in [1], wherein the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3), LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3). A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in

[13]

[12] .

[14] Furthermore, reaction inhibitors, Contains organic peroxide (Z), The copolymer (S) further satisfies the following requirements (iii) to (v): The organic peroxide (Z) is contained in an amount of 0.2 to 6 parts by mass per 100 parts by mass of the copolymer (S). The above requirement (iii) can be obtained by the following formula (1) (n C ) is between 4.5 and 40, (n C ) = (Mw) × {(Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and complex viscosity η at frequency ω = 100 rad / s * (ω=100) The ratio P(η) to (Pa·sec) * (ω=0.1) / η * (ω=100) The following equation (2) satisfies the intrinsic viscosity [η] and the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) (the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S)): P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. 1000C The copolymer composition described in [1], wherein the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3), LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3).

[15] The copolymer composition according to

[14] , comprising 0.01 to 10 parts by mass of the hydrosilyl group-containing compound (Y), 0.001 to 1 part by mass of the platinum-based catalyst, and 0.001 to 5 parts by mass of the reaction inhibitor per 100 parts by mass of the copolymer (S). A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in

[16]

[14] or

[15] .

[17] The copolymer (S) and the hydrosilyl group-containing compound (Y) are kneaded at 80 to 170°C for 1 to 10 minutes to obtain the first-stage formulation; and A method for producing a copolymer composition according to any one of [1] to [5], [8],

[10] ,

[12] ,

[14] and

[15] , comprising adding a platinum-based catalyst to the first-stage formulation and kneading at 10 to 130°C for 1 to 30 minutes to obtain a second-stage formulation, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The above requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefins (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. The manufacturing method wherein requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 10% by mass relative to the total constituent units of the copolymer (S); [ka] [ka] In equation (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, and multiple R 1 and R 2 Each of these is independently a monovalent alkyl group, and R a It is an aralkyl group, and the two Rs are each independently R 1 ,R 2 , hydrogen atom, and R aThe group is selected from the group consisting of the following, and these constituent units may be arranged in a block-like manner or randomly, however, 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.

[18] A method for producing the copolymer composition according to

[17] , wherein the amount of the hydrocarbon compound (Y) is 0.1 to 100 parts by mass and the platinum catalyst is 0.001 to 10 parts by mass per 100 parts by mass of the copolymer (S).

[19] A method for producing a copolymer composition according to

[17] or

[18] , wherein in order to obtain the second-stage formulation, a reaction inhibitor is further added to the first-stage formulation and kneaded at 10 to 130°C for 1 to 30 minutes to obtain the second-stage formulation.

[20] A method for producing the copolymer composition according to

[19] , wherein 0.05 to 5 parts by mass of the reaction inhibitor is used per 100 parts by mass of the copolymer (S). A crosslinked molded article obtained by crosslinking a copolymer composition obtained by the manufacturing method described in any one of the items

[21]

[17] to

[20] .

[22] A kneaded product comprising the copolymer composition described in any one of [1] to [5], [8],

[10] ,

[12] ,

[14] and

[15] is obtained by melt-kneading the copolymer (S), the hydrosilyl group-containing compound (Y), and the platinum-based catalyst; A primary molded body is obtained by press-molding the aforementioned kneaded material at 120-200°C for 1-20 minutes to perform primary crosslinking; and A method for producing a crosslinked molded article, comprising heating the primary molded article in a heat transfer medium at 120 to 160°C for 10 to 24 hours to perform secondary crosslinking, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The above requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefins (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. The above requirement (ii) is a manufacturing method in which the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 10% by mass relative to the total constituent units of the copolymer (S); [ka] [ka] In equation (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, and multiple R 1 and R 2 Each of these is independently a monovalent alkyl group, and R a It is an aralkyl group, and the two Rs are each independently R 1 ,R 2 , hydrogen atom, and R a The group is selected from the group consisting of the following, and these constituent units may be arranged in a block-like manner or randomly, however, 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.

[23] A method for producing a crosslinked molded article according to

[22] , wherein the amount of the hydrosilyl group-containing compound (Y) is 0.1 to 100 parts by mass and the platinum-based catalyst is 0.001 to 10 parts by mass per 100 parts by mass of the copolymer (S).

[24] A method for producing a crosslinked molded article according to

[22] or

[23] , wherein the kneaded product is obtained by further adding a reaction inhibitor and melt-kneading.

[25] A method for producing a crosslinked molded article according to

[24] , wherein 0.05 to 5 parts by mass of the reaction inhibitor is used per 100 parts by mass of the copolymer (S).

[26] The copolymer composition, method for producing the copolymer composition, foamed molded article, method for producing a foamed molded article, crosslinked molded article, or method for producing a crosslinked molded article, with respect to the total mass of the copolymer composition, the content of the copolymer (S) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, as described in any one of [1] to

[25] .

[27] The content of the ethylene (A)-derived constituent units is preferably 50 to 80% by mass, more preferably 60 to 75% by mass, and even more preferably 65 to 72% by mass, with respect to the total mass of the copolymer (S), as described in any one of [1] to

[26] , the copolymer composition, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[28] The content of the constituent units derived from α-olefin (B) having 3 to 20 carbon atoms is preferably 20 to 50% by mass, more preferably 25 to 40% by mass, and even more preferably 28 to 35% by mass, with respect to the total mass of the copolymer (S), as described in any one of [1] to

[27] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[29] The content of the constituent units derived from the non-conjugated polyene (C) is preferably 0.1 to 8.0% by mass, more preferably 0.5 to 5.0% by mass, even more preferably 1.0 to 3.0% by mass, and particularly preferably 1.2 to 2.0% by mass, with respect to the total mass of the copolymer (S). The copolymer composition according to any one of [1] to

[28] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[30] The molar ratio is preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, even more preferably 55 / 45 to 78 / 22, and particularly preferably 63 / 37 to 76 / 24. The copolymer composition according to any one of [1] to

[29] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[31] The α-olefin (B) having 3 to 20 carbon atoms is preferably at least one selected from the group consisting of 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, more preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, and even more preferably propylene, the copolymer composition according to any one of [1] to

[30] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[32] The non-conjugated polyene (C) preferably comprises at least one selected from the group consisting of 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene, more preferably comprising VNB, and even more preferably being VNB, the copolymer composition according to any one of [1] to

[31] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[33] The weight-average molecular weight of the copolymer (S) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, even more preferably 50,000 to 400,000, and particularly preferably 60,000 to 200,000. The copolymer composition according to any one of [1] to

[32] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[34] The content of the hydrosilyl group-containing compound (Y) is preferably 0.3 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, and even more preferably 0.7 to 2.5% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[33] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[35] The content of the aralkyl group is preferably 5 to 20% by mass, more preferably 8 to 18% by mass, and even more preferably 10 to 15% by mass, based on the total mass of the hydrosilyl group-containing compound (Y), the copolymer composition according to any one of [1] to

[34] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[36] The aralkyl group is preferably at least one selected from the group consisting of a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group, more preferably a linear or branched phenylpropyl group, and even more preferably -CH2-CH(CH3)-C6H5, the copolymer composition according to any one of [1] to

[35] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[37] The alkyl group content is preferably 15 to 40% by mass, more preferably 20 to 38% by mass, and even more preferably 25 to 35% by mass, with respect to the total mass of the hydrosilyl group-containing compound (Y), as described in any one of [1] to

[36] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[38] The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group, the copolymer composition according to any one of [1] to

[37] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[39] In formula (a), m is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 6, the copolymer composition according to any one of [1] to

[38] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[40] In formula (a), n is preferably 0 to 10, more preferably 2 to 9, and even more preferably 4 to 8, the copolymer composition according to any one of [1] to

[39] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[41] In formula (a), p is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0, the copolymer composition according to any one of [1] to

[40] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[42] In formula (a), each of the two Rs is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group, the copolymer composition according to any one of [1] to

[41] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[43] The content of the platinum-based catalyst is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.5% by mass, and even more preferably 0.03 to 0.1% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[42] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[44] The platinum-based catalyst is preferably at least one selected from the group consisting of elemental platinum (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, and a platinum-based catalyst supported on a support, and more preferably at least one selected from the group consisting of a complex of chloroplatinic acid with 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, and a complex of chloroplatinic acid with 1,3-divinyltetramethyldisiloxane, the copolymer composition according to any one of [1] to

[43] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[45] The copolymer composition according to any one of [1] to

[44] , further comprising a sodium bicarbonate blowing agent, the copolymer composition, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[46] The content of the sodium bicarbonate foaming agent is preferably 0.1 to 2.0% by mass, more preferably 0.3 to 1.5% by mass, and even more preferably 0.7 to 1.0% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[45] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[47] A copolymer composition according to any one of [1] to

[46] , wherein the copolymer composition further comprises a reaction inhibitor; a method for producing a copolymer composition; a foamed molded article; a method for producing a foamed molded article; a crosslinked molded article; or a method for producing a crosslinked molded article.

[48] ​​The content of the reaction inhibitor is preferably 0.005 to 0.3% by mass, more preferably 0.008 to 0.2% by mass, and even more preferably 0.01 to 0.15% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[47] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[49] The copolymer composition according to any one of [1] to

[48] , further comprising a hindered phenol antioxidant, the copolymer composition, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[50] The content of the hindered phenol antioxidant is preferably 0.1 to 3.0% by mass, more preferably 0.3 to 2.0% by mass, and even more preferably 0.5 to 1.0% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[49] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[51] The copolymer composition according to any one of [1] to

[50] , further comprising carbon black, the copolymer composition, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[52] The content of the carbon black is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and even more preferably 5 to 40% by mass, with respect to the total mass of the copolymer composition, the copolymer composition according to any one of [1] to

[51] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[53] The copolymer composition according to any one of [1] to

[52] , wherein the copolymer composition further comprises a paraffinic process oil, the copolymer composition, a foamed molded article, a foamed molded article, a crosslinked molded article, or a crosslinked molded article.

[54] The content of the paraffin-based process oil is preferably 1 to 90% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 35% by mass, with respect to the total mass of the copolymer composition, as described in any one of [1] to

[53] , the copolymer composition, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[55] The copolymer composition according to any one of [1] to

[54] , wherein the copolymer composition further comprises an organic peroxide, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[56] The content of the organic peroxide is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 4.0% by mass, and even more preferably 0.5 to 3.0% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[55] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[57] A copolymer composition according to any one of [1] to

[56] , wherein the copolymer composition further comprises a reinforcing agent; a method for producing a copolymer composition; a foamed molded article; a method for producing a foamed molded article; a crosslinked molded article; or a method for producing a crosslinked molded article.

[58] The content of the reinforcing agent is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, with respect to the total mass of the copolymer composition, as described in any one of [1] to

[57] , the copolymer composition, a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[59] A copolymer composition according to any one of [1] to

[58] , wherein the copolymer composition further comprises a hygroscopic agent; a method for producing a copolymer composition; a foamed molded article; a method for producing a foamed molded article; a crosslinked molded article; or a method for producing a crosslinked molded article.

[60] The content of the hygroscopic agent is preferably 0.5 to 3.0% by mass, more preferably 0.8 to 2.5% by mass, and even more preferably 1.0 to 2.0% by mass, with respect to the total mass of the copolymer composition. The copolymer composition according to any one of [1] to

[59] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[61] The copolymer composition, wherein the solvent content is preferably 0 to 5% by mass, more preferably 0 to 1% by mass, and even more preferably substantially 0% by mass, based on the total mass of the copolymer composition, the copolymer composition according to any one of [1] to

[60] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[62] The copolymer composition according to any one of [1] to

[61] , a method for producing a copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.[1]

[63] The method for producing the copolymer composition according to any one of

[17] to

[20] and

[26] to

[62] , wherein the first-stage formulation is preferably obtained under conditions of 100 to 170°C for 3 to 8 minutes, and more preferably under conditions of 120 to 160°C for 4 to 7 minutes.

[64] The method for producing the copolymer composition according to any one of

[17] to

[20] and

[26] to

[63] , wherein the second-stage formulation is preferably obtained under conditions of 10 to 100°C for 1 to 10 minutes, more preferably under conditions of 30 to 80°C for 3 to 8 minutes, and even more preferably under conditions of 40 to 60°C for 4 to 7 minutes.

[65] The method for producing a foamed molded article according to any one of [7] and

[26] to

[64] , wherein the melt extrusion is preferably carried out at 30°C or higher and less than 150°C for 5 to 30 minutes, more preferably at 40 to 140°C for 5 to 20 minutes, and even more preferably at 50 to 130°C for 7 to 15 minutes.

[66] The method for producing a foamed molded article according to any one of [7] and

[26] to

[65] , wherein the crosslinking is preferably carried out under conditions of 150 to 200°C for 1 to 30 minutes, more preferably under conditions of 160 to 195°C for 5 to 20 minutes, and even more preferably under conditions of 170 to 190°C for 7 to 15 minutes.

[67] The method for producing a crosslinked molded article according to any one of

[22] to

[62] , wherein the kneading is preferably carried out under conditions of less than 150°C for 5 to 30 minutes, more preferably under conditions of 40 to 140°C for 5 to 20 minutes, and even more preferably under conditions of 50 to 130°C for 7 to 15 minutes.

[68] The iodine value of the copolymer (S) is preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 3.5. The copolymer composition according to any one of [1] to

[67] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[69] The copolymer composition according to any one of [1] to

[68] , the number of silicon atom-bonded hydrogen atoms in one molecule of the hydrosilyl group-containing compound (Y) is preferably 2 to 10, more preferably 3 to 8, and even more preferably 5 to 7. A method for producing a copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[70] The copolymer composition according to any one of [1] to

[69] , the number of aralkyl groups in one molecule of the hydrosilyl group-containing compound (Y) is preferably 2 to 10, more preferably 3 to 8, and even more preferably 4 to 5. A method for producing a copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article.

[71] The copolymer (S) preferably has at least one substructure selected from formula (I) and formula (II) in its molecule, and more preferably has two or more, the copolymer composition according to any one of [1] to

[70] , a method for producing the copolymer composition, a foamed molded article, a method for producing a foamed molded article, a crosslinked molded article, or a method for producing a crosslinked molded article. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a copolymer composition containing an ethylene-α-olefin-non-conjugated polyene copolymer that is excellent in terms of the physical properties and processability of the resulting molded article, a method for producing the same, a foamed molded article obtained from this copolymer composition, a method for producing the same, and a crosslinked molded article and a method for producing the same. [Modes for carrying out the invention]

[0008] <First aspect> A copolymer composition according to a first aspect of the present invention comprises a copolymer (S), a hydrosilyl group-containing compound (Y), and a platinum-based catalyst.

[0009] [Copolymer (S)] The copolymer (S) in this embodiment has constituent units derived from ethylene (A), constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from unconjugated polyene (C). The copolymer composition in this embodiment may contain two or more copolymers (S).

[0010] It is preferable that the total mass percentage concentration of the constituent units of the copolymer (S) consisting of ethylene (A), α-olefins (B) having 3 to 20 carbon atoms, and non-conjugated polyenes (C) is 100% by mass.

[0011] The copolymer (S) in this embodiment satisfies the following requirements (i) and (ii). (i) The ratio [A] / [B], which is the number of moles of constituent units derived from ethylene (A) to the number of moles of constituent units derived from α-olefins (B) with 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. (ii) The mass percentage concentration of constituent units derived from the non-conjugated polyene (C) is 0.07 to 10% by mass relative to the total constituent units of the copolymer (S).

[0012] Examples of α-olefins (B) having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as "α-olefins (B)") 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. Of 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 copolymer (S) exhibits excellent mechanical properties, and a molded article with rubber elasticity can be obtained. These α-olefins may be used individually or in combination of two or more.

[0013] The non-conjugated polyene (C) is a non-conjugated polyene containing a total of two or more substructures selected from the following formulas (I) and (II) in its molecule. The copolymer (S) is crosslinked by a hydrosilylation reaction with a hydrosilyl group-containing compound (Y), and therefore has at least one, preferably two or more, carbon-carbon double bonds in its molecule. In particular, it is preferable that the copolymer (S) contains at least one, and more preferably two or more, substructures selected from the following formulas (I) and (II) derived from the non-conjugated polyene (C) in its molecule.

[0014] [ka]

[0015] Examples of non-conjugated polyenes (C) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene. Of these, it is preferable that the non-conjugated polyene (C) contains VNB, and more preferably VNB, because it is readily available, forms good hydrosilyl crosslinks, and improves the heat resistance of the polymer composition. The non-conjugated polyene (C) may be used alone or in combination of two or more types.

[0016] The copolymer (S) in this embodiment may further contain constituent units (CX) derived from a non-conjugated polyene (CX) that contains only one substructure selected from the group consisting of general formulas (I) and (II) in the molecule, to the extent that it does not impair the effect of the main body. Examples of such non-conjugated polyenes (CX) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, and 5-(2-ethyl-3-butenyl) Examples include 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene.

[0017] Of these, ENB is preferred because it is readily available, the crosslinking rate during hydrosilyl crosslinking is easy to control, and good mechanical properties can be easily obtained. The unconjugated polyene (CX) may be used alone or in combination of two or more types. In this embodiment, if the copolymer (S) contains constituent units derived from a non-conjugated polyene (CX), its mass percentage concentration is preferably 0 to 20% by mass, more preferably 0 to 8% by mass, and even more preferably 0.01 to 8% by mass, relative to the total constituent units of the copolymer (S).

[0018] Requirement (i) specifies that the ratio [A] / [B], which is the ratio of the number of moles [A] of ethylene (A)-derived constituent units [B] in the copolymer (S) in this embodiment to the number of moles [B] of α-olefin (B), satisfies 40 / 60 to 99.9 / 0.1.

[0019] [A] / [B] is preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, and even more preferably 55 / 45 to 78 / 22. The copolymer (S) is preferred because it satisfies requirement (i), resulting in a foam obtained by hydrosilyl crosslinking of copolymer (S) exhibiting excellent rubber elasticity, mechanical strength, and flexibility. Furthermore, the ratio [A] / [B] of the number of moles of constituent units derived from ethylene (A) in the copolymer (S) to the number of moles of constituent units derived from α-olefin (B) is: 13 This can be determined by 13C-NMR.

[0020] Requirement (ii) specifies that in the copolymer (S), the mass percentage concentration of constituent units derived from the unconjugated polyene (C) is 0.07 to 10% by mass relative to all constituent units of the copolymer (S). The mass percentage concentration of the constituent units derived from this non-conjugated polyene (C) is preferably 0.1 to 8.0 mass%, and more preferably 0.5 to 5.0 mass%. The total content of constituent units derived from ethylene (A), α-olefin (B), and non-conjugated polyene (C) in the copolymer (S) shall not exceed 100% by mass of the total mass of the copolymer (S).

[0021] Copolymer (S) is preferable because, by satisfying requirement (ii), the foam obtained from the copolymer composition according to this embodiment has sufficient hardness and excellent mechanical properties. Furthermore, when copolymer (S) is hydrosilyl crosslinked, it exhibits a fast crosslinking rate, which is preferable because it allows for efficient production of foam. Furthermore, the mass percentage concentration of constituent units derived from the non-conjugated polyene (C) in the copolymer (S) is: 13 This can be determined by 1C-NMR. Similarly, the content of constituent units derived from ethylene (A) in the copolymer (S), and the content of constituent units derived from α-olefins (B) having 3 to 20 carbon atoms, 13 This can be determined by 13C-NMR.

[0022] In this embodiment, the copolymer (S) preferably satisfies the following requirements (iii) to (v) in addition to requirements (i) and (ii) above. Hereinafter, a copolymer (S) that satisfies all of requirements (i) to (v) may be referred to as copolymer (S1). (iii) (n C ) is between 4.5 and 40. (n C ) = (Mw) × {(Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from unconjugated polyene (C) relative to the total mass of constituent units constituting copolymer (S), and the molecular weight of (C) is the molecular weight of unconjugated polyene (C). (iv) Complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelasticity measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and complex viscosity η at frequency ω = 100 rad / s * (ω=100) The ratio P(η) to (Pa·sec) * (ω=0.1) / η * (ω=100) The following formula (2) satisfies the intrinsic viscosity [η] and the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) (the content (mass%) of the constituent units constituting the copolymer (S) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units (S)). P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2) (v) Long chain branching number per 1000 carbon atoms obtained using 3D-GPC (LCB) 1000C The natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following equation (3). LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3)

[0023] Requirement (iii) is obtained by the following formula (1) (nC Specify the range of to be 4.5 or more and 40 or less. (n C ) = (Mw) × {(mass percentage concentration of (C) / 100} / molecular weight of (C) ··· (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) with respect to the total mass of the structural units constituting the copolymer (S) of the structural units derived from the non-conjugated polyene (C), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). Note that (Mw) is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). (n C ) is preferably 4.5 or more and 40 or less, and more preferably 4.5 or more and 35 or less.

[0024] (n C ) obtained by the above formula (1) is the number of structural units derived from the non-conjugated polyene (C) per weight-average molecular weight (Mw) of the copolymer (S). (n C ) being at least the lower limit makes it easy to obtain a sufficient crosslinking rate when hydrosilylation crosslinking. Also, being at most the upper limit makes it less likely for excessive crosslinking to occur, and the resulting foam exhibits better mechanical properties. When requirement (iii) is satisfied, the copolymer (S) has a low long-chain branching content, a high crosslinking rate of hydroxy crosslinking, excellent physical property balance such as the mechanical properties of the resulting foam, and is less likely to cause post-crosslinking, especially being excellent in heat aging resistance, which is preferable.

[0025] When the copolymer (S) contains the structural unit (CX), (n C+cx ) obtained by the following formula (1’) is preferably 4.5 or more and 40 or less, and more preferably 4.5 or more and 35 or less. (n C+cx ) = (Mw) × [{(mass percentage concentration of (C) / 100} / molecular weight of (C) + {(mass percentage concentration of (CX) / 100} / molecular weight of (CX)] ··· (1’) The (n C+cx ) obtained by the above formula (1’) is the total number of the number of structural units derived from the non-conjugated polyene (C) and the number of structural units derived from the non-conjugated polyene (CX) per weight average molecular weight (Mw) of the copolymer (S).

[0026] Requirement (iv) is the complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190 °C) of the copolymer (S) using a rheometer * (ω=0.1) (Pa·sec), and the complex viscosity η at a frequency ω = 100 rad / s * (ω=100) (Pa·sec), and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η], and the mass percent concentration of the structural units derived from the non-conjugated polyene (C) (content with respect to the total mass of the structural units constituting the copolymer (S) of the structural units derived from the non-conjugated polyene (C): mass %) satisfy the following formula (2). P / ([η] 2.9 ) ≤ mass percent concentration of (C) × 6 ··· Formula (2)

[0027] As the rheometer, a viscoelastic measurement device Ares (manufactured by Rheometric Scientific) was used, and the measurement was carried out at 190 °C and a strain of 1.0% while changing the frequency. The intrinsic viscosity [η] is a value measured in decalin at 135 °C.

[0028] It is more preferable that the copolymer (S) satisfies the following formula (2’). P / ([η] 2.9 ) ≤ mass percent concentration of (C) × 5.7 ··· Formula (2’) The ratio P(η * (ω=0.1) / η * (ω=100) ) represents the frequency dependence of viscosity, and P / ([η] 2.9Although influenced by factors such as short-chain branching and molecular weight, the value tends to be higher when there are many long-chain branches.

[0029] Generally, in ethylene-α-olefin-non-conjugated polyene copolymers, the more constituent units derived from non-conjugated polyenes they tend to contain, the more long-chain branching they have. However, the copolymer (S) in this embodiment is thought to satisfy formula (2) above because it has fewer long-chain branching units than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers.

[0030] Requirement (v) is the number of long-chain branches per 1000 carbon atoms (LCB) of copolymer (S), obtained using 3D-GPC. 1000C We specify that the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following equation (3). LCB 1000C ≤1 - 0.07 × Ln(Mw)···Equation (3)

[0031] The above formula (3) determines the upper limit of the long-chain branching content per unit carbon number of copolymer (S). In other words, requirement (v) means that the proportion of long-chain branching in copolymer (S) is small. By satisfying requirement (v), copolymer (S) exhibits excellent curing properties when hydrosilyl crosslinking is performed. Furthermore, the foam obtained using this copolymer exhibits excellent heat aging resistance. The copolymer (S) more preferably satisfies the following formula (3'). LCB 1000C ≦1-0.071×Ln(Mw)...Equation (3')

[0032] In equations (3) and (3') above, Mw and (LCB 1000C The values ​​shown are those obtained by structural analysis using 3D-GPC. Specifically, the absolute molecular weight distribution was determined using a 3D-high temperature GPC instrument, model PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was determined simultaneously using a viscometer. The main measurement conditions are as follows.

[0033] Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Bridge-type viscometer PL-BV400 (Manufactured by Polymer Laboratories)

[0034] Column: TSKgel GMH HR -H(S)HT x 2 bottles + TSKgel GMH HR -M(S)×1 piece (Each piece has an inner diameter of 7.8mmφ and a length of 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: Ca 1.5 mg / mL Sample filtration: Filtered using a 1.0 μm pore size sintered filter.

[0035] The dn / dc value required to determine the absolute molecular weight was determined for each sample using the dn / dc value of standard polystyrene (molecular weight 190,000), which is 0.053, and the response intensity of a differential refractometer per unit injection mass.

[0036] The long-chain branching parameter g'i for each eluted component was calculated from equation (v-1) based on the relationship between the intrinsic viscosity obtained from a viscometer and the absolute molecular weight obtained from a light scattering photometer.

[0037]

number

[0038]

number

[0039] Furthermore, using g'w, we can determine the number of branching points per molecular chain (BrNo) and the number of long-chain branches per 1000 carbon atoms (LCB). 1000C The degree of branching λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer equation (v-5), and LCB was also calculated. 1000C The calculation of λ was performed using equations (v-6) and (v-7). g is the long-chain branching parameter obtained from the radius of inertia Rg, and the following simple correlation is made between it and g' obtained from the intrinsic viscosity. Various values ​​have been proposed for ε in the equations depending on the shape of the molecule. Here, the calculation was performed assuming ε=1 (i.e., g'=g).

[0040]

number

[0041] λ = BrNo / M …(V-6) LCB 1000C =λ × 14000 …(V-7) In equation (V-7), 14000 is methylene (CH 2 This unit represents the molecular weight of 1000 molecules.

[0042] The intrinsic viscosity [η] of the copolymer (S) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g, and even more preferably 0.5 to 4.0 dL / g. The weight-average molecular weight (Mw) of the copolymer (S) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, and even more preferably 50,000 to 400,000.

[0043] In this embodiment, there are no particular limitations on the method for producing the copolymer (S), but it is preferable that it is obtained by copolymerizing monomers in the presence of a metallocene compound, and more preferably that it is obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound. Specifically, for example, it can be manufactured by the method described in International Publication No. 2015 / 122495.

[0044] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) in the present invention is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The copolymer composition of this embodiment may contain two or more hydrosilyl group-containing compounds (Y).

[0045] [ka]

[0046] In equation (a), n and p are 0 or positive numbers, m is a number in the range of 1 to 20, and the sum of n, m, and p is between 5 and 50. 1 , R 2 Each of these is an independent monovalent alkyl group, and they may be the same or different. a is an aralkyl group, and R is R 1 ,R 2 , hydrogen atom, R a It is a group selected from the following. However, when n=1, at least one of R is a hydrogen atom, and when n=0, both of R are hydrogen atoms.

[0047] Such hydrosilyl group-containing compounds (Y) are linear organohydrogenpolysiloxanes 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 the molecule.

[0048] By selectively using a hydrosilyl group-containing compound (Y) in combination with a copolymer (S), it is possible to obtain molded articles with particularly excellent physical properties such as scorch resistance, moldability, elongation at fracture, and compression molding strain, and in particular, the applicability to weatherstrip sponge materials is improved.

[0049] In formula (a), m is the number of diorganosiloxy units having silicon atom bonded aralkyl groups, and is a number in the range of 1 to 20, may be a number in the range of 2 to 10, and is particularly preferably a number in the range of 3 to 6.

[0050] In formula (a), n is the number of organohydrogensiloxy units having silicon-bonded hydrogen atoms in the side chain, and may be 0 or 1. When n=1, at least one of R is a hydrogen atom, and when n=0, both of R are hydrogen atoms, resulting in a structure with at least 2 silicon-bonded hydrogen atoms in the molecule.

[0051] Furthermore, even if n is a number other than 0 or 1, it is not prevented that one or both of the R atoms at both ends of the molecular chain are silicon-bonded hydrogen atoms. Moreover, it is preferable that n is a number other than 0 or 1, and more preferably that n ≥ m. More specifically, n may be a number in the range of 3 to 10, and is particularly preferable to be a number in the range of 3 to 9.

[0052] In formula (a), p is the number of diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms, and may be 0, or may be in the range of the number obtained by dividing the total degree of polymerization of diorganosiloxane units, which is expressed as the sum of n, m, and p described later, by the values ​​of n and m. For example, p may be a number in the range of 0 to 12, a number in the range of 0 to 10, a number in the range of 0 to 5, a number in the range of 0 to 2, and is preferred.

[0053] The hydrosilyl group-containing compound (Y) has a relatively low degree of siloxane polymerization, and the sum of the above values ​​of n, m, and p is 5 to 50, preferably 5 to 20, and may be 5 to 15. The hydrosilyl group-containing compound (Y), which is the crosslinking agent of the present invention, is particularly preferably a number in the range of 3 to 6 for m, a number in the range of 3 to 9 for n, and a number in the range of 0 to 2 for p.

[0054] In equation (a), R is R 1 ,R 2 , hydrogen atom, Ra It may be any of the groups selected from , except that if n=0 or 1, both or one of R is a hydrogen atom. R in the formula 1 ,R 2 is a monovalent alkyl group, which may be the same or different, and some of the hydrogen atoms bonded to the carbon atoms may be substituted with halogen atoms. Such alkyl groups may be alkyl groups having 1 to 20 carbon atoms, and industrially, they may be methyl groups.

[0055] In equation (a), R a R is an aralkyl group, preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms. Examples of such aralkyl groups include benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups, and it is particularly preferable that the aralkyl group contains at least one branched unit represented by -CH(CH3)- in the alkylene group between the aryl group such as a phenyl group and the silicon atom. In the present invention, R is particularly preferable. a This is an aralkyl group represented as -CH2-CH(CH3)-C6H5.

[0056] The aralkyl group is a characteristic functional group that gives hydrosilyl group-containing compounds (Y) usefulness as crosslinking agents. In particular, the presence of the aralkyl group together with silicon-bonded hydrogen atoms in this component, where n, m, and p are within the above ranges, significantly improves the physical properties of the resulting molded product.

[0057] [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 the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y).

[0058] Specific platinum-based catalysts can be any known catalysts typically used in addition-hardening curing, such as the fine-powdered metal-platinum catalyst described in U.S. Patent No. 2,970,150, the chloroplatinic acid catalyst described in U.S. Patent No. 2,823,218, the platinum-hydrocarbon complex compounds described in U.S. Patent No. 3,159,601 and U.S. Patent No. 159,662, the chloroplatinic acid-olefin complex compounds described in U.S. Patent No. 3,516,946, and the platinum-vinylsiloxane complex compounds described in U.S. Patent No. 3,775,452 and U.S. Patent No. 3,814,780.

[0059] More specifically, examples include elemental platinum (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or platinum-based catalysts supported on carriers such as alumina and silica. The copolymer composition of this embodiment may contain two or more platinum-based catalysts.

[0060] [Foaming agent] The copolymer composition of this embodiment may contain a blowing agent. Examples of blowing agents include sodium bicarbonate-based blowing agents, ADCA (azodicarbonamide), DPT (N,N'-dinitropentamethylenetetramine), and OBSH (4,4'-oxybisbenzenesulfonyl hydrazide). Among these, sodium bicarbonate-based blowing agents are preferred because they enable the reduction of specific gravity and increase of crosslink density in the foamed molded product.

[0061] [Reaction inhibitor] The copolymer composition of this embodiment may contain a reaction inhibitor. The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation addition reaction to an alkene) between the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). The inclusion of a reaction inhibitor is preferable in that it stabilizes the processability of the composition during kneading and molding.

[0062] Specific examples of reaction inhibitors include, for example, benzotriazole; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octin-3,6-diol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 1-ethynylcyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; acrylonitrile; N,N-diallylacetamide, N,N-diallylacetamide Examples of amide compounds include lylbenzamide, N,N,N',N'-tetraallyl-o-phthalate diamide, N,N,N',N'-tetraallyl-m-phthalate diamide, N,N,N',N'-tetraallyl-p-phthalate diamide, etc.; and other organic peroxides such as sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, and hydroperoxides. Among these compounds, 3,5-dimethyl-1-hexyn-3-ol is particularly preferred. The copolymer composition of this embodiment may contain two or more reaction inhibitors.

[0063] [Antioxidant] The copolymer composition of this embodiment may contain an antioxidant. A hindered phenol-based antioxidant is preferred as the antioxidant. The copolymer composition of this embodiment, by including a hindered phenol-based antioxidant, can further yield a foamed molded article with high water absorption and excellent compression set. The copolymer composition according to this embodiment may contain two or more antioxidants.

[0064] Examples of hindered phenol antioxidants include 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene (manufactured by ADEKA Corporation, product name: ADEKA Stab AO-330, melting point: 243~245℃) and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by A Corporation). DEKA Corporation (product name: Adekastab AO-20, melting point: 220~222℃), 4,4'-butylidenebis(6-tert-butyl-m-cresol) (ADEKA Corporation (product name: Adekastab AO-40, melting point: 210~214℃), N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine (BASF Japan Ltd. (product name: Irganox) Examples include MD1024 (melting point: 224-229°C), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Ltd., trade name: Irganox1010, melting point: 110-130°C), dibutylhydroxytoluene, and 2,5-di-tert-butylhydroquinone (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name: Nocrac NS-7, melting point: 200°C or higher).

[0065] [Anti-aging agent] The copolymer composition of this embodiment may contain an antioxidant. As an anti-aging agent, known anti-aging agents commonly used in rubber compositions can be used. Specifically, examples include sulfur-based anti-aging agents and amine-based anti-aging agents. Anti-aging agents may be used individually, but it is preferable to use two or more in combination to maintain heat aging resistance over long periods at high temperatures.

[0066] The sulfur-based antioxidant can be used in an amount of preferably 0.2 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and particularly preferably 0.2 to 6 parts by mass, per 100 parts by mass of copolymer (S). Using the sulfur-based antioxidant within this range is preferable because it significantly improves heat aging resistance and does not inhibit crosslinking of the copolymer composition.

[0067] The amine-based antioxidant is preferably used in an amount of 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and particularly preferably 0.2 to 3 parts by mass, per 100 parts by mass of copolymer (S). Using the amine-based antioxidant within this range is preferable because it significantly improves heat aging resistance and does not inhibit crosslinking of the copolymer composition.

[0068] [Reinforcement agent] The copolymer composition of this embodiment may contain a reinforcing agent to improve physical properties such as tensile stress at fracture and tensile elongation at fracture. The reinforcing agent is a known rubber reinforcing agent that is incorporated into the rubber composition, and specifically includes carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine talc powder, and differential silicic acid. The copolymer composition according to this embodiment may contain two or more reinforcing agents.

[0069] [Softener] The copolymer composition of this embodiment may contain a softening agent. The softener is a known softener that is incorporated into the rubber composition. Specifically, these include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; 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 its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricants, tall oil, and sub(factis). Of these, petroleum-based softeners are preferred, and paraffin-based process oils are particularly preferred. The copolymer composition according to this embodiment may contain two or more softening agents.

[0070] [Desiccant] The copolymer composition of this embodiment may contain a desiccant. Examples of desiccants include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. Of these, calcium oxide is preferred. The amount of desiccant added is preferably 0.5 to 15 parts by weight, more preferably 1.0 to 12 parts by weight, and even more preferably 1.0 to 10 parts by weight, per 100 parts by weight of copolymer (S). The copolymer composition according to this embodiment may contain two or more desiccants.

[0071] [Organic peroxide] The copolymer composition of this embodiment may contain an organic peroxide. Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0072] [Crosslinking agent] The copolymer composition of this embodiment may contain a crosslinking aid together with the organic peroxide. Examples of crosslinking aids include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds; and divinylbenzene. Such crosslinking aids are preferably used in an amount of 0.5 to 2 moles, more preferably about equimolars, per mole of organic peroxide used.

[0073] [Filler] The copolymer composition of this embodiment may contain fillers in order to reduce the compounding cost. Examples of fillers include talc and clay. These fillers may be used individually or in combination of two or more. Such fillers are preferably used in an amount of 1 to 500 parts by mass, more preferably 1 to 400 parts by mass, and even more preferably 1 to 300 parts by mass, per 100 parts by mass of copolymer (S). When the amount of filler is within the above range, the mechanical properties of the resulting molded article, such as tensile strength, tear strength, and abrasion resistance, can be improved.

[0074] [Processing aid] The copolymer composition of this embodiment may contain processing aids. As processing aids, a wide range of substances commonly used in rubber processing can be used. Specifically, examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. These processing aids may be used individually or in combination of two or more. The processing aid can be appropriately blended in an amount of preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of copolymer (S). When the amount of processing aid is within the above range, the processability, such as kneadability, extrusionability, and injection moldability, is excellent.

[0075] [Activating agent] The copolymer composition of this embodiment may contain an activator. Examples of activators include glycols such as polyethylene glycol and diethylene glycol; and amines such as di-n-butylamine and triethanolamine. These activators may be used individually or in combination of two or more. The activator can be appropriately blended in an amount of preferably 0.2 to 15 parts by mass, preferably 0.3 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass, per 100 parts by mass of copolymer (S).

[0076] [Other compounding agents, etc.] In addition to the above components, the copolymer composition of this embodiment may appropriately contain rubber compounding agents known on their own, such as metal salts of α,β-unsaturated organic acids, crosslinking accelerators, processing aids, plasticizers, tackifiers, etc., as long as the purpose of this embodiment is not impaired.

[0077] [Other resins] The copolymer composition of this embodiment may contain resins or rubbers other than copolymer (S) to the extent that it does not impair the effects of this embodiment. The amount of resins or rubbers other than copolymer (S) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and preferably not blended at all, per 100 parts by mass of copolymer (S).

[0078] Examples of resins other than copolymers (S) include general-purpose resins such as polyethylene, polypropylene, and polystyrene. Examples of rubber include silicone rubber, ethylene-propylene random copolymer rubber (EPR), natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, and chloroprene rubber.

[0079] [Composition] In the copolymer composition of this embodiment, the amount of hydrosilyl group-containing compound (Y) blended per 100 parts by mass of copolymer (S) is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 75 parts by mass, even more preferably 0.1 to 50 parts by mass, even more preferably 0.2 to 30 parts by mass, even more preferably 0.2 to 20 parts by mass, particularly preferably 0.5 to 10 parts by mass, and most preferably 0.5 to 5 parts by mass.

[0080] In the copolymer composition of this embodiment, the amount of platinum-based catalyst blended per 100 parts by mass of copolymer (S) is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5.0 parts by mass, even more preferably 0.01 to 3.0 parts by mass, even more preferably 0.02 to 1.0 parts by mass, even more preferably 0.03 to 0.7 parts by mass, particularly preferably 0.05 to 0.6 parts by mass, and most preferably 0.1 to 0.5 parts by mass.

[0081] [Effects and Effects] The copolymer composition of this embodiment suppresses the crosslinking reaction at relatively low temperatures (e.g., 50-130°C) during kneading and molding, thereby preventing scorching (burning or premature, unexpected crosslinking reactions) caused by heat during processing and storage. Furthermore, it exhibits excellent crosslinking properties, enabling crosslinking in a short time at crosslinking temperatures (e.g., 150-200°C). Therefore, by employing various known molding methods, it can be molded at a much faster rate than conventional copolymer compositions.

[0082] <Second aspect> A copolymer composition according to a second aspect of the present invention comprises a copolymer (S), a hydrosilyl group-containing compound (Y), a platinum-based catalyst, and a sodium bicarbonate-based blowing agent. The copolymer composition according to the second aspect of the present invention may further contain a reaction inhibitor. It may also contain a hindered phenol antioxidant.

[0083] Furthermore, the foamed molded article according to the second aspect of the present invention is a molded article made of a foam obtained by crosslinking and foaming the copolymer composition of the second aspect. Furthermore, a method for producing a foamed molded article according to a second aspect of the present invention is characterized by melt-extruding the copolymer composition of the second aspect and crosslinking it in a hot air vulcanizing tank.

[0084] [Copolymer (S)] The copolymer (S) in this embodiment is the same as the copolymer (S) in the first embodiment, and the preferred embodiment is also the same as the first embodiment. That is, it has a constituent unit derived from ethylene (A) as described in the first embodiment, a constituent unit derived from α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from non-conjugated polyene (C), and satisfies the above requirements (i) and (ii). The copolymer composition of this embodiment may contain two or more copolymers (S).

[0085] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) in the copolymer composition of this embodiment is the same as the hydrosilyl group-containing compound (Y) in the first embodiment. In other words, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural characteristics as those described in the first embodiment. The preferred embodiment of the hydrosilyl group-containing compound (Y) in this embodiment is the same as in the first embodiment. The copolymer composition of this embodiment may contain two or more hydrosilyl group-containing compounds (Y).

[0086] [Platinum catalyst] The platinum-based catalyst for hydrosilyl crosslinking in this embodiment is the same as the platinum-based catalyst for hydrosilyl crosslinking in the first embodiment, and the same applies to the preferred embodiment. The copolymer composition of this embodiment may contain two or more platinum-based catalysts.

[0087] [Baking soda-based foaming agent] The sodium bicarbonate-based blowing agent in the copolymer composition of this embodiment is a sodium bicarbonate-based blowing agent that satisfies the following requirement (b). (b) The cumulative roughness at 10% of the cumulative distribution curve based on the number of irregularities is 0.9 or less, and the cumulative equivalent diameter at 90% of the cumulative distribution curve based on the number of equivalent diameters is 43 μm or more. The copolymer composition of this embodiment may contain two or more sodium bicarbonate-based foaming agents.

[0088] In requirement (b), the degree of roughness is the ratio of the envelope perimeter to the perimeter, measured by dynamic image analysis using methyl ethyl ketone as the dispersion solvent. The perimeter is the length of the projected contour line of the particle, and the envelope perimeter is the length of the perimeter of the figure formed by connecting the shortest possible points of the particle's convex parts. Furthermore, the equivalent diameter of a circle is the diameter of a circle that has an area equal to the projected area of ​​the particle.

[0089] A cumulative 10% roughness score of 0.9 or less means that a certain amount of particles with low (high) roughness are included. A cumulative equivalent circle diameter of 90% being 43 μm or larger means that a certain amount of particles with a large equivalent circle diameter are included.

[0090] The perimeter and envelope perimeter for determining the degree of unevenness, as well as the projected area of ​​the particles for determining the equivalent diameter, were measured using a particle shape image analyzer PITA3 (manufactured by Seishin Corporation) with MEK as the dispersion solvent, and the dynamic image analysis method (wet method, observation magnification 4x). A commercially available baking soda-based foaming agent that meets requirement (b) is Cellbon FE-507R (product name) manufactured by Eiwa Chemical Industries, Ltd.

[0091] [Combined preparations, etc.] Reaction inhibitors, antioxidants, anti-aging agents, reinforcing agents, softeners, hygroscopic agents, organic peroxides, crosslinking aids, fillers, processing aids, surfactants, and other compounding agents, as well as other resins, can be appropriately blended in the same manner as in the first embodiment.

[0092] [Composition] In the copolymer composition of this embodiment, the preferred amount of hydrosilyl group-containing compound (Y) per 100 parts by mass of copolymer (S) is the same as in the first embodiment. Furthermore, in the copolymer composition of this embodiment, the preferred amount of platinum-based catalyst per 100 parts by mass of copolymer (S) is the same as in the first embodiment.

[0093] In the copolymer composition of this embodiment, the amount of sodium bicarbonate-based blowing agent blended per 100 parts by mass of copolymer (S) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 9 parts by mass, even more preferably 0.1 to 8 parts by mass, even more preferably 0.5 to 7.5 parts by mass, even more preferably 1.0 to 7.0 parts by mass, particularly preferably 1.5 to 6.5 parts by mass, and most preferably 1.5 to 6.0 parts by mass.

[0094] In the copolymer composition of this embodiment, the amount of reaction inhibitor blended per 100 parts by mass of copolymer (S) is preferably 0 to 2 parts by mass, more preferably 0 to 1.8 parts by mass, even more preferably 0 to 1.6 parts by mass, even more preferably 0 to 1.4 parts by mass, even more preferably 0 to 1.2 parts by mass, particularly preferably 0 to 1.0 parts by mass, and most preferably 0 to 0.8 parts by mass.

[0095] In the copolymer composition of this embodiment, the amount of hindered phenol-based antioxidant blended per 100 parts by mass of copolymer (S) is preferably 0.07 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 1 to 4 parts by mass.

[0096] In the copolymer composition of this embodiment, the amount of reinforcing agent blended per 100 parts by mass of copolymer (S) is preferably 70 to 200 parts by mass, and more preferably 70 to 150 parts by mass. In the copolymer composition of this embodiment, the amount of softener blended per 100 parts by mass of copolymer (S) is preferably 60 to 120 parts by mass, and more preferably 60 to 110 parts by mass.

[0097] [Foam molded product] To obtain a molded article consisting of a foam obtained by crosslinking and foaming the copolymer composition of this embodiment, known general processing methods (molding methods) for rubber compounding can be employed. Specifically, these are as follows. Using internal mixers such as Banbury mixers, kneaders, and intermixes, for example, a copolymer (S) and other components are kneaded at a temperature of 80 to 170°C for 3 to 10 minutes. Then, a hydrosilyl group-containing compound (Y), a platinum-based catalyst, a reaction inhibitor, a reinforcing agent, a softening agent, and a sodium bicarbonate-based blowing agent are added in the above-mentioned amounts, and other compounding agents, other rubbers or resins, etc., as needed. The mixture is then kneaded at a roll temperature of 50 to 130°C for 5 to 30 minutes using rolls such as open rolls or a kneader, and then dispensed in portions. In this way, a composition in the form of ribbons or sheets is usually obtained.

[0098] The obtained composition can be pre-molded into a desired shape using various molding methods, such as an extrusion machine, calender roll, press, injection molding machine, or transfer molding machine. Alternatively, the molded product can be introduced into a vulcanization tank and heated to crosslink it, thereby obtaining a foamed molded product consisting of a crosslinked and foamed copolymer composition.

[0099] Any known heating method can be used without limitation, but it is particularly preferable to heat the rubber composition at a temperature of 150-200°C for 1-30 minutes using a heating bath with heating modes such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt chamber). For molding and crosslinking, molds may or may not be used. If molds are not used, the rubber composition is usually molded, crosslinked, and foamed continuously.

[0100] The foamed molded articles obtained from the copolymer composition of this embodiment can be used for a variety of applications. Specifically, they can be suitably used in applications such as high-foaming sealants, automotive sealants, civil engineering and construction sealants, and various industrial sealants. They are particularly suitable for weatherstrip sponge materials (preferably with a foaming ratio of 1.3 to 4.0 times), and also for high-foaming sponge materials used in sponges, dam rubber, etc. (preferably with a foaming ratio exceeding 3.0 times and not exceeding 30 times). Examples of such foamed molded products include weatherstrip sponge materials such as door sponges, opening trim sponges, hood seal sponges, and trunk seal sponges; and highly foamed sponge materials such as heat insulating sponges and dam rubber.

[0101] [Effects and Effects] The foamed molded article obtained from the copolymer composition of this embodiment exhibits excellent sponge properties, including low specific gravity and high water absorption. Furthermore, it has a low compression set. Although the reason is not entirely clear, the copolymer composition of this embodiment contains a sodium bicarbonate-based blowing agent that satisfies requirement (b), allowing the crosslinking reaction and the blowing agent decomposition reaction to proceed simultaneously. It is also thought that this is because the crosslinking density tends to increase.

[0102] <Third aspect> A copolymer composition according to a third aspect of the present invention comprises a copolymer (S1) shown as a preferred embodiment of copolymer (S) in the first aspect, having an intrinsic viscosity [η] of 2.0 to 4.0 dL / g, a hydrosilyl group-containing compound (Y), a platinum-based catalyst, carbon black, a paraffin-based process oil, and, if necessary, a reaction inhibitor. Furthermore, the Mooney viscosity "ML(1+4)100℃" of the composition obtained by mixing the components excluding the hydrosilyl group-containing compound (Y), catalyst, and reaction inhibitor, as determined by the method described in JIS K 6300-1:2013, is 8 to 200. Furthermore, the crosslinked molded article according to the third aspect of the present invention is characterized by being obtained by crosslinking the copolymer composition of the third aspect.

[0103] [Copolymer (S)] The copolymer (S) in this embodiment is copolymer (S1) and has an intrinsic viscosity [η] within a specific range. That is, it has constituent units derived from ethylene (A) as described in the first embodiment, constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from unconjugated polyene (C), and satisfies requirements (i) and (ii) above, as well as requirements (iii) to (v), and has an intrinsic viscosity [η] of 2.0 to 4.0 dL / g.

[0104] The intrinsic viscosity [η] of the copolymer (S) is 2.0 to 4.0 dL / g, which makes it easy to adjust the Mooney viscosity "ML(1+4)100℃" of the composition, which is obtained by mixing the components excluding the hydrosilyl group-containing compound (Y), catalyst, and reaction inhibitor, to a range of 8 to 200, as determined by the method described in JIS K 6300-1:2013. In this embodiment, the intrinsic viscosity [η] of the copolymer (S) is preferably 2.2 to 3.5 dL / g, and more preferably 2.4 to 3.0 dL / g.

[0105] The copolymer (S) in this embodiment is the same as the copolymer (S) in the first embodiment including the preferred embodiments, except that it is the copolymer (S1) and the range of the intrinsic viscosity is defined. The copolymer composition of this embodiment may contain two or more copolymers (S1) having an intrinsic viscosity [η] within the above range.

[0106] [Hydrogensilyl group-containing compound (Y)] The hydrogensilyl group-containing compound (Y) in the copolymer composition of this embodiment is the same as the hydrogensilyl group-containing compound (Y) in the first embodiment. That is, the hydrogensilyl group-containing compound (Y) in this embodiment has the same structural features as those described in the first embodiment. The preferred embodiment of the hydrogensilyl group-containing compound (Y) in this embodiment is the same as that in the first embodiment. The copolymer composition of this embodiment may contain two or more hydrogensilyl group-containing compounds (Y).

[0107] [Platinum catalyst] The platinum-based catalyst for hydrosilylation crosslinking in this embodiment is the same as the platinum-based catalyst for hydrosilylation crosslinking in the first embodiment, and the preferred embodiments are also the same. The copolymer composition of this embodiment may contain two or more platinum-based catalysts.

[0108] [Reinforcing agent] The copolymer composition of this embodiment contains carbon black as a reinforcing agent. It is preferable that the copolymer composition contains 20% by mass or more of carbon black, more preferably 30% by mass or more, and particularly preferably contains only carbon black with respect to the total reinforcing agent contained. The carbon black may be surface-treated with a silane coupling agent.

[0109] [Softening agent] The copolymer composition of this embodiment contains paraffinic process oil as a softening agent. The copolymer composition of this embodiment preferably contains 5% by mass or more of paraffinic process oil, more preferably 10% by mass or more, and particularly preferably contains only paraffinic process oil, based on the total amount of softening agent.

[0110] Other softeners besides paraffinic process oils include petroleum-based softeners such as process oils, lubricating oils, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; 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 its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricants, tall oil, and sub(factis).

[0111] [Combined preparations, etc.] Reaction inhibitors, antioxidants, anti-aging agents, reinforcing agents other than carbon black, softeners other than paraffinic process oils, hygroscopic agents, organic peroxides, crosslinking aids, fillers, processing aids, surfactants, and other compounding agents, as well as other resins, can be appropriately blended in the same manner as in the first embodiment.

[0112] [Composition] In the copolymer composition of this embodiment, the preferred amount of hydrosilyl group-containing compound (Y) per 100 parts by mass of copolymer (S) is the same as in the first embodiment. Furthermore, in the copolymer composition of this embodiment, the preferred amount of platinum-based catalyst per 100 parts by mass of copolymer (S) is the same as in the first embodiment.

[0113] In the copolymer composition of this embodiment, the amount of carbon black blended per 100 parts by mass of copolymer (S) is 0.1 to 200 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 30 to 150 parts by mass. Superior mechanical strength is achieved when the carbon black content is above the lower limit. Superior processability is achieved when the carbon black content is below the upper limit.

[0114] In the copolymer composition of this embodiment, the amount of paraffinic process oil blended with 100 parts by mass of copolymer (S) is 0.1 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 20 to 80 parts by mass. Superior processability is achieved when the amount of paraffin-based process oil is above the lower limit. Superior mechanical strength is achieved when the amount of paraffin-based process oil is below the upper limit.

[0115] [Mooney Viscosity] The Mooney viscosity "ML(1+4)100℃" of a composition obtained by mixing the copolymer composition of this embodiment, excluding the hydrosilyl group-containing compound (Y), catalyst, and reaction inhibitor, is 8 to 200. Hereinafter, M is in Mooney units, L is the rotor shape, (1+4) means preheating for 1 minute and rotor rotation for 4 minutes, and 100℃ indicates the measurement temperature. A Mooney viscometer SMV-202 (manufactured by Shimadzu Corporation) was used for the measurement. The "ML(1+4)100℃" of the mixed composition is preferably 20 to 150, and more preferably 40 to 100. When "ML(1+4)100℃" is above the lower limit, the kneading processability is excellent. When it is below the upper limit, the molding processability, such as extrusion processability and injection moldability, is excellent.

[0116] [Crosslinked molded product] The copolymer composition of this embodiment can be pre-molded into a desired shape by various molding methods such as an extrusion molding machine, calender roll, press, injection molding machine, or transfer molding machine, or simultaneously with molding, by introducing the molded product into a vulcanizing tank and heating it to crosslink the copolymer composition, thereby obtaining a crosslinked molded product.

[0117] Any known heating method can be used without limitation, but it is particularly preferable to heat the material at a temperature of 150-200°C for 1-30 minutes using a heating bath with heating modes such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt bath). For molding and crosslinking, a mold may or may not be used. If a mold is not used, the copolymer composition is usually molded and crosslinked continuously.

[0118] The crosslinked molded articles obtained from the copolymer composition of this embodiment can be used in a variety of applications. Specifically, they are suitably used in weatherstrip sponges and the like.

[0119] [Effects and Effects] The copolymer composition according to this embodiment exhibits excellent moldability, such as extrusion moldability, press moldability, and injection moldability, as well as processability, such as roll processability. Furthermore, the crosslinked molded article obtained by crosslinking this copolymer composition exhibits excellent low-temperature properties (flexibility at low temperatures, rubber elasticity, etc.), mechanical properties, and heat resistance stability. The reason is not entirely clear, but it is thought that factors such as a high crosslink density and a uniform crosslink structure are contributing factors.

[0120] <Fourth aspect> A copolymer composition according to a fourth aspect of the present invention comprises a copolymer (S1) shown as a preferred embodiment of copolymer (S) in the first aspect, having an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g, a hydrosilyl group-containing compound (Y), a platinum-based catalyst, and a paraffin-based process oil. Furthermore, the "Mooney viscosity ML(1+4)100℃" obtained by the method described in JIS K 6300-1:2013 is between 0.1 and 8. Furthermore, the crosslinked molded article according to the fourth aspect of the present invention is characterized by being obtained by crosslinking the copolymer composition of the fourth aspect.

[0121] [Copolymer (S)] The copolymer (S) in this embodiment is the copolymer (S1) and has an intrinsic viscosity [η] within a specific range. That is, it has a structural unit derived from ethylene (A) described in the first embodiment, a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C). In addition to the above requirements (i) and (ii), it satisfies the above requirements (iii) to (v) and has an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g.

[0122] Since the intrinsic viscosity [η] of the copolymer (S) is 0.5 dL / g or more and less than 2.0 dL / g, it becomes easy to adjust the Mooney viscosity “ML(1+4)100 °C” of the copolymer composition, which is determined by the method described in JIS K 6300-1:2013, within the range of 0.1 to 8. The intrinsic viscosity [η] of the copolymer (S) in this embodiment is preferably 0.6 to 1.5 dL / g, and more preferably 0.7 to 1.3 dL / g.

[0123] The copolymer (S) in this embodiment is the copolymer (S1), and is the same as the copolymer (S) in the first embodiment including preferred embodiments, except that the range of the intrinsic viscosity is defined. The copolymer composition of this embodiment may contain two or more copolymers (S1) having an intrinsic viscosity [η] within the above range.

[0124] [Hydrogensilyl group-containing compound (Y)] The hydrogensilyl group-containing compound (Y) in the copolymer composition of this embodiment is the same as the hydrogensilyl group-containing compound (Y) in the first embodiment. That is, the hydrogensilyl group-containing compound (Y) in this embodiment has the same structural characteristics as those described in the first embodiment. The preferred embodiments of the hydrogensilyl group-containing compound (Y) in this embodiment are the same as those in the first embodiment. The copolymer composition of this embodiment may contain two or more hydrogensilyl group-containing compounds (Y).

[0125] [Platinum catalyst] The platinum-based catalyst for hydrosilyl crosslinking in this embodiment is the same as the platinum-based catalyst for hydrosilyl crosslinking in the first embodiment, and the same applies to the preferred embodiment. The copolymer composition of this embodiment may contain two or more platinum-based catalysts.

[0126] [Softener] The copolymer composition of this embodiment contains paraffinic process oil as a softening agent. The copolymer composition of this embodiment preferably contains 5% by mass or more of paraffinic process oil, more preferably 10% by mass or more, and particularly preferably contains only paraffinic process oil, based on the total amount of softening agent.

[0127] Other softeners besides paraffinic process oils include petroleum-based softeners such as process oils, lubricating oils, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; 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 its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricants, tall oil, and sub(factis).

[0128] [Combined preparations, etc.] Reaction inhibitors, antioxidants, anti-aging agents, reinforcing agents, softeners other than paraffin-based process oils, hygroscopic agents, organic peroxides, crosslinking aids, fillers, processing aids, surfactants, and other compounding agents, as well as other resins, can be appropriately blended in the same manner as in the first embodiment.

[0129] [Composition] In the copolymer composition of this embodiment, the preferred amount of hydrosilyl group-containing compound (Y) per 100 parts by mass of copolymer (S) is the same as in the first embodiment. Furthermore, in the copolymer composition of this embodiment, the preferred amount of platinum-based catalyst per 100 parts by mass of copolymer (S) is the same as in the first embodiment.

[0130] In the copolymer composition of this embodiment, the amount of carbon black blended per 100 parts by mass of copolymer (S) is 30 to 100 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 30 to 80 parts by mass. When the amount of carbon black used is within the above range, it offers an excellent balance between processability and mechanical strength.

[0131] In the copolymer composition of this embodiment, the amount of paraffinic process oil blended with 100 parts by mass of copolymer (S) is 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, and even more preferably 30 to 80 parts by mass. Superior machinability is achieved when the oil content is above the lower limit. Superior mechanical strength is achieved when the paraffin-based process oil content is below the upper limit.

[0132] [Mooney Viscosity] The Mooney viscosity "ML(1+4)100℃" of the copolymer composition according to this embodiment is 0.1 to 8. Hereinafter, M is the Mooney unit, L is the rotor shape, (1+4) means preheating for 1 minute and rotor rotation for 4 minutes, and 100℃ indicates the measurement temperature. A Mooney viscometer SMV-202 (manufactured by Shimadzu Corporation) was used for the measurement. If "ML(1+4)100℃" falls within the above range, it can be easily molded into the desired shape by hand, much like working with clay.

[0133] [Crosslinked molded product] The copolymer composition of this embodiment can be pre-molded into a desired shape by various molding methods such as an extrusion molding machine, calender roll, press, injection molding machine, or transfer molding machine, or simultaneously with molding, by introducing the molded product into a vulcanizing tank and heating it to crosslink the copolymer composition, thereby obtaining a crosslinked molded product.

[0134] Any known heating method can be used without limitation, but it is particularly preferable to heat the material at a temperature of 150-200°C for 1-30 minutes using a heating bath with heating modes such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt bath). For molding and crosslinking, a mold may or may not be used. If a mold is not used, the copolymer composition is usually molded and crosslinked continuously.

[0135] The crosslinked molded articles obtained from the copolymer composition of this embodiment can be used for a variety of applications. Specifically, they are suitable for use in golf club grips, cane grips, toothbrush grips, tableware (spoons, forks, chopsticks) grips, broom grips, teacup grips, and the like.

[0136] [Effects and Effects] According to the copolymer composition of this embodiment, the compression set of the crosslinked molded article obtained by crosslinking this copolymer composition is small. Furthermore, when this copolymer composition is crosslinked, it becomes hard enough to be molded by hand, like clay, thus enabling handmade-like molding. The reason for the low compression set is not entirely clear, but it is thought to be due to the high crosslink density and the uniformity of the crosslink structure.

[0137] <Fifth aspect> A copolymer composition according to a fifth aspect of the present invention comprises a copolymer (S1) shown as a preferred embodiment of copolymer (S) in the first aspect, having an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g, a hydrosilyl group-containing compound (Y), a platinum-based catalyst, carbon black, and a paraffin-based process oil. Furthermore, the Brookfield rotational viscosity at 25°C, as determined by the method described in JIS K 7117:1999, is 6000 Pa·s or less. Furthermore, the crosslinked molded article according to the fifth aspect of the present invention is characterized by being obtained by crosslinking the copolymer composition of the fifth aspect.

[0138] [Copolymer (S)] The copolymer (S) in this embodiment is copolymer (S1) and has an intrinsic viscosity [η] within a specific range. That is, it has constituent units derived from ethylene (A) as described in the first embodiment, constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from unconjugated polyene (C), and satisfies requirements (i) and (ii) above, as well as requirements (iii) to (v), and has an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g.

[0139] The intrinsic viscosity [η] of the copolymer (S) being 0.5 dL / g or more and less than 2.0 dL / g makes it easy to adjust the Brookfield rotational viscosity at 25°C of the copolymer composition, as determined by the method described in JIS K 7117:1999, to 6000 Pa·s or less. In this embodiment, the intrinsic viscosity [η] of the copolymer (S) is preferably 0.6 to 1.5 dL / g, and more preferably 0.7 to 1.3 dL / g.

[0140] The copolymer (S) in this embodiment is the same as the copolymer (S) in the first embodiment, including the preferred embodiment, except that the copolymer (S1) has a defined range of intrinsic viscosity. The copolymer composition of this embodiment may contain two or more copolymers (S1) having an intrinsic viscosity [η] within the above range.

[0141] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) in the copolymer composition of this embodiment is the same as the hydrosilyl group-containing compound (Y) in the first embodiment. In other words, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural characteristics as those described in the first embodiment. The preferred embodiment of the hydrosilyl group-containing compound (Y) in this embodiment is the same as in the first embodiment. The copolymer composition of this embodiment may contain two or more hydrosilyl group-containing compounds (Y).

[0142] [Platinum catalyst] The platinum-based catalyst for hydrosilyl crosslinking in this embodiment is the same as the platinum-based catalyst for hydrosilyl crosslinking in the first embodiment, and the same applies to the preferred embodiment. The copolymer composition of this embodiment may contain two or more platinum-based catalysts.

[0143] [Reinforcement agent] The copolymer composition of this embodiment contains carbon black as a reinforcing agent. The copolymer composition of this embodiment preferably contains 5 by mass or more of carbon black, more preferably 10 by mass or more, and particularly preferably contains only carbon black, relative to the total amount of reinforcing agents. The carbon black may be surface-treated with a silane coupling agent.

[0144] [Softener] The copolymer composition of this embodiment contains paraffinic process oil as a softening agent. The copolymer composition of this embodiment preferably contains 5% by mass or more of paraffinic process oil, more preferably 10% by mass or more, and particularly preferably contains only paraffinic process oil, based on the total amount of softening agent. Other softeners besides paraffinic process oils include petroleum-based softeners such as process oils, lubricating oils, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; 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 its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricants, tall oil, and sub(factis).

[0145] [Combined preparations, etc.] Reaction inhibitors, antioxidants, anti-aging agents, reinforcing agents other than carbon black, softeners other than paraffinic process oils, hygroscopic agents, organic peroxides, crosslinking aids, fillers, processing aids, surfactants, and other compounding agents, as well as other resins, can be appropriately blended in the same manner as in the first embodiment.

[0146] [Composition] In the copolymer composition of this embodiment, the preferred amount of hydrosilyl group-containing compound (Y) per 100 parts by mass of copolymer (S) is the same as in the first embodiment. Furthermore, in the copolymer composition of this embodiment, the preferred amount of platinum-based catalyst per 100 parts by mass of copolymer (S) is the same as in the first embodiment.

[0147] In the copolymer composition of this embodiment, the amount of carbon black blended per 100 parts by mass of copolymer (S) is 0.1 to 200 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 10 to 180 parts by mass. When the amount of carbon black included is within the above range, it provides an excellent balance of fluidity, mechanical strength, and compression set.

[0148] In the copolymer composition of this embodiment, the amount of paraffinic process oil blended with 100 parts by mass of copolymer (S) is 100 to 400 parts by mass, more preferably 200 to 365 parts by mass, and even more preferably 245 to 325 parts by mass. When the amount of paraffin-based process oil used is within the above range, a good balance of fluidity, mechanical strength, and compression set is achieved.

[0149] [Brookfield rotational viscosity] The Brookfield rotational viscosity (Type B viscosity) of the copolymer composition according to this embodiment, as determined by the method described in JIS K 7117:1999, is 6000 Pa·s or less at 25°C. The Brookfield rotational viscosity is preferably 50 to 5800 Pa·s, and more preferably 50 to 5600 Pa·s. Excellent fluidity is achieved when the Brookfield rotational viscosity is within this range. A Brookfield rotational viscometer Model DV-II (manufactured by Brookfield Engineering Laboratories, Inc.) was used for the measurements.

[0150] [Crosslinked molded product] The copolymer composition of this embodiment can be pre-molded into a desired shape by various molding methods such as an extrusion molding machine, calender roll, press, injection molding machine, or transfer molding machine, or simultaneously with molding, by introducing the molded product into a vulcanizing tank and heating it to crosslink the copolymer composition, thereby obtaining a crosslinked molded product.

[0151] Any known heating method can be used without limitation, but it is particularly preferable to heat the material at a temperature of 150-200°C for 1-30 minutes using a heating bath with heating modes such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt bath). For molding and crosslinking, a mold may or may not be used. If a mold is not used, the copolymer composition is usually molded and crosslinked continuously.

[0152] The crosslinked molded articles obtained from the copolymer composition of this embodiment can be used in a variety of applications. Specifically, they are suitably used in potting materials, rubber coatings, and the like.

[0153] [Effects and Effects] According to the copolymer composition of this embodiment, excellent rubber properties can be obtained in a crosslinked molded article obtained by crosslinking this copolymer composition. The reason is not entirely clear, but it is thought that the uniformity of the cross-linking structure is a contributing factor.

[0154] <Sixth aspect> A copolymer composition according to a sixth aspect of the present invention comprises a copolymer which is copolymer (S1) shown as a preferred embodiment of copolymer (S) in the first aspect, The compound contains a hydrosilyl group-containing compound (Y), a platinum-based catalyst, a reaction inhibitor, and an organic peroxide. In this specification and in the claims, "parts by mass" refers to parts by mass calculated on a solid content basis, excluding solvents. Furthermore, a numerical range represented by "~" means a range of numbers whose lower and upper limits are the numbers before and after the "~".

[0155] [Copolymer (S)] The copolymer (S) in this embodiment has constituent units derived from ethylene (A), constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from unconjugated polyene (C).

[0156] With respect to all constituent units of the copolymer (S), the total mass percentage concentration of constituent units derived from ethylene (A), constituent units derived from α-olefins (B) having 3 to 20 carbon atoms, and constituent units derived from non-conjugated polyenes (C) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 92% by mass or more, and particularly preferably 100% by mass.

[0157] Examples of α-olefins (B) having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as "α-olefins (B)") 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. Of 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 copolymer (S) exhibits excellent mechanical properties, and a molded article with rubber elasticity can be obtained. These α-olefins may be used individually or in combination of two or more.

[0158] A non-conjugated polyene (C) is a non-conjugated polyene that contains a total of two or more substructures selected from the following formulas (I) and (II) in its molecule.

[0159] [ka]

[0160] Examples of non-conjugated polyenes (C) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene. Of these, it is preferable that the non-conjugated polyene (C) contains VNB, and more preferably VNB, because it is readily available, forms good hydrosilyl crosslinks, and improves the heat resistance of the polymer composition. The non-conjugated polyene (C) may be used alone or in combination of two or more types.

[0161] The copolymer (S) in this embodiment may further contain constituent units (CX) derived from a non-conjugated polyene (CX) that contains only one substructure selected from the group consisting of general formulas (I) and (II) in the molecule, to the extent that the effects of this embodiment are not impaired. Examples of such non-conjugated polyenes (CX) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, and 5-(2-ethyl-3-butenyl) Examples include 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene.

[0162] Of these, ENB is preferred because it is readily available, the crosslinking rate during hydrosilyl crosslinking is easy to control, and good mechanical properties can be easily obtained. The unconjugated polyene (CX) may be used alone or in combination of two or more types. In this embodiment, if the copolymer (S) contains constituent units derived from a non-conjugated polyene (CX), its mass percentage concentration is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0.01 to 8% by mass, relative to the total constituent units of the copolymer (S).

[0163] The copolymer (S) in this embodiment satisfies the following requirements (i) to (v). (i) The ratio [A] / [B], which is the number of moles of constituent units derived from ethylene (A) to the number of moles of constituent units derived from α-olefins (B) with 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.1. (ii) The mass percentage concentration of constituent units derived from the non-conjugated polyene (C) is 0.07 to 10% by mass relative to the total constituent units of the copolymer (S).

[0164] (iii) (n C ) is between 4.5 and 40. (n C ) = (Mw) × {(Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from unconjugated polyene (C) relative to the total mass of constituent units constituting copolymer (S), and the molecular weight of (C) is the molecular weight of unconjugated polyene (C).

[0165] (iv) Complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelasticity measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and complex viscosity η at frequency ω = 100 rad / s * (ω=100) The ratio P(η) to (Pa·sec) * (ω=0.1) / η * (ω=100) The following formula (2) satisfies the intrinsic viscosity [η] and the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) (the content (mass%) of the constituent units constituting the copolymer (S) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units (S)). P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2)

[0166] (v) Long chain branching number per 1000 carbon atoms obtained using 3D-GPC (LCB) 1000C The natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following equation (3). LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3)

[0167] Requirement (i) specifies that the ratio [A] / [B], which is the ratio of the number of moles [A] of ethylene (A)-derived constituent units [B] in the copolymer (S) in this embodiment to the number of moles [B] of α-olefin (B), satisfies 40 / 60 to 99.9 / 0.1.

[0168] [A] / [B] is preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, and even more preferably 55 / 45 to 78 / 22. The copolymer (S) is preferred because, when requirement (i) is met, the molded article obtained by hydrosilyl crosslinking of copolymer (S) exhibits excellent rubber elasticity and has excellent mechanical strength and flexibility. Furthermore, the ratio [A] / [B] of the number of moles of constituent units derived from ethylene (A) in the copolymer (S) to the number of moles of constituent units derived from α-olefin (B) is: 13 This can be determined by 13C-NMR.

[0169] Requirement (ii) specifies that in the copolymer (S), the mass percentage concentration of constituent units derived from the unconjugated polyene (C) is 0.07 to 10% by mass relative to all constituent units of the copolymer (S). The mass percentage concentration of the constituent units derived from this non-conjugated polyene (C) is preferably 0.1 to 8.0 mass%, and more preferably 0.5 to 5.0 mass%.

[0170] Copolymer (S) is preferable because, by satisfying requirement (ii), the crosslinked molded article obtained from the copolymer composition according to this embodiment has sufficient hardness and excellent mechanical properties. Furthermore, when copolymer (S) is hydrosilyl crosslinked, it exhibits a fast crosslinking rate, which is preferable because it allows for the efficient production of crosslinked molded articles. Furthermore, the mass percentage concentration of constituent units derived from the non-conjugated polyene (C) in the copolymer (S) is: 13 This can be determined by 13C-NMR.

[0171] The mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is preferably such that the weight-average molecular weight (Mw) of the copolymer (S) satisfies the following formula (4). Mass percentage concentration of 6 - 0.45 × Ln(Mw) ≤ (C) ... Equation (4)

[0172] Requirement (iii) is obtained by the following formula (1) (n C The range of ) is specified as 4.5 or greater and 40 or less. (n C ) = (Mw) × {(Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). Note that (Mw) is the weight-average molecular weight in polystyrene terms, measured by gel permeation chromatography (GPC). (n C ) is preferably 4.5 or more and 40 or less, and more preferably 4.5 or more and 35 or less.

[0173] (n C ) is the number of constituent units derived from the unconjugated polyene (C) per weight-average molecular weight (Mw) of the copolymer (S). (n C When the value is above the lower limit, it is easier to obtain a sufficient crosslinking rate when performing hydrosilyl crosslinking. Furthermore, when it is below the upper limit, excessive crosslinking is less likely to occur, and the resulting crosslinked molded article exhibits superior mechanical properties. When requirement (iii) is met, the copolymer (S) is preferable because it has a low long-chain branching content, a fast hydroxy-crosslinking rate, and an excellent balance of physical properties such as the mechanical properties of the resulting crosslinked molded article, as well as being less prone to post-crosslinking and particularly excellent in heat aging resistance.

[0174] If the copolymer (S) contains constituent units (CX), then (n) can be calculated using the following formula (1'). C+cx It is preferable that the ratio is between 4.5 and 40, and more preferably between 4.5 and 35. (n C+cx ) = (Mw) × [{(Mass percentage concentration of (C) / 100} / Molecular weight of (C) + {(Mass percentage concentration of (CX) / 100} / Molecular weight of (CX)] ... (1') (n C+cx ) is the total number of constituent units derived from non-conjugated polyenes (C) and non-conjugated polyenes (CX) per weight-average molecular weight (Mw) of the copolymer (S).

[0175] Requirement (iv) is the complex viscosity η of copolymer (S) at a frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. * (ω=0.1) (Pa·sec) and complex viscosity η at frequency ω = 100 rad / s * (ω=100) The ratio P(η) to (Pa·sec) * (ω=0.1) / η * (ω=100) The following formula (2) is specified to satisfy the intrinsic viscosity [η] and the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) (content relative to the total mass of the constituent units constituting the copolymer (S) of the constituent units derived from the non-conjugated polyene (C): mass%). P / ([η] 2.9 Mass percentage concentration of ) ≤ (C) × 6 ... Equation (2)

[0176] As a rheometer, an Ares viscoelasticity measuring device (manufactured by Rheometric Scientific) was used, and measurements were performed at 190°C and 1.0% strain, while varying the frequency. The intrinsic viscosity [η] is a value measured in decalin at 135°C.

[0177] The copolymer (S) more preferably satisfies the following formula (2'). P / ([η]2.9 Mass percentage concentration of ) ≤ (C) × 5.7 ... Equation (2') ratio P(η * (ω=0.1) / η * (ω=100) ) represents the frequency dependence of viscosity and corresponds to the left side of equations (2) and (2'), P / ([η] 2.9 Although influenced by factors such as short-chain branching and molecular weight, the value tends to be higher when there are many long-chain branches.

[0178] Generally, in ethylene-α-olefin-non-conjugated polyene copolymers, the more constituent units derived from non-conjugated polyenes they tend to contain, the more long-chain branching they have. However, the copolymer (S) in this embodiment is thought to satisfy formula (2) above because it has fewer long-chain branching units than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers.

[0179] Requirement (v) is the number of long-chain branches per 1000 carbon atoms (LCB) of copolymer (S), obtained using 3D-GPC. 1000C We specify that the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following equation (3). LCB 1000C ≤1 - 0.07 × Ln(Mw)···Equation (3)

[0180] The above formula (3) determines the upper limit of the long-chain branching content per unit carbon number of copolymer (S). In other words, requirement (v) means that the proportion of long-chain branching in copolymer (S) is small. By satisfying requirement (v), copolymer (S) exhibits excellent curing properties when hydrosilyl crosslinking is performed. Furthermore, the crosslinked molded article obtained using this copolymer exhibits excellent heat aging resistance. The copolymer (S) more preferably satisfies the following formula (3'). LCB 1000C ≦1-0.071×Ln(Mw)...Equation (3')

[0181] In equations (3) and (3') above, Mw and (LCB 1000CThe values ​​shown are those obtained by structural analysis using 3D-GPC. Specifically, the absolute molecular weight distribution was determined using a 3D-high temperature GPC instrument, model PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was determined simultaneously using a viscometer. The main measurement conditions are as follows.

[0182] Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Bridge-type viscometer PL-BV400 (Manufactured by Polymer Laboratories)

[0183] Column: TSKgel GMH HR -H(S)HT x 2 bottles + TSKgel GMH HR -M(S)×1 piece (Each piece has an inner diameter of 7.8mmφ and a length of 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: Ca 1.5 mg / mL Sample filtration: Filtered using a 1.0 μm pore size sintered filter.

[0184] The dn / dc value required to determine the absolute molecular weight was determined for each sample using the dn / dc value of standard polystyrene (molecular weight 190,000), which is 0.053, and the response intensity of a differential refractometer per unit injection mass.

[0185] The long-chain branching parameter g'i for each eluted component was calculated from equation (v-1) based on the relationship between the intrinsic viscosity obtained from a viscometer and the absolute molecular weight obtained from a light scattering photometer.

[0186]

number

[0187]

number

[0188] Furthermore, using g'w, we can determine the number of branching points per molecular chain (BrNo) and the number of long-chain branches per 1000 carbon atoms (LCB). 1000C The degree of branching λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer equation (v-5), and LCB was also calculated. 1000C The calculation of λ was performed using equations (v-6) and (v-7). g is the long-chain branching parameter obtained from the radius of inertia Rg, and the following simple correlation is made between it and g' obtained from the intrinsic viscosity. Various values ​​have been proposed for ε in the equations depending on the shape of the molecule. Here, the calculation was performed assuming ε=1 (i.e., g'=g).

[0189]

number

[0190] λ = BrNo / M …(V-6) LCB 1000C =λ × 14000 …(V-7) In equation (V-7), 14000 is methylene (CH 2 This unit represents the molecular weight of 1000 molecules.

[0191] The intrinsic viscosity [η] of the copolymer (S) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g, and even more preferably 0.5 to 4.0 dL / g. The weight-average molecular weight (Mw) of the copolymer (S) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, and even more preferably 50,000 to 400,000.

[0192] The copolymer (S) in this embodiment may also preferably satisfy requirement (vi) represented by the following formula (5). (vi) Log{η * (ω=0.01)} / log{η * (ω=10)}≦0.0753 × {Apparent iodine value derived from unconjugated polyene (C)} + 1.42 … Equation (5)

[0193] In equation (5), η * (ω=0.01) This is the complex viscosity η at a frequency ω = 0.01 rad / s, obtained by linear viscoelasticity measurement (190°C) using a rheometer. * (Pa·sec) Also, η * (ω=10) This is the complex viscosity η at a frequency ω = 10 rad / s, obtained by linear viscoelasticity measurement (190°C) using a rheometer. * (Pa·sec) Here, η * (ω=0.01) and η * (ω=10) The complex viscosity η in requirement (iv) is * (ω=0.1) and complex viscosity η * (ω=100) The same method can be used to determine the other parameters, except for the measurement frequency.

[0194] In equation (5), the apparent iodine value derived from the unconjugated polyene (C) is calculated by the following formula. Apparent iodine value derived from (C) = weight fraction of (C) × 253.81 / molecular weight of (C)

[0195] In equation (5) above, the left side represents the shear rate dependence, which is an indicator of the amount of long-chain branching, and the right side represents an indicator of the content of unconjugated polyenes (C) that are not consumed as long-chain branching during polymerization. If requirement (vi) is met, it is preferable because the degree of long-chain branching is not too high. If requirement (vi) is not met, it indicates that a large proportion of the copolymerized non-conjugated polyene (C) was consumed in the formation of long-chain branching.

[0196] The copolymer composition of this embodiment may contain two or more copolymers (S). For example, two or more copolymers (S) with different (a) ethylene / α-olefin molar ratios (3-20 carbon atoms), (b) iodine values, or (c) intrinsic viscosity [η] may be mixed and used. In particular, (c) may be a mixture of a low intrinsic viscosity component and a high intrinsic viscosity component.

[0197] In this embodiment, there are no particular limitations on the method for producing the copolymer (S), but it is preferable that it is obtained by copolymerizing monomers in the presence of a metallocene compound, and more preferably that it is obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound. Specifically, for example, it can be manufactured by the method described in International Publication No. 2015 / 122495.

[0198] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) in the present invention is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The copolymer composition of this embodiment may contain two or more hydrosilyl group-containing compounds (Y).

[0199] [ka]

[0200] In equation (a), n and p are 0 or positive numbers, m is a number in the range of 1 to 20, and the sum of n, m, and p is between 5 and 50. 1 , R 2 Each of these is an independent monovalent alkyl group, and they may be the same or different. a is an aralkyl group, and R is R 1 ,R 2 , hydrogen atom, R aIt is a group selected from the following. However, when n=1, at least one of R is a hydrogen atom, and when n=0, both of R are hydrogen atoms.

[0201] Such hydrosilyl group-containing compounds (Y) are linear organohydrogenpolysiloxanes 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 the molecule.

[0202] By selectively using a hydrosilyl group-containing compound (Y) in combination with a copolymer (S), it is possible to obtain molded articles with particularly excellent physical properties such as scorch resistance, moldability, elongation at fracture, and compression molding strain, and in particular, the applicability to weatherstrip sponge materials is improved.

[0203] In formula (a), m is the number of diorganosiloxy units having silicon atom bonded aralkyl groups, and is a number in the range of 1 to 20, may be a number in the range of 2 to 10, and is particularly preferably a number in the range of 3 to 6.

[0204] In formula (a), n is the number of organohydrogensiloxy units having silicon-bonded hydrogen atoms in the side chain, and may be 0 or 1. When n=1, at least one of R is a hydrogen atom, and when n=0, both of R are hydrogen atoms, resulting in a structure with at least 2 silicon-bonded hydrogen atoms in the molecule.

[0205] Furthermore, even if n is a number other than 0 or 1, it is not prevented that one or both of the R atoms at both ends of the molecular chain are silicon-bonded hydrogen atoms. Moreover, it is preferable that n is a number other than 0 or 1, and more preferably that n ≥ m. More specifically, n may be a number in the range of 3 to 10, and is particularly preferable to be a number in the range of 3 to 9.

[0206] In formula (a), p is the number of diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms, and may be 0, or may be in the range of the number obtained by dividing the total degree of polymerization of diorganosiloxane units, which is expressed as the sum of n, m, and p described later, by the values ​​of n and m. For example, p may be a number in the range of 0 to 12, a number in the range of 0 to 10, a number in the range of 0 to 5, a number in the range of 0 to 2, and is preferred.

[0207] The hydrosilyl group-containing compound (Y) has a relatively low degree of siloxane polymerization, and the sum of the above values ​​of n, m, and p is 5 to 50, preferably 5 to 20, and may be 5 to 15. The hydrosilyl group-containing compound (Y), which is the crosslinking agent of the present invention, is particularly preferably a number in the range of 3 to 6 for m, a number in the range of 3 to 9 for n, and a number in the range of 0 to 2 for p.

[0208] In equation (a), R is R 1 ,R 2 , hydrogen atom, R a It may be any of the groups selected from , except that if n=0 or 1, both or one of R is a hydrogen atom. R in the formula 1 ,R 2 is a monovalent alkyl group, which may be the same or different, and some of the hydrogen atoms bonded to the carbon atoms may be substituted with halogen atoms. Such alkyl groups may be alkyl groups having 1 to 20 carbon atoms, and industrially, they may be methyl groups.

[0209] In equation (a), R a R is an aralkyl group, preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms. Examples of such aralkyl groups include benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups, and it is particularly preferable that the alkylene structure between the aryl group such as a phenyl group and the silicon atom contains at least one branched unit represented by -CH(CH3)-. In the present invention, R is particularly preferable. aThis is an aralkyl group represented as -CH2-CH(CH3)-C6H5.

[0210] The aralkyl group is a characteristic functional group that gives hydrosilyl group-containing compounds (Y) usefulness as crosslinking agents. In particular, the presence of the aralkyl group together with silicon-bonded hydrogen atoms in this component, where n, m, and p are within the above ranges, significantly improves the physical properties of the resulting molded product.

[0211] In the copolymer composition of this embodiment, the amount of hydrosilyl group-containing compound (Y) per 100 parts by mass of copolymer (S) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 8 parts by mass.

[0212] [Platinum-based catalyst] Platinum-based catalysts for hydrosilyl crosslinking are addition reaction catalysts that promote the addition reaction (hydrosilylation reaction of alkenes) between the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). No particular restrictions are placed on the use of such catalysts.

[0213] Specific platinum-based catalysts can be any known catalysts typically used in addition-hardening curing, such as the fine-powdered metal-platinum catalyst described in U.S. Patent No. 2,970,150, the chloroplatinic acid catalyst described in U.S. Patent No. 2,823,218, the platinum-hydrocarbon complex compounds described in U.S. Patent No. 3,159,601 and U.S. Patent No. 159,662, the chloroplatinic acid-olefin complex compounds described in U.S. Patent No. 3,516,946, and the platinum-vinylsiloxane complex compounds described in U.S. Patent No. 3,775,452 and U.S. Patent No. 3,814,780.

[0214] More specifically, examples include elemental platinum (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or platinum supported on a support such as alumina or silica. The copolymer composition of this embodiment may contain two or more platinum-based catalysts.

[0215] In the copolymer composition of this embodiment, the amount of platinum-based catalyst blended per 100 parts by mass of copolymer (S) is preferably 0.001 to 1 part by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.005 to 0.8 parts by mass.

[0216] [Organic peroxide (Z)] Examples of organic peroxides (Z) include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0217] The organic peroxide (Z) is preferably one whose decomposition products generated during crosslinking are low molecular weight compounds with sufficiently high vapor pressures. Using such an organic peroxide (Z) results in a crosslinked molded article that is less likely to retain odor. In this specification and in the claims, the amount of organic peroxide (Z) is calculated based on a purity of 100% by mass. Organic peroxides are usually sold at a purity of approximately 40% by mass for ease of handling. In the case of a product with a purity of 40% by mass, the amount of organic peroxide is obtained by multiplying the mass of the product by 0.4.

[0218] In the copolymer composition of this embodiment, the amount of organic peroxide (Z) blended per 100 parts by mass of copolymer (S) is 0.2 to 6 parts by mass, preferably 0.2 to 4.8 parts by mass, and more preferably 0.2 to 4 parts by mass.

[0219] In the copolymer composition of this embodiment, the total amount of the hydrosilyl group-containing compound (Y) and the organic peroxide (Z) per 100 parts by mass of copolymer (S) is preferably 0.01 to 0.15 equivalents, more preferably 0.01 to 0.1 equivalents, and even more preferably 0.02 to 0.1 equivalents.

[0220] In the copolymer composition of this embodiment, the equivalent ratio [Y / Z] of the amount of hydrosilyl group-containing compound (Y) to organic peroxide (Z) is preferably 23 / 77 to 99 / 1, and more preferably 47 / 53 to 99 / 1.

[0221] [Reaction inhibitor] The copolymer composition of this embodiment preferably contains a reaction inhibitor. The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation addition reaction to an alkene) between the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). The inclusion of a reaction inhibitor is preferable in that it stabilizes the processability of the composition during kneading and molding.

[0222] Specific examples of reaction inhibitors include, for example, benzotriazole; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octin-3,6-diol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 1-ethynylcyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; acrylonitrile; amide compounds such as N,N-diallylacetamide, N,N-diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalate diamide, N,N,N',N'-tetraallyl-m-phthalate diamide, and N,N,N',N'-tetraallyl-p-phthalate diamide; and others such as sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, and tetramethyltetravinylcyclotetrasiloxane. Among these compounds, 3,5-dimethyl-1-hexyn-3-ol is particularly preferred. The copolymer composition of this embodiment may contain two or more reaction inhibitors.

[0223] In the copolymer composition of this embodiment, the amount of reaction inhibitor blended per 100 parts by mass of copolymer (S) 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.

[0224] [Antioxidant] The copolymer composition of this embodiment may contain an antioxidant. A hindered phenol-based antioxidant is preferred as the antioxidant. The copolymer composition of this embodiment, by including a hindered phenol-based antioxidant, can further yield a crosslinked molded article with high water absorption and excellent compression set. The copolymer composition according to this embodiment may contain two or more antioxidants.

[0225] Examples of hindered phenol antioxidants include 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene ((Manufactured by ADEKA Corporation, product name: ADEKA Stab AO-330, melting point: 243~245℃), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione ((Co., Ltd.) (ADEKA Corporation, product name: Adeka Stab AO-20, melting point: 220~222℃), 4,4'-butylidenebis(6-tert-butyl-m-cresol) (ADEKA Corporation, product name: Adeka Stab AO-40, melting point: 210~214℃), N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine (BASF Japan Ltd., product name: Irganox) Examples include MD1024 (melting point: 224-229°C), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Ltd., trade name: Irganox1010, melting point: 110-130°C), dibutylhydroxytoluene, and 2,5-di-tert-butylhydroquinone (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name: Nocrac NS-7, melting point: 200°C or higher).

[0226] If the copolymer composition of this embodiment contains an antioxidant, the amount of antioxidant blended per 100 parts by mass of copolymer (S) 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.

[0227] [Anti-aging agent] The copolymer composition of this embodiment may contain an antioxidant. As an anti-aging agent, known anti-aging agents commonly used in rubber compositions can be used. Specifically, examples include sulfur-based anti-aging agents, phenol-based anti-aging agents, and amine-based anti-aging agents. Anti-aging agents may be used individually, but it is preferable to use two or more in combination to maintain heat aging resistance over long periods at high temperatures.

[0228] When the copolymer composition of this embodiment contains a sulfur-based antioxidant, it can be used in an amount of preferably 0.2 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and particularly preferably 0.2 to 6 parts by mass, per 100 parts by mass of copolymer (S). Using a sulfur-based antioxidant within the above range greatly improves heat aging resistance.

[0229] When the copolymer composition of this embodiment contains a phenolic antioxidant, it can be used in an amount of preferably 0.2 to 5 parts by mass, more preferably 0.5 to 4 parts by mass, and particularly preferably 0.5 to 3 parts by mass, per 100 parts by mass of copolymer (S). Using a phenolic antioxidant within the above range greatly improves heat aging resistance.

[0230] When the copolymer composition of this embodiment contains an amine-based antioxidant, it is preferably used in an amount of 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and particularly preferably 0.2 to 3 parts by mass, per 100 parts by mass of copolymer (S). Using an amine-based antioxidant within the above range greatly improves heat aging resistance.

[0231] [Reinforcement agent] The copolymer composition of this embodiment may contain a reinforcing agent to improve physical properties such as tensile stress at fracture and tensile elongation at fracture. The reinforcing agent is a known rubber reinforcing agent that is incorporated into the rubber composition, and specifically includes carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine talc powder, and differential silicic acid. The copolymer composition according to this embodiment may contain two or more reinforcing agents.

[0232] In particular, the inclusion of carbon black is preferable. Including carbon black improves the processability of the copolymer composition and allows for the acquisition of a copolymer composition with improved mechanical properties such as tensile strength, tear strength, and abrasion resistance.

[0233] As carbon black, known products such as Asahi #50HG, Asahi #55G, Asahi #60UG (all manufactured by Asahi Carbon Co., Ltd.), Seast SVH, Seast V, Seast G-SO (all manufactured by Tokai Carbon Co., Ltd.) can be used. These can be used individually or in combination. In addition, carbon black that has been surface-treated with a silane coupling agent can also be used.

[0234] When the copolymer composition of this embodiment contains carbon black, it is preferably used in the range of 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, and particularly preferably 10 to 100 parts by mass, per 100 parts by mass of copolymer (S). If the amount of carbon black is within the above range, a copolymer composition with excellent dynamic modulus (dynamic modulus / static modulus), processability, mechanical properties, etc. can be obtained.

[0235] [Softener] The copolymer composition of this embodiment may contain a softening agent. The softener is a known softener that is incorporated into the rubber composition. Specifically, these include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; 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 its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricants, tall oil, and sub(factis). Of these, petroleum-based softeners are preferred, and paraffin-based process oils are particularly preferred. The copolymer composition according to this embodiment may contain two or more softening agents.

[0236] When the copolymer composition of this embodiment contains a softening agent, it is preferably used in the range of 5 to 150 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 10 to 120 parts by mass, per 100 parts by mass of copolymer (S). If the amount of softening agent is within the above range, a copolymer composition with low tack and excellent processability, heat aging resistance, mechanical properties, etc. can be obtained.

[0237] [Desiccant] The copolymer composition of this embodiment may contain a desiccant. Examples of desiccants include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. Of these, calcium oxide is preferred. The amount of desiccant added is preferably 0.5 to 15 parts by weight, more preferably 1.0 to 12 parts by weight, and even more preferably 1.0 to 10 parts by weight, per 100 parts by weight of copolymer (S). The copolymer composition according to this embodiment may contain two or more desiccants.

[0238] [Crosslinking agent] The copolymer composition of this embodiment may contain a crosslinking aid. Examples of crosslinking aids include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds; and divinylbenzene. Such crosslinking aids are preferably used in an amount of 0.5 to 2 moles, more preferably about equimolars, per mole of organic peroxide used.

[0239] [Filler] The copolymer composition of this embodiment may contain fillers in order to reduce the compounding cost. Examples of fillers include talc and clay. These fillers may be used individually or in combination of two or more. Such fillers are preferably used in an amount of 1 to 500 parts by mass, more preferably 1 to 400 parts by mass, and even more preferably 1 to 300 parts by mass, per 100 parts by mass of copolymer (S). When the amount of filler is within the above range, the mechanical properties of the resulting molded article, such as tensile strength, tear strength, and abrasion resistance, can be improved.

[0240] [Processing aid] The copolymer composition of this embodiment may contain processing aids. As processing aids, a wide range of substances commonly used in rubber processing can be used. Specifically, these include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. These processing aids may be used individually or in combination of two or more.

[0241] The processing aid can be appropriately blended in an amount of preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of copolymer (S). When the amount of processing aid is within the above range, the processability such as kneading processability, extrusion processability, and injection moldability is excellent.

[0242] [Activating agent] The copolymer composition of this embodiment may contain an activator. Examples of activators include glycols such as polyethylene glycol and diethylene glycol; and amines such as di-n-butylamine and triethanolamine. These activators may be used individually or in combination of two or more. The activator can be appropriately blended in an amount of preferably 0.2 to 15 parts by mass, preferably 0.3 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass, per 100 parts by mass of copolymer (S).

[0243] [Foaming agent] The copolymer composition of this embodiment may contain a foaming agent. Examples of foaming agents include sodium bicarbonate-based foaming agents, ADCA (azodicarbonamide), DPT (N,N'-dinitropentamethylenetetramine), and OBSH (4,4'-oxybisbenzenesulfonyl hydrazide). Among these, sodium bicarbonate-based foaming agents are preferred because they enable the creation of foamed molded products with low specific gravity and high crosslink density.

[0244] If the copolymer composition of this embodiment contains a blowing agent, the amount of blowing agent blended per 100 parts by mass of copolymer (S) is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 10 parts by mass, even more preferably 0.1 to 10 parts by mass, and particularly preferably 0.2 to 10 parts by mass.

[0245] [Other compounding agents, etc.] In addition to the above components, the copolymer composition of this embodiment may appropriately contain rubber compounding agents known on their own, such as metal salts of α,β-unsaturated organic acids, crosslinking accelerators, plasticizers, tackifiers, etc., as long as the purpose of this embodiment is not impaired.

[0246] [Other resins] The copolymer composition of this embodiment may contain resins or rubbers other than copolymer (S) to the extent that it does not impair the effects of this embodiment. The amount of resins or rubbers other than copolymer (S) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and preferably not blended at all, per 100 parts by mass of copolymer (S).

[0247] Examples of resins other than copolymers (S) include general-purpose resins such as polyethylene, polypropylene, and polystyrene. Examples of rubber include silicone rubber, ethylene-propylene random copolymer rubber (EPR), natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, and chloroprene rubber.

[0248] [Manufacturing of copolymer compositions] To obtain the copolymer composition of this embodiment, a method similar to that used for general rubber compositions can be employed. Specifically, the method is as follows: The copolymer can be prepared by kneading, for example, a copolymer (S) and other components at a temperature of 80-170°C for 3-10 minutes using internal mixers such as Banbury mixers, kneaders, and intermixers, then adding a hydrosilyl group-containing compound (Y), a platinum-based catalyst, and optionally other compounding agents such as reaction inhibitors, reinforcing agents, and softeners, as well as other rubbers or resins, and then kneading at a roll temperature of 50-130°C for 5-30 minutes using rolls such as open rolls or a kneader, followed by dispensing. In this way, a copolymer composition in the form of ribbons or sheets is usually obtained.

[0249] To obtain the copolymer composition of this embodiment, it is also preferable to knead the copolymer (S), the hydrosilyl group-containing compound (Y), and other components as needed (first kneading), and then knead the resulting mixture with a platinum-based catalyst and reaction inhibitor for hydrosilyl crosslinking, an organic peroxide, and other components as needed (second kneading). The organic peroxide may be added during either the first or second mixing stage.

[0250] Specifically, a copolymer (S), a hydrosilyl group-containing compound (Y), and other components as needed are kneaded at 80-170°C for 1-10 minutes, preferably at 110-170°C for 3-8 minutes (first kneading). Then, a platinum-based catalyst and reaction inhibitor for hydrosilyl crosslinking, and other components as needed are added to the resulting mixture and kneaded at 10-100°C for 1-10 minutes, preferably at 20-80°C for 3-7 minutes (second kneading).

[0251] When adding reinforcing agents, softening agents, etc., they may be added during either the first or second mixing stage, but it is preferable to add them during the first mixing stage. When adding other rubber compounding agents, such as metal salts of α,β-unsaturated organic acids, hygroscopic agents, antioxidants, fillers, processing aids, surfactants, plasticizers, and tackifiers, it is preferable to add them during the first mixing stage, and it is preferable to add crosslinking aids, crosslinking accelerators, and foaming agents during the second mixing stage.

[0252] For the first mixing stage, any known mixing device capable of processing at high temperatures can be used. Specifically, examples include Banbury mixers, kneaders, and extruders. Mixing equipment used for the second mixing stage includes rollers, kneaders, and extruders, which allow for easy temperature control.

[0253] By kneading in two stages, a first kneading and a second kneading, the copolymer (S) and the hydrosilyl group-containing compound (Y) can be kneaded at a high temperature in the first kneading stage, allowing for the rapid removal of water, which acts as a crosslinking inhibitor in the hydrosilyl group-containing compound (Y). Therefore, a copolymer composition can be obtained without increasing the amount of hydrosilyl group-containing compound (Y), thus reducing manufacturing costs.

[0254] Furthermore, by dividing the mixing of each component into a first and second mixing stage, the mixing time can be shortened compared to mixing all components together. In addition, by adding a platinum-based catalyst and reaction inhibitor for hydrosilyl crosslinking, along with an organic peroxide, during the second mixing stage, the progress of crosslinking during the first mixing stage can be suppressed, allowing the temperature during the first mixing stage to be increased and enabling the removal of moisture in a shorter time.

[0255] [Effects and Effects] In this embodiment, the copolymer composition exhibits suppressed crosslinking reactions at relatively low temperatures (e.g., 50-130°C) during kneading and molding, thereby preventing scorching (burning or premature, unexpected crosslinking reactions) caused by heat during processing and storage. On the other hand, at crosslinking temperatures (e.g., 150-200°C), crosslinking can be achieved in a sufficiently short time. Therefore, the copolymer composition of this embodiment exhibits excellent storage stability and productivity.

[0256] <Crosslinked molded body> A crosslinked molded article according to one aspect of the present invention is a crosslinked molded article obtained by crosslinking the copolymer composition of the present invention. A crosslinked molded article can be obtained by pre-molding the copolymer composition of the present invention into a desired shape using various molding machines such as an extrusion machine, calender roll, press molding machine, injection molding machine, or transfer molding machine, or by introducing the molded article into a vulcanizing tank and heating it to crosslink it simultaneously with the molding. If the copolymer composition of the present invention contains a foaming agent, foaming will also proceed along with crosslinking, and a foamed crosslinked molded article (foamed molded article) will be obtained.

[0257] Any known heating method can be used without limitation, but it is particularly preferable to heat the material at a temperature of 150-200°C for 1-30 minutes using a heating bath with heating modes such as far-infrared heating furnaces, hot air, glass bead fluidized beds, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt chamber). For molding and crosslinking, molds may or may not be used. If molds are not used, the rubber composition is usually molded and crosslinked continuously.

[0258] It is also preferable to perform primary crosslinking of the copolymer composition of the present invention by press molding, remove it from the mold to obtain a primary molded body, and then perform secondary crosslinking of the obtained primary molded body in a heat transfer medium. Specifically, the copolymer composition of the present invention can be press-molded at 120-200°C for 1-20 minutes, preferably at 150-200°C for 10-18 minutes, to perform primary crosslinking and remove from the mold to obtain a primary molded body. The obtained primary molded body can then be secondary crosslinked in a heat transfer medium at 120-160°C for 10-24 hours, preferably at 140-160°C for 15-20 minutes. The heat transfer fluids used for secondary crosslinking include air, steam, paraffin-based process oil, and molten salt.

[0259] When primary crosslinking is performed by press molding, the crosslinked material does not become hot due to shear heating. Therefore, it is possible to suppress the generation of low-molecular-weight siloxanes and the degradation of the polymer. Furthermore, in press molding where crosslinking occurs in a sealed state, some of the generated low-molecular-weight siloxane remains inside the crosslinked material. However, by performing secondary crosslinking in a heat transfer medium, it is possible to volatilize the low-molecular-weight siloxane and obtain a crosslinked material with a low amount of low-molecular-weight siloxane.

[0260] The cross-linked molded articles of this embodiment can be used in a variety of applications. Specifically, they are suitably used in tire rubber, O-rings, industrial rolls, packings (e.g., condenser packings), gaskets, belts (e.g., heat-insulating belts, copier belts, conveyor belts), hoses such as automotive hoses (e.g., water hoses, brake reservoir hoses, radiator hoses, air hoses), 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 (ignition cables, cabtyre cables, high-tension cables), wire covering materials (high-voltage wire covering materials, low-voltage wire covering materials, marine wire covering materials), glass run channels, colored surface materials, paper feed rolls, roofing sheets, and the like.

[0261] [Effects and Effects] The crosslinked molded articles obtained from the copolymer composition of the present invention exhibit high tensile elongation at the breaking point and excellent rubber properties.

[0262] <Seventh aspect> A method for producing a copolymer composition according to a seventh aspect of the present invention is characterized by kneading a copolymer (S) and a hydrosilyl group-containing compound (Y) at 80 to 170°C for 1 to 10 minutes, preferably at a temperature of 110 to 170°C for 4 to 8 minutes (first kneading), then adding a platinum-based catalyst for hydrosilyl crosslinking to the resulting kneaded product, and kneading at 10 to 130°C for 1 to 30 minutes, preferably at 10 to 100°C for 1 to 10 minutes, more preferably at a temperature of 20 to 80°C for 3 to 7 minutes (second kneading). In the second kneading, a reaction inhibitor may be added and kneaded further. The manufacturing method of this embodiment can be applied to the production of copolymer compositions of the first to sixth embodiments. Furthermore, the crosslinked molded article according to the eighth aspect of the present invention is a molded article obtained by crosslinking a copolymer composition obtained by the manufacturing method of the seventh aspect.

[0263] [Copolymer (S)] The copolymer (S) used in the manufacturing method of this embodiment is the same as the copolymer (S) in the first embodiment. In other words, the copolymer (S) in this embodiment has constituent units derived from ethylene (A) as described in the first embodiment, constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from non-conjugated polyene (C), and satisfies the above requirements (i) and (ii). The preferred embodiment of the copolymer (S) in this embodiment is the same as in the first embodiment. The method for producing the copolymer composition according to this embodiment may use two or more copolymers (S).

[0264] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) used in the manufacturing method of this embodiment is the same as the hydrosilyl group-containing compound (Y) in the first embodiment. In other words, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural characteristics as those described in the first embodiment. The preferred embodiment of the hydrosilyl group-containing compound (Y) in this embodiment is the same as in the first embodiment. The method for producing the copolymer composition according to this embodiment may also use two or more hydrosilyl group-containing compounds (Y).

[0265] [Platinum catalyst] The platinum-based catalyst for hydrosilyl crosslinking used in the manufacturing method of this embodiment is the same as the platinum-based catalyst for hydrosilyl crosslinking in the first embodiment, and the same applies to the preferred embodiment. The manufacturing method according to this embodiment may use two or more platinum-based catalysts.

[0266] [Reaction inhibitor] The reaction inhibitor used in the manufacturing method of this embodiment is the same as the reaction inhibitor in the first embodiment, and the same applies to the preferred embodiment. The manufacturing method according to this embodiment may use two or more reaction inhibitors.

[0267] [Combined preparations, etc.] Antioxidants, anti-aging agents, reinforcing agents, softeners, hygroscopic agents, organic peroxides, crosslinking aids, fillers, processing aids, surfactants, and other compounding agents, as well as other resins, can be appropriately blended in the same manner as in the first embodiment.

[0268] [Composition] The amount of hydrosilyl group-containing compound (Y) used in the first kneading is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, even more preferably 0.1 to 20 parts by mass, even more preferably 0.1 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, even more preferably 1 to 10 parts by mass, especially preferably 2 to 10 parts by mass, and most preferably 3 to 10 parts by mass, per 100 parts by mass of copolymer (S).

[0269] The platinum-based catalyst used in the second kneading is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5.0 parts by mass, even more preferably 0.01 to 3.0 parts by mass, even more preferably 0.02 to 1.0 parts by mass, even more preferably 0.03 to 0.7 parts by mass, particularly preferably 0.05 to 0.6 parts by mass, and most preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of copolymer (S).

[0270] The reaction inhibitor used in the second kneading is more preferably 0.005 to 5.0 parts by mass, even more preferably 0.01 to 3.0 parts by mass, even more preferably 0.02 to 1.0 parts by mass, even more preferably 0.03 to 0.7 parts by mass, particularly preferably 0.05 to 0.6 parts by mass, and most preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of copolymer (S).

[0271] [Kneading] For the first mixing stage, any known mixing device capable of processing at high temperatures can be used. Specifically, examples include Banbury mixers, kneaders, and extruders. Mixing equipment used for the second mixing stage includes rollers, kneaders, and extruders, which allow for easy temperature control.

[0272] When adding reinforcing agents, softening agents, etc., they may be added during either the first or second mixing stage, but it is preferable to add them during the first mixing stage. Other rubber compounding agents, such as organic peroxides, metal salts of α,β-unsaturated organic acids, hygroscopic agents, antioxidants, crosslinking aids, crosslinking accelerators, fillers, processing aids, surfactants, plasticizers, tackifiers, and foaming agents, may be added during either the first or second mixing stage.

[0273] [Crosslinked molded product] The copolymer composition obtained by the manufacturing method of this embodiment can be pre-molded into a desired shape by various molding methods such as an extrusion molding machine, calender roll, press, injection molding machine, or transfer molding machine, or simultaneously with molding, by introducing the molded product into a vulcanizing tank and heating it to crosslink the copolymer composition, thereby obtaining a crosslinked molded product.

[0274] Any known heating method can be used without limitation, but it is particularly preferable to heat the material at a temperature of 150-200°C for 1-30 minutes using a heating bath with heating modes such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt bath). For molding and crosslinking, a mold may or may not be used. If a mold is not used, the copolymer composition is usually molded and crosslinked continuously.

[0275] The crosslinked molded articles obtained from the copolymer composition produced by the manufacturing method of this embodiment can be used in a variety of applications. Specifically, they are suitably used in tire rubber, O-rings, industrial rolls, packing (e.g., condenser packing), gaskets, belts (e.g., heat insulating belts, copier belts, conveyor belts), hoses such as automotive hoses (e.g., water hoses, brake reservoir hoses, radiator hoses, air hoses), 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 (ignition cables, cabtyre cables, high-tension cables), wire covering materials (high-voltage wire covering materials, low-voltage wire covering materials, marine wire covering materials), glass run channels, colored surface materials, paper feed rolls, roofing sheets, and the like.

[0276] [Effects and Effects] In this embodiment, the crosslinked molded article is kneaded at high temperature with the copolymer (S) and the hydrosilyl group-containing compound (Y) during the first kneading stage. This allows for the rapid removal of water, which acts as a crosslinking inhibitor in the hydrosilyl group-containing compound (Y). Therefore, a copolymer composition can be obtained without increasing the amount of hydrosilyl group-containing compound (Y), thereby reducing manufacturing costs.

[0277] In this embodiment, the kneading of each component is divided into a first kneading and a second kneading, which allows for a reduction in kneading time compared to when the first and second kneading are not separated. Furthermore, by adding a platinum-based catalyst and reaction inhibitor for hydrosilyl crosslinking during the second kneading, the progress of crosslinking during the first kneading is suppressed, allowing the temperature during the first kneading to be raised and enabling the removal of moisture in a shorter time.

[0278] The crosslinked molded article obtained by crosslinking the copolymer composition obtained by the manufacturing method of this embodiment exhibits low compression set. The reason for this is not entirely clear, but it is thought to be due to a high crosslink density and a uniform crosslink structure.

[0279] <Eighth aspect> A method for producing a copolymer composition according to the eighth aspect of the present invention is a method for producing a crosslinked molded article characterized by melt-kneading a copolymer (S), a hydrosilyl group-containing compound (Y), and a platinum-based catalyst, then press-molding at 120-200°C for 1-20 minutes, preferably at 150-200°C for 10-18 minutes to perform primary crosslinking and removing the molded article, and then secondary crosslinking the obtained primary molded article in a heat transfer medium at 120-160°C for 10-24 hours, preferably at 140-160°C for 15-20 minutes. A reaction inhibitor may be further added to the copolymer (S), hydrosilyl group-containing compound (Y), and platinum-based catalyst and melt-kneaded. The heat transfer fluids used for secondary crosslinking include air, steam, paraffin-based process oil, and molten salt. The manufacturing method of this embodiment can be applied to the production of crosslinked molded articles using copolymer compositions of the first to sixth embodiments.

[0280] [Copolymer (S)] The copolymer (S) used in the manufacturing method of this embodiment is the same as the copolymer (S) in the first embodiment. In other words, the copolymer (S) in this embodiment has constituent units derived from ethylene (A) as described in the first embodiment, constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, and constituent units derived from non-conjugated polyene (C), and satisfies the above requirements (i) and (ii). The preferred embodiment of the copolymer (S) in this embodiment is the same as in the first embodiment. The method for producing the copolymer composition according to this embodiment may use two or more copolymers (S).

[0281] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) used in the manufacturing method of this embodiment is the same as the hydrosilyl group-containing compound (Y) in the first embodiment. In other words, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural characteristics as those described in the first embodiment. The preferred embodiment of the hydrosilyl group-containing compound (Y) in this embodiment is the same as in the first embodiment. The method for producing the copolymer composition according to this embodiment may also use two or more hydrosilyl group-containing compounds (Y).

[0282] [Platinum catalyst] The platinum-based catalyst for hydrosilyl crosslinking used in the manufacturing method of this embodiment is the same as the platinum-based catalyst for hydrosilyl crosslinking in the first embodiment, and the same applies to the preferred embodiment. The manufacturing method according to this embodiment may use two or more platinum-based catalysts.

[0283] [Reaction inhibitor] The reaction inhibitor used in the manufacturing method of this embodiment is the same as the reaction inhibitor in the first embodiment, and the same applies to the preferred embodiment. The manufacturing method according to this embodiment may use two or more reaction inhibitors.

[0284] [Combined preparations, etc.] Antioxidants, anti-aging agents, reinforcing agents, softeners, hygroscopic agents, organic peroxides, crosslinking aids, fillers, processing aids, surfactants, and other compounding agents, as well as other resins, can be appropriately blended in the same manner as in the first embodiment.

[0285] [Composition] The hydrosilyl group-containing compound (Y) used in the method for producing the crosslinked molded article of this embodiment is preferably 0.1 to 30 parts by mass, and more preferably 3 to 10 parts by mass, per 100 parts by mass of copolymer (S). The platinum-based catalyst is preferably present in an amount of 0.001 to 10 parts by mass, and more preferably in an amount of 0.1 to 0.5 parts by mass, per 100 parts by mass of copolymer (S). The reaction inhibitor is preferably present in amounts of 0 to 2 parts by mass, and more preferably in amounts of 0 to 0.8 parts by mass, per 100 parts by mass of copolymer (S).

[0286] [Kneading] In the manufacturing method for the cross-linked molded article according to this embodiment, any known kneading apparatus capable of processing at high temperatures can be used for kneading. Specifically, examples include Banbury mixers, kneaders, and internal mixers such as intermixes.

[0287] [Crosslinked molded product] The cross-linked molded articles obtained by the manufacturing method of this embodiment can be used in a variety of applications. Specifically, they are suitably used in tire rubber, O-rings, industrial rolls, packings (e.g., condenser packings), gaskets, belts (e.g., heat insulating belts, copier belts, conveyor belts), hoses such as automotive hoses (e.g., water hoses, brake reservoir hoses, radiator hoses, air hoses), 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 (ignition cables, cabtyre cables, high-tension cables), wire covering materials (high-voltage wire covering materials, low-voltage wire covering materials, marine wire covering materials), glass run channels, colored surface materials, paper feed rolls, roofing sheets, and the like.

[0288] [Effects and Effects] In the manufacturing method of this embodiment, primary crosslinking is performed by press molding, so the crosslinked body does not become hot due to shear heating. Therefore, it is possible to suppress the generation of low molecular weight siloxanes and the degradation of the polymer. Furthermore, when primary crosslinking is performed by injection molding, the crosslinked material becomes extremely hot due to shear heating because it is injected into the mold at high speed from the nozzle, which accelerates the generation of low-molecular-weight siloxanes and the degradation of the polymer.

[0289] Furthermore, in primary crosslinking press molding, crosslinking is performed in a sealed state, so some of the generated low-molecular-weight siloxane remains inside the crosslinked material. However, in the manufacturing method of this embodiment, secondary crosslinking is performed in a heat transfer medium, which volatilizes the low-molecular-weight siloxane, making it possible to obtain a crosslinked material with a low amount of low-molecular-weight siloxane.

[0290] The crosslinked molded articles obtained by the manufacturing method of this embodiment exhibit low compression set. The reason for this is not entirely clear, but it is thought that the high crosslink density and uniform crosslink structure are contributing factors.

[0291] The copolymer composition of the present invention preferably has a duro-A hardness of 70 or less, more preferably 3 to 65, and even more preferably 5 to 60, as measured by the method described in the examples. The copolymer composition of the present invention preferably has a duro-C hardness of 50 or less, more preferably 10 to 40, and even more preferably 15 to 35, as measured by the method described in the examples. The copolymer composition of the present invention preferably has a tensile elongation at break EB (%) measured by the method described in the examples of 600% or less, more preferably 100-600%, and even more preferably 150-500%. The copolymer composition of the present invention preferably has a tensile breaking stress TB (MPa) of 15 MPa or less, more preferably 0.5 to 15 MPa, and even more preferably 0.7 to 13 MPa, as measured by the method described in the examples. The copolymer composition of the present invention preferably has an anti-counterfeiting product of 5000 or less, more preferably 100 to 5000, and even more preferably 200 to 4500, as calculated by the method described in the examples. The copolymer composition of the present invention preferably has an M25 of 1.0 MPa or less, more preferably 0.03 to 0.60 MPa, and even more preferably 0.05 to 0.55 MPa, as measured by the method described in the examples. The copolymer composition of the present invention preferably has an M50 of 1.0 MPa or less, more preferably 0.05 to 0.90 MPa, and even more preferably 0.08 to 0.85 MPa, as measured by the method described in the examples. The copolymer composition of the present invention preferably has an M100 of 3.0 MPa or less, more preferably 0.05 to 2.5 MPa, and even more preferably 0.1 to 2.0 MPa, as measured by the method described in the examples. The copolymer composition of the present invention preferably has an M200 of 5.5 MPa or less, more preferably 0.1 to 5.0 MPa, and even more preferably 0.2 to 4.5 MPa, as measured by the method described in the examples. The copolymer composition of the present invention preferably has an M300 of 9.0 MPa or less, more preferably 0.3 to 8.5 MPa, and even more preferably 0.5 to 8.0 MPa, as measured by the method described in the examples. The copolymer composition of the present invention, when heat-treated at 150°C for 22 hours under conditions of a compressibility of 25% as measured by the method described in the examples, preferably has a CS of 60% or less, more preferably 3 to 55%, and even more preferably 5 to 50%. The copolymer composition of the present invention, when heat-treated at 120°C for 72 hours under conditions of a compressibility of 25% as measured by the method described in the examples, preferably has a CS of 20% or less, more preferably 3 to 18%, and even more preferably 5 to 15%. The copolymer composition of the present invention preferably has a CS of 20% or less, more preferably 1 to 15%, and even more preferably 3 to 13%, when heat-treated at 100°C for 22 hours under conditions of 50% compressibility, as measured by the method described in the examples. The copolymer composition of the present invention, when heat-treated at 70°C for 22 hours under conditions of 50% compressibility as measured by the method described in the examples, preferably has a CS of 30% or less, more preferably 1 to 25%, and more preferably 3 to 20%. The copolymer composition of the present invention has a specific gravity (Mg (megagrams) / m³) as measured by the method described in the examples. 3 ) is 0.65 Mg / m³ 3 The following are preferred: 0.1 to 0.60 Mg / m³ 3 Preferably, 0.2 to 0.55 Mg / m³ 3 This is preferable. The copolymer composition of the present invention preferably has a water absorption rate of 10% or more, more preferably 15-70%, and even more preferably 20-50%, as measured by the method described in the examples. The copolymer composition of the present invention preferably has a low molecular weight component content (ppm) of 10 ppm or less, more preferably 5 ppm or less, and more preferably 3 ppm or less, as measured by the method described in the examples. The copolymer composition of the present invention has a crosslinking density of 0.1 × 10 as measured by the method described in the examples. 19 ~20×10 19 pieces / cc is preferred, and 0.3 × 10 19 ~15×10 19 pieces / cc is more preferable, 0.5 × 10 19 ~13×10 19 Pieces / cc is even more preferable. The copolymer composition of the present invention preferably has a B-type viscosity of 500 to 7000 Pa·s, more preferably 800 to 6500 Pa·s, and even more preferably 1000 to 6000 Pa·s, as measured by the method described in the examples. [Examples]

[0292] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0293] <Measurement method> The physical properties of the uncrosslinked copolymer compositions and molded articles obtained in each example were evaluated using the following measurement methods.

[0294] [Crosslinking behavior of copolymer compositions] Using the uncrosslinked copolymer compositions in each example, the following values ​​were determined from the crosslinking curves measured at the crosslinking temperatures and times shown in each table, in accordance with JIS K6300-2. An MDR2000 (Alpha Technologies) was used for the measurements.

[0295] "S' max (dNm): Maximum torque value S' max That is the case. "S' min (dNm): Minimum torque value S' min That is the case. "S' max -S' min (dNm): Maximum torque value S' max and minimum torque value S' min That is the difference. "tcx1" (min): Minimum torque value S' min From, "S' max -S'min The torque value equivalent to x1% of " and the minimum torque value S' min The time it takes to reach a torque value equivalent to the sum of the two. For example, "tc10" is the minimum torque value S'. min From, "S' max -S' min A torque value equivalent to 10% of " and the minimum torque value S' min This is the time it takes to reach a torque value equivalent to the sum of the two. "tsx2" (min): Minimum torque value S' min The time it takes for the torque value to increase by x2 (dNm) from a certain point. For example, "ts1" is the minimum torque value S'. min This is the time it takes for the torque value to increase by 1 (dNm). "MCR" (dNm / min): This is the maximum rate of change of torque in the bridge curve.

[0296] [Hardness test (Duro-A hardness)] In accordance with JIS K 6253-3, the hardness (Type A durometer, HA) of sheet-like molded products was measured using six 2mm thick sheet-like rubber molded products with smooth surfaces, stacked with the flat portions facing each other to a thickness of approximately 12mm. However, test pieces containing foreign matter, air bubbles, or scratches were not used. Furthermore, the dimensions of the measurement surface of the test piece were such that measurement could be taken with the tip of the indenter at a distance of 12mm or more from the edge of the test piece.

[0297] [Hardness test (Duro-C hardness)] In accordance with JIS K 7312, six 2mm thick sheet-like molded rubber products with smooth surfaces were used under the conditions of spindle No. 7, 1 rpm, and 25°C. The flat portions were stacked to a thickness of approximately 6mm. However, test pieces containing foreign matter, air bubbles, or scratches were not used. Furthermore, the dimensions of the measurement surface of the test piece were such that measurement could be taken with the tip of the indenter at a distance of 12mm or more from the edge of the test piece.

[0298] [Tensile test] For each example, a dumbbell-shaped test specimen of type 3, as described in JIS K 6251 (1993), was prepared by punching out molded bodies. Using this specimen, a tensile test was performed under the conditions of a measurement temperature of 25°C and a tensile speed of 500 mm / min, according to the method specified in Section 3 of JIS K 6251, and the modulus (MPa), tensile stress at fracture TB (MPa), and tensile elongation at fracture EB (%) were measured. The product of TB and EB was defined as the tension product. The number after the "M" indicating the modulus represents the growth rate; for example, "M25" means the modulus when the growth rate is 25% (25% modulus).

[0299] [Compression set (CS) of tubular molded bodies] A tubular molded body was cut 30 mm in the length direction, and the resulting test specimen was mounted in a compression set measurement mold. The test specimen was compressed so that its height was half of its height before load application (compression ratio 50%), and the mold was placed in a gear oven at the temperature shown in each table for the time shown in each table. Next, the test specimen was removed from the mold, allowed to cool for 30 minutes, and then its height was measured. The compression set (CS) (%) was calculated using the following formula. Compression set (CS) (%) = {(t0-t1) / (t0-t2)} × 100 t0: Height of the test specimen before testing. t1: Height of the test specimen after heat treatment and cooling for 30 minutes. t2: Height of the test specimen when it is attached to the measuring mold.

[0300] [Compression set (CS) of sheet-like molded articles] Five sheets of 2mm thick molded material were stacked and mounted in a compression set measurement mold. The specimens were compressed to 3 / 4 of their height before load application (compression ratio 25%), and the mold was placed in a gear oven at the temperature shown in each table for the time shown in each table. Next, the specimens were removed from the mold, allowed to cool for 30 minutes, and then the height of the specimens was measured. The compression set (CS) (%) was calculated using the following formula. Compression set (CS) (%) = {(t0-t1) / (t0-t2)} × 100 t0: Height of the test specimen before testing. t1: Height of the test specimen after heat treatment and cooling for 30 minutes. t2: Height of the test specimen when it is attached to the measuring mold.

[0301] [Specific gravity of foamed molded material] The specific gravity of the foamed molded body was measured using a 20 mm x 20 mm test specimen from a hot-air crosslinked tubular foamed molded body, in accordance with the water displacement method (JIS K 6268).

[0302] [Water absorption rate of foamed molded material] A 20mm x 20mm test specimen was punched out from a hot-air crosslinked tubular foam molded body, and the surface dirt was wiped off with alcohol. This test specimen was then subjected to a reduced pressure of -625mmHg at a depth of 50mm below the water surface and held there for 3 minutes. Subsequently, the pressure was returned to atmospheric pressure, and after 3 minutes, the weight of the water-absorbed test specimen was measured, and the water absorption rate was calculated using the following formula. (Water absorption rate)={(W2−W1) / W1} W1: Weight before immersion (g). W2: Weight after immersion (g).

[0303] [Low molecular weight component content] Samples taken from each molded product were accurately weighed at 1.0 g into 10 mL headspace vials, sealed, and then measured for low molecular weight components under the following headspace GC / MS conditions. Static headspace GC / MS Heating temperature / time: 190°C x 5 minutes, Quantification: Calculation by conversion using toluene Analytical instrument (manufactured by Agilent Technologies) Headspace sampler: G1888 (manufactured by Agilent Technologies) GC / MS:HP6890N / NP5973 Column: HP-3MS 0.25mm x 30mm, film thickness 0.25μm

[0304] [Crosslink density] The crosslinking density ν was calculated from the Flory-Rehner equation (I) below, which utilizes equilibrium swelling. In equation (I), V RThis was determined by extracting a cross-linked 2mm sheet with toluene at 37°C for 72 hours.

[0305]

number

[0306] [Crosslinking rate of copolymer composition] For each example, the uncrosslinked copolymer composition was used, and the following values ​​were determined from the crosslinking curve measured when heated to a predetermined crosslinking temperature in accordance with JIS K6300-2. An MDR2000 (Alpha Technologies) was used for the measurements.

[0307] "S' max (dNm): Maximum torque value S' max That is the case. "S' min (dNm): Minimum torque value S' min That is the case. "S' max -S' min (dNm): Maximum torque value S' max and minimum torque value S' min That is the difference. "125℃ (TS1) min": Under the condition of a temperature of 125℃, this is the time it takes for the torque value to increase by 1 (dNm) from the minimum torque value S'min, relative to the start of measurement. "180℃ (tc90) min": This is the time it takes to reach a torque value equivalent to 90% of "S'max-S'min" under the condition of a temperature of 180℃, with the starting point of measurement as the reference point.

[0308] [Odor] The uncrosslinked copolymer composition in each example was press-molded at 50°C for 10 minutes to obtain a 3 mm thick sheet-like molded body with a smooth surface. This was then crosslinked by heating it in a gear oven at 240°C for 6 minutes to obtain the crosslinked molded body for each example. The odor of each cross-linked molded product obtained was evaluated according to the following criteria. ○: No unpleasant odor. ×: Has an unpleasant odor.

[0309] [Surface stickiness] The uncrosslinked copolymer composition in each example was press-molded at 50°C for 10 minutes to obtain a 3 mm thick sheet-like molded body with a smooth surface. This was then crosslinked by heating it in a gear oven at 240°C for 6 minutes to obtain the crosslinked molded body for each example. The surface of each cross-linked molded product obtained was touched with a finger and evaluated according to the following criteria. ○: No stickiness when touched with hands. ×: It feels sticky when touched with hands.

[0310] [Scratch resistance] The uncrosslinked copolymer composition in each example was press-molded at 50°C for 10 minutes to obtain a 3 mm thick sheet-like molded body with a smooth surface. This was then crosslinked by heating it in a gear oven at 240°C for 6 minutes to obtain the crosslinked molded body for each example. The surface of each cross-linked molded product obtained was scratched with a brass rod having a flat, circular tip with a diameter of 3 mm immediately after being removed from the gear oven, and evaluated according to the following criteria. The evaluation was performed by a panel of three people, and the average was calculated.

[0311] 5: No scratches. 4: There are very slight scratches. 3: Slightly scratched. 2: Scratches present. 1: There are clear scratches.

[0312] [Hardness test (Duro-A hardness)] The uncrosslinked copolymer compositions from each example were press-molded at 180°C for 10 minutes to obtain 2 mm thick sheet-like molded bodies. Six crosslinked molded bodies from each example were stacked to form 12 mm thick test specimens, and their hardness (Duro-A) was measured according to JIS K 6253-3. The dimensions of the measurement surface of the test specimen were such that the indenter tip could be positioned at least 12 mm away from the edge of the specimen for measurement.

[0313] [Tensile test] The uncrosslinked copolymer compositions in each example were press-molded at 180°C for 10 minutes to obtain sheet-like molded bodies with a thickness of 2 mm. The crosslinked molded bodies obtained in each example were punched out to prepare Type 3 dumbbell test specimens as described in JIS K 6251 (1993). Tensile tests were performed using these specimens according to the method specified in Section 3 of JIS K 6251, under conditions of a measurement temperature of 23°C and a tensile speed of 500 mm / min, and the tensile stress at fracture TB (MPa) and tensile elongation at fracture EB (%) were measured.

[0314] [Compression set (CS) of sheet-like molded articles] In each example, the uncrosslinked copolymer composition was crosslinked by heating it at 180°C for 15 minutes using a press molding machine equipped with a cylindrical mold. A crosslinked body with a diameter of 29 mm and a height (thickness) of 12.5 mm was prepared as a test specimen in accordance with JIS K 6262. The specimen was compressed by 25% relative to its height before loading (12.5 mm), and then heat-treated for 72 hours in a gear oven at 120°C with a spacer. The specimen was then removed, left at room temperature for 30 minutes, and its height was measured. The compression set (%) was then calculated using the following formula. Compression set (%) = {(t0-t1) / (t0-t2)} × 100 t0: Height of the test specimen before testing. t1: Height after treating the test specimen under the above conditions and leaving it at room temperature for 30 minutes. t2: Height of the test specimen when it is attached to the measuring mold.

[0315] <Copolymer> The copolymers used in each example were produced using the methods described in the following production examples. Table 1 shows the numerical values ​​for requirements (i) to (v) of the copolymers obtained in each production example.

[0316] [Manufacturing Example 1: Manufacturing of copolymer (S-1)] Copolymer (S-1) was produced in the same manner as in Production Example 1 of Japanese Patent Publication No. 2018-131527.

[0317] [Manufacturing Example 2: Manufacturing of Copolymer (S-2)] In the method for producing ethylene-propylene-VNB copolymer described in Example 1 (paragraphs

[0386] to

[0391] ) of International Publication No. 2019 / 180802, copolymer (S-2) was produced by changing the hydrogen feed rate to 50 liters / hr.

[0318] [Manufacturing Example 3: Manufacturing of Copolymer (A-1)] A stainless steel polymerization reactor with a substantial internal volume of 100 liters and equipped with stirring blades (stirring speed = 250 rpm) was used to continuously perform ternary copolymerization of ethylene, propylene, and 5-vinyl-2-norbornene. From the side of the polymerization reactor, hexane was added to the liquid phase at a rate of 60 liters per hour, ethylene at 3.0 kg, propylene at 9.0 kg, and VNB at 550 g per hour. Additionally, 50 liters of hydrogen, 95 mmol of VOCl3, and 443 mmol of Al(Et)2Cl were used as catalysts. 1.5 Cl 1.5 It was continuously supplied at a rate of 127 millimoles.

[0319] As a result, copolymer (A-1), which is an ethylene-propylene-VNB random copolymer rubber, was obtained in a homogeneous solution state. Subsequently, a small amount of methanol was added to the polymerization solution continuously withdrawn from the bottom of the polymerizer to stop the polymerization reaction. The polymer was then separated from the solvent by steam stripping, and the copolymer (A-1) was produced by vacuum drying at 55°C for 48 hours.

[0320] [Table 1]

[0321] <Crosslinking agent> The crosslinking agents used in each example are as follows:

[0322] [Crosslinking agent (Y-1-1)] 536 g of methylhydrogenpolysiloxane, represented by the following formula (a-1-1), was charged into the reactor and heated to 40°C while stirring under a nitrogen flow. 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.

[0323] [ka]

[0324] 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 for 2 hours to remove the low-boiling components, and 673 g of the crosslinking agent (Y-1-1) was obtained.

[0325] The resulting crosslinking agent (Y-1-1) is 29 Si-NMR confirmed that the compound is represented by the following formula (a-1). The viscosity of the obtained crosslinking agent (Y-1-1) was measured at 25°C using an Ubbelohde-type viscosity tube in accordance with JIS-Z-8803, and the result was 26 mm 2 It was / s.

[0326] [ka]

[0327] [Crosslinking agent (Y-1-2)] 370 g of methylhydrogenpolysiloxane represented by the following formula (a-2-1) was charged into the reactor and heated to 80°C while stirring under a nitrogen flow. 0.45 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 280 g of α-methylstyrene was added dropwise while maintaining the reaction temperature at 80-120°C.

[0328] [ka]

[0329] After the dropwise addition was complete, the mixture was stirred at 145°C for 1 hour. Then, 0.5 g of the reaction solution was taken, and the reaction rate of the Si-H groups was confirmed to be approximately 50% 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 145°C for 1 hour to remove the low-boiling components, and 600 g of the crosslinking agent (Y-1-2) was obtained.

[0330] The resulting crosslinking agent (Y-1-2) is 29 Si-NMR confirmed that the compound is represented by the formula (a-2) below. The viscosity of the obtained crosslinking agent (Y-1-2) was measured at 25°C using an Ubbelohde-type viscosity tube in accordance with JIS-Z-8803, and the result was 72 mmHg. 2 It was / s.

[0331] [ka]

[0332] [Crosslinking agent (Y-2)] The compound is represented by the following formula (a-3).

[0333] [ka]

[0334] <Other ingredients> The other components used in each example are as follows:

[0335] Organic peroxide (Z-1): NOF Corporation, Perhexa 25B-40, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (purity 40% by mass), half-life at 1 minute, temperature 179.8°C Organic peroxide (Z-2): Manufactured by NOF Corporation, Perkmyl® D-40, dicumyl peroxide (purity 40% by mass), half-life temperature 175.2°C.

[0336] Catalyst 1: A complex of chloroplatinic acid and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. Catalyst 2: Toray Dow SRX212 Catalyst, complex salt of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane Reaction inhibitor 1: Ethyl-1-octin-3-ol Reaction inhibitor 2: 1-ethynyl-1-cyclohexanol, manufactured by Nisshin Chemical Industry Co., Ltd.

[0337] Process oil 1: Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd., paraffin-based process oil Process oil 2: Diana Process PS-430, manufactured by Idemitsu Kosan Co., Ltd., paraffin-based process oil Process oil 3: Diana Process PW-32, manufactured by Idemitsu Kosan Co., Ltd., paraffin-based process oil

[0338] Carbon Black 1: Manufactured by Asahi Carbon Co., Ltd., Asahi #60G Carbon Black 2: Manufactured by Asahi Carbon Co., Ltd., Asahi #50HG Carbon Black 3: Manufactured by Asahi Carbon Co., Ltd., Asahi #60UG, FEF Carbon Black Heavy calcium carbonate: Manufactured by Shiraishi Calcium Co., Ltd., Whiteon SB Calcium carbonate: Manufactured by Shiraishi Kogyo Co., Ltd., Shiratsuya CC Precipitation-type silica: Manufactured by Tosoh Silica Co., Ltd., NipSeal VN3 Calcium oxide 1: Manufactured by Inoue Lime Industry Co., Ltd., Vesta PP Calcium oxide 2: Manufactured by Inoue Lime Industry Co., Ltd., Vesta BS

[0339] Antioxidant: Irganox 1010, manufactured by BASF Japan Ltd. Titanium dioxide: Manufactured by Ishihara Sangyo Co., Ltd., R-820 Blue composite oxide pigment: Manufactured by Dainichi Seika Co., Ltd., dipyroxide blue Red pigment: PIGMOTEX RED 102 ET, manufactured by Sanyo Shikkei Co., Ltd. Yellow pigment: PIGMOTEX YELLOW 83 ET, manufactured by Sanyo Pigment Co., Ltd. Calcined kaolin: Manufactured by BASF Japan Ltd., TRANSLINK-37

[0340] Baking soda 1: Manufactured by Eiwa Kasei Kogyo Co., Ltd., FE-507R Baking soda 2: Manufactured by Eiwa Kasei Kogyo Co., Ltd., FE-507 Table 2 shows the values ​​obtained from the cumulative distribution curves of the number of irregularities and the number of equivalent circle diameters for baking soda 1 and baking soda 2.

[0341] [Table 2]

[0342] <Examples 1-1 to 1-7> [Preparation of uncrosslinked compositions] In the first stage, the raw materials shown in Tables 3 and 4 (Raw Material 1) 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 stage formulation. The Mooney viscosity of the first stage formulation is shown in Tables 3 and 4.

[0343] Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C, 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 Tables 3 and 4 were added to this, and the mixture was kneaded for 10 minutes to obtain the uncrosslinked compositions for each example.

[0344] [Preparation of sheet-like cross-linked molded articles] Each example of the uncrosslinked composition was pressed in a mold at 180°C for 10 minutes using a press molding machine to obtain a sheet-like crosslinked molded body with a thickness of 2 mm.

[0345] [evaluation] For each example of the uncrosslinked composition, the crosslinking behavior was measured when the crosslinking temperature was 90°C and the crosslinking time was 90 minutes (low-temperature crosslinking), and when the crosslinking temperature was 180°C and the crosslinking time was 30 minutes (high-temperature crosslinking). The results are shown in Tables 3 and 4. As shown in Tables 3 and 4, it was found that the resulting molded articles exhibited excellent physical properties and processability in Examples 1-1 to 1-7.

[0346] As shown in Tables 3 and 4, Examples 1-1 to 1-7, using crosslinking agents (Y-1-1) or (Y-1-2), had higher ts values ​​in low-temperature crosslinking than Example 1-8, which used crosslinking agent (Y-2), indicating superior scorch resistance. Furthermore, the tc90 in high-temperature crosslinking for Examples 1-1 to 1-7 was 10 minutes or less, indicating that a sufficient crosslinking rate could be obtained during crosslinking. Furthermore, Examples 1-1 to 1-7 showed a greater anti-countermeasures volume and superior elongation characteristics compared to Example 1-8.

[0347] [Table 3]

[0348] [Table 4]

[0349] <Examples 2-1 to 2-4> [Preparation of uncrosslinked compositions] In the first stage, the raw materials shown in Raw Materials 1 of Table 5 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 stage formulation.

[0350] Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C, 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 5 were added to this, and the mixture was kneaded for 10 minutes to obtain the uncrosslinked compositions for each example.

[0351] [Preparation of tubular foam molded bodies] The uncrosslinked compositions of each example were extruded into tubes using a 50mmφ extruder [manufactured by Mitsuba Seisakusho Co., Ltd.; L / D=16] equipped with a tubular die (inner diameter 10mm, wall thickness 1mm) under the conditions of die temperature 80°C, cylinder temperature 60°C, and screw temperature 50°C. These molded bodies were crosslinked in a HAV (hot air vulcanization) at a 230°C atmosphere for 5 minutes to obtain tubular foamed molded bodies.

[0352] [evaluation] For each example of the uncrosslinked composition, the crosslinking behavior was measured at a crosslinking temperature of 180°C and a crosslinking time of 15 minutes. The results are shown in Table 5. As shown in Table 5, all examples showed excellent physical properties and processability of the resulting molded articles. As shown in Table 5, in all examples, tc90 was 10 minutes or less, indicating that a sufficient bridging speed could be obtained during bridging.

[0353] Furthermore, Table 5 shows the results of evaluating the sponge properties of the sheet-like foamed molded bodies in each example. In particular, as shown in Table 5, examples 2-1 and 2-2, which used baking soda 1, had a lower specific gravity than examples 2-3 and 2-4, which used baking soda 2. Furthermore, their water absorption rate was higher than that of example 2-3. Furthermore, Table 5 shows the results of evaluating the compression set (CS) of the tubular foam molded bodies in each example. In particular, as shown in Table 5, Examples 2-1 and 2-2 had smaller compression set (CS) than Example 2-3.

[0354] [Table 5]

[0355] <Examples 3-1 to 3-3> [Preparation of the uncrosslinked composition of Example 3-1] In the first stage, the raw materials shown in Raw Materials 1 of Table 5 were kneaded at 120°C for 5 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 stage mixture.

[0356] Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a surface temperature of 50°C for both the front and rear rolls, a rotation speed of 16 rpm for the front roll, and a rotation speed of 18 rpm for the rear roll). The raw materials shown in Raw Materials 2 of Table 6 were added to this, and after kneading for 5 minutes, the mixture was separated into ribbons to obtain an uncrosslinked composition.

[0357] [Preparation of uncrosslinked compositions for Examples 3-2 and 3-3] In the first stage, the raw materials shown in Raw Materials 1 of Table 5 were kneaded at 120°C for 5 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 stage mixture.

[0358] Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C and a rear roll surface temperature of 50°C, a front roll rotation speed of 16 rpm and a rear roll rotation speed of 18 rpm). The raw materials shown in Raw Materials 2 of Table 6 were added to this, and after kneading for 10 minutes, it was separated into ribbons to obtain the uncrosslinked compositions of each example.

[0359] [Preparation of sheet-like cross-linked molded articles] Each example of the uncrosslinked composition was pressed in a mold at 180°C for 10 minutes using a press molding machine to obtain a sheet-like crosslinked molded body with a thickness of 2 mm.

[0360] [evaluation] For each example of the uncrosslinked composition, the crosslinking behavior (high-temperature crosslinking) was measured when the crosslinking temperature was 180°C and the crosslinking time was 15 minutes. The results are shown in Table 6. As shown in Table 6, all examples showed excellent physical properties and processability of the resulting molded articles. As shown in Table 6, in all examples, tc90 was 10 minutes or less, indicating that a sufficient bridging speed could be obtained during bridging. Furthermore, Table 6 shows the results of evaluating the physical properties of the crosslinked molded articles for each example. In particular, as shown in Table 6, Example 3-1, in which the crosslinking agent was kneaded in the first stage, had a smaller compression set (CS) than Examples 3-2 and 3-3, in which the crosslinking agent was kneaded in the second stage.

[0361] [Table 6]

[0362] <Examples 4-1 to 4-4> [Preparation of uncrosslinked compositions] In the first stage, the raw materials shown in Raw Materials 1 of Table 7 were kneaded at 120°C for 5 minutes using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.) to obtain the first stage formulation.

[0363] Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C, 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 7 were added to this, and the mixture was kneaded for 5 minutes to obtain the uncrosslinked compositions for each example.

[0364] [Preparation of the crosslinked molded product in Example 4-1] An uncrosslinked composition was pressed in a mold at 180°C for 15 minutes using a press molding machine to obtain a 2 mm thick sheet-like primary crosslinked body. Next, the primary crosslinked body was subjected to secondary crosslinking at 150°C for 16 hours in a high-temperature constant-temperature oven (product name: horizontal high-temperature oven PHH-202, manufactured by ESPEC Corporation) to obtain the crosslinked molded body of Example 4-1.

[0365] [Preparation of the crosslinked molded product in Example 4-2] The primary crosslinked material obtained in Example 4-1 was used as the crosslinked molded product in Example 4-2.

[0366] [Preparation of the crosslinked molded product in Example 4-3] The primary crosslinked material obtained in Example 4-1 was subjected to secondary crosslinking at 180°C for 2 hours in a high-temperature constant-temperature oven (product name: horizontal high-temperature oven PHH-202, manufactured by ESPEC Corporation) to obtain the crosslinked molded product of Example 4-3.

[0367] [Preparation of the cross-linked molded product in Example 4-4] The primary crosslinked body obtained in Example 4-1 was subjected to secondary crosslinking at 200°C for 0.5 hours in a high-temperature constant-temperature oven (product name: horizontal high-temperature oven PHH-202, manufactured by ESPEC Corporation) to obtain the crosslinked molded body of Example 4-4.

[0368] [evaluation] The compression set (CS) and low molecular weight component content of the cross-linked molded articles were measured for each example. The results are shown in Table 7. As shown in Table 7, all examples showed excellent physical properties and processability of the resulting molded articles. In particular, as shown in Table 7, the crosslinked molded article of Example 4-1, obtained by performing secondary crosslinking in a heat transfer medium maintained at a relatively low temperature of 150°C for 16 hours, exhibited low compression set and contained extremely small amounts of low molecular weight components.

[0369] [Table 7]

[0370] <Examples 5-1 to 5-6> [Preparation of uncrosslinked compositions] As the first step, the raw materials shown in Raw Materials 1 of Tables 8 and 9 were kneaded for 10 minutes using 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). Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C, 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 Tables 8 and 9 were added to this, and the mixture was kneaded for 10 minutes to obtain the uncrosslinked compositions for each example. The Mooney viscosity of the uncrosslinked compositions for each example is shown in Tables 8 and 9.

[0371] [Preparation of sheet-like cross-linked molded articles] Each example of the uncrosslinked composition was pressed in a mold at 170°C for 10 minutes using a press molding machine to obtain a sheet-like crosslinked molded body with a thickness of 2 mm.

[0372] [evaluation] For each example of the uncrosslinked composition, the crosslinking behavior was measured at a crosslinking temperature of 170°C and a crosslinking time of 10 minutes. The results are shown in Tables 8 and 9. As shown in Tables 8 and 9, in all examples, tc90 was 10 minutes or less, indicating that a sufficient bridging speed could be obtained during bridging.

[0373] Furthermore, the results of evaluating the physical properties of the cross-linked molded articles in each example are shown in Tables 8 and 9. As shown in Tables 8 and 9, it was found that all of the examples yielded molded articles with excellent physical properties and processability. In particular, as shown in Tables 8 and 9, Examples 5-1 to 5-5, in which the Mooney viscosity of the uncrosslinked composition was in the range of 0.1 to 8, had lower compression set (CS) compared to Example 5-6, in which the Mooney viscosity of the uncrosslinked composition was high. Note that the compression set (CS) was evaluated for sheet-like crosslinked molded articles.

[0374] [Table 8]

[0375] [Table 9]

[0376] <Examples 6-1 to 6-7> [Preparation of uncrosslinked compositions] As the first step, the raw materials shown in Raw Materials 1 of Table 10 were kneaded at room temperature for 10 minutes using a defoaming conditioning mixer, Awatori Neri Taro (manufactured by Shinky Co., Ltd., AR-250, rotation / revolution propellerless mixing type). Next, in the second step, the mixture obtained in the first step was wound onto a three-roll mill (AIMEX Co., Ltd., BR-230BV, roll dimensions φ86.5 × 230 mmL), and the raw materials shown in Raw Materials 2 of Table 10 were added to it. The mixture was kneaded at room temperature for 10 minutes to obtain the uncrosslinked compositions for each example. The B-type viscosity of the uncrosslinked compositions for each example is shown in Table 10.

[0377] [Preparation of sheet-like cross-linked molded articles] Each example of the uncrosslinked composition was pressed in a mold at 170°C for 10 minutes using a press molding machine to obtain a sheet-like crosslinked molded body with a thickness of 2 mm.

[0378] [evaluation] For each example of the uncrosslinked composition, the crosslinking behavior was measured at various crosslinking temperatures and crosslinking times shown in Tables 11 and 12. The results are shown in Tables 11 and 12. As shown in Tables 11 and 12, it was found that the resulting molded articles exhibited excellent physical properties and processability in Examples 6-1 to 6-6. As shown in Tables 11 and 12, it was found that the crosslinking reaction did not proceed at 90°C, but proceeded at 120°C or higher. The compression set (CS) was evaluated for sheet-like crosslinked molded articles.

[0379] Furthermore, Table 13 shows the results of evaluating the physical properties of the cross-linked molded articles for each example. As shown in Table 13, it was found that the resulting molded articles in Examples 6-1 to 6-6 exhibited excellent physical properties and processability. As shown in Table 13, Examples 6-1 to 6-6, which used copolymer (S-2), were found to have lower hardness and higher EB compared to Example 6-7, which used copolymer (A-1).

[0380] [Table 10]

[0381] [Table 11]

[0382] [Table 12]

[0383] [Table 13]

[0384] <Examples 1-4> The copolymer compositions for each example were prepared as follows. As the first step, the raw materials shown in Raw Materials 1 of Table 14 were kneaded using a BB-4 type mixer (manufactured by Kobe Steel, Ltd.). The kneading conditions were a rotor speed of 50 rpm and a floating weight pressure of 3 kg / cm². 2 The mixture was kneaded for 5 minutes, and the first stage of the formulation was obtained at a discharge temperature of 150°C.

[0385] Next, in the second step, the mixture obtained in the first step was wound onto an 8-inch roll (manufactured by Nippon Roll Co., Ltd., with a front roll surface temperature of 50°C, a rear roll surface temperature of 50°C, a front roll rotation speed of 18 rpm, and a rear roll rotation speed of 15 rpm). The raw materials shown in Raw Materials 2 of Table 14 were added to this, and the mixture was kneaded for 5 minutes to obtain an uncrosslinked copolymer composition.

[0386] [evaluation] The odor of each copolymer composition was evaluated. Furthermore, the crosslinking rate and the physical properties of the crosslinked molded articles were measured and evaluated. The results are shown in Table 14. As shown in Table 14, all examples demonstrated excellent physical properties and processability of the resulting molded articles. As shown in Table 14, Examples 1-4, which used the hydrosilyl group-containing compound (Y-1-1), did not show excessively large "180°C (tc90) minutes" values, and "125°C (TS1) minutes" was approximately 20 minutes or more, demonstrating sufficient scorch resistance while maintaining an appropriate crosslinking rate.

[0387] Furthermore, Examples 1-4, which used the hydrosilyl group-containing compound (Y-1-1), showed sufficient EB values, similar to Example 9, which also used the hydrosilyl group-containing compound (Y-1-1) but did not contain organic peroxides. Furthermore, Examples 1-4 and 9, which used organic peroxide (Z-1), did not have any odor problems.

[0388] [Table 14] [Industrial applicability]

[0389] According to the present invention, it is possible to provide an ethylene-α-olefin-non-conjugated polyene copolymer composition that is excellent in terms of the physical properties and processability of the resulting molded article, a foamed molded article obtained from this copolymer composition and a method for producing the same, and a crosslinked molded article and a method for producing the same.

Claims

1. Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S), A copolymer composition comprising 0.1 to 100 parts by mass of the hydrosilyl group-containing compound (Y), 0.001 to 10 parts by mass of the platinum-based catalyst, and 1 to 30 parts by mass of a sodium bicarbonate-based blowing agent, per 100 parts by mass of the copolymer (S); 【Chemistry 1】 【Chemistry 2】 In equation (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, and multiple R １ and R ２ Each is independently a monovalent alkyl group, and Ra is -CH in the alkylene group between the aryl group and the silicon atom. ２ -CH(CH ３ An aralkyl group containing at least one branched unit represented by ), where the two Rs are each independently R １ , R ２ , hydrogen atom, and R ａ The group is selected from the group consisting of the following, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

2. The copolymer composition according to claim 1, further comprising 0 to 2 parts by mass of a reaction inhibitor per 100 parts by mass of the copolymer (S).

3. Furthermore, the copolymer composition according to claim 1, comprising 0.07 to 10 parts by mass of a hindered phenol antioxidant per 100 parts by mass of the copolymer (S).

4. A foamed molded article comprising a foam obtained by crosslinking and foaming a copolymer composition, The copolymer composition is Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is a foamed molded article in which the mass percentage concentration of constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S); 【Transformation 3】 【Chemistry 4】 In formula (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, the multiple R1 and R2 are each independently monovalent alkyl groups, Ra is an aralkyl group containing at least one branched unit represented by -CH2-CH(CH3)- in the alkylene group between the aryl group and the silicon atom, the two R are each independently selected from the group consisting of R1, R2, a hydrogen atom, and Ra, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

5. A method for producing a foamed molded article, comprising melt-extruding a copolymer composition and crosslinking it, The copolymer composition is Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The manufacturing method wherein requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S); 【Transformation 5】 【Transformation 6】 In formula (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, the multiple R1 and R2 are each independently monovalent alkyl groups, Ra is an aralkyl group containing at least one branched unit represented by -CH2-CH(CH3)- in the alkylene group between the aryl group and the silicon atom, the two R are each independently selected from the group consisting of R1, R2, a hydrogen atom, and Ra, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

6. Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) to (v). The intrinsic viscosity [η] is 2.0 to 4.0 dL / g. Furthermore, per 100 parts by mass of the copolymer (S), the mixture contains 0.1 to 200 parts by mass of carbon black, 0.1 to 200 parts by mass of paraffinic process oil, and, if necessary, a reaction inhibitor. The Mooney viscosity "ML(1+4)100℃" of a composition obtained by mixing the components excluding the hydrosilyl group-containing compound (Y), the platinum-based catalyst, and the reaction inhibitor, as determined by the method described in JIS K 6300-1:2013, is between 8 and 200. The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S), The above requirement (iii) can be obtained by the following formula (1) (n Ｃ ) is between 4.5 and 40, (n Ｃ )) = (Mw) × {(mass percent concentration of (C) / 100} / (molecular weight of (C))... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa·sec) and the complex viscosity η at frequency ω = 100 rad / s ＊ （ω＝１００） The ratio P(η) to (Pa·sec) ＊ （ω＝０．１） / η ＊ （ω＝１００） The following formula (2) satisfies the following conditions: P / ([η] ２．９ ) ≤ (C) mass percentage concentration × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. １０００Ｃ A copolymer composition in which the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3); LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3). 【Transformation 7】 【Transformation 8】 In formula (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, the multiple R1 and R2 are each independently monovalent alkyl groups, Ra is an aralkyl group containing at least one branched unit represented by -CH2-CH(CH3)- in the alkylene group between the aryl group and the silicon atom, the two R are each independently selected from the group consisting of R1, R2, a hydrogen atom, and Ra, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

7. A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in claim 6.

8. Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) to (v). The intrinsic viscosity [η] is 0.5 dL / g or more and less than 2.0 dL / g. Furthermore, the copolymer (S) contains 10 to 100 parts by mass of paraffinic process oil per 100 parts by mass. The Mooney viscosity "ML(1+4)100℃" obtained by the method described in JIS K 6300-1:2013 is between 0.1 and 8. The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S), The above requirement (iii) can be obtained by the following formula (1) (n Ｃ ) is between 4.5 and 40, (n Ｃ ) = (Mw) × {Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa·sec) and the complex viscosity η at frequency ω = 100 rad / s ＊ （ω＝１００） The ratio P(η) to (Pa·sec) ＊ （ω＝０．１） / η ＊ （ω＝１００） The following formula (2) satisfies the following conditions: P / ([η] ２．９ ) ≤ (C) mass percentage concentration × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. １０００Ｃ A copolymer composition in which the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3); LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3). 【Chemistry 9】 【Chemistry 10】 In formula (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, the multiple R1 and R2 are each independently monovalent alkyl groups, Ra is an aralkyl group containing at least one branched unit represented by -CH2-CH(CH3)- in the alkylene group between the aryl group and the silicon atom, the two R are each independently selected from the group consisting of R1, R2, a hydrogen atom, and Ra, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

9. A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in claim 8.

10. Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) to (v). The intrinsic viscosity [η] is 0.5 dL / g or more and less than 2.0 dL / g. Furthermore, the copolymer (S) contains 0.1 to 200 parts by mass of carbon black and 100 to 400 parts by mass of paraffinic process oil per 100 parts by mass. The Brookfield rotational viscosity at 25°C, as determined by the method described in JIS K 7117:1999, is 6000 Pa·s or less. The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S), The above requirement (iii) can be obtained by the following formula (1) (n Ｃ ) is between 4.5 and 40, (n Ｃ ) = (Mw) × {Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa·sec) and the complex viscosity η at frequency ω = 100 rad / s ＊ （ω＝１００） The ratio P(η) to (Pa·sec) ＊ （ω＝０．１） / η ＊ （ω＝１００） The following formula (2) satisfies the following conditions: P / ([η] ２．９ ) ≤ (C) mass percentage concentration × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. １０００Ｃ A copolymer composition in which the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3); LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3). 【Chemistry 11】 【Chemistry 12】 In formula (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, the multiple R1 and R2 are each independently monovalent alkyl groups, Ra is an aralkyl group containing at least one branched unit represented by -CH2-CH(CH3)- in the alkylene group between the aryl group and the silicon atom, the two R are each independently selected from the group consisting of R1, R2, a hydrogen atom, and Ra, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

11. A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in claim 10.

12. Copolymer (S); Hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule. Furthermore, a reaction inhibitor, Contains organic peroxide (Z), The copolymer (S) satisfies the following requirements (i) to (v): The organic peroxide (Z) is contained in an amount of 0.2 to 6 parts by mass per 100 parts by mass of the copolymer (S). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S), The above requirement (iii) can be obtained by the following formula (1) (n Ｃ ) is between 4.5 and 40, (n Ｃ ) = (Mw) × {Mass percentage concentration of (C) / 100} / Molecular weight of (C) ... (1) However, in formula (1), (Mw) is the weight-average molecular weight of the copolymer (S), the mass percentage concentration of (C) is the content (mass%) of the constituent units derived from the non-conjugated polyene (C) relative to the total mass of the constituent units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The above requirement (iv) is the complex viscosity η at frequency ω = 0.1 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa·sec) and the complex viscosity η at frequency ω = 100 rad / s ＊ （ω＝１００） The ratio P(η) to (Pa·sec) ＊ （ω＝０．１） / η ＊ （ω＝１００） The following formula (2) satisfies the following conditions: P / ([η] ２．９ ) ≤ (C) mass percentage concentration × 6 ... Equation (2) The above requirement (v) is the number of long chain branches per 1000 carbon atoms (LCB) obtained using 3D-GPC. １０００Ｃ A copolymer composition in which the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3); LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3). 【Chemistry 13】 【Chemistry 14】 In formula (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, the multiple R1 and R2 are each independently monovalent alkyl groups, Ra is an aralkyl group containing at least one branched unit represented by -CH2-CH(CH3)- in the alkylene group between the aryl group and the silicon atom, the two R are each independently selected from the group consisting of R1, R2, a hydrogen atom, and Ra, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

13. The copolymer composition according to claim 12, comprising 0.01 to 10 parts by mass of the hydrosilyl group-containing compound (Y), 0.001 to 1 part by mass of the platinum-based catalyst, and 0.001 to 5 parts by mass of the reaction inhibitor, per 100 parts by mass of the copolymer (S).

14. A crosslinked molded article characterized by being obtained by crosslinking the copolymer composition described in claim 12 or 13.

15. The copolymer (S) and the hydrosilyl group-containing compound (Y) are kneaded at 80 to 170°C for 1 to 10 minutes to obtain the first-stage formulation; and A method for producing a copolymer composition according to any one of claims 1 to 4, 6, 8, 10, 12, and 13, comprising adding a platinum-based catalyst to the first-stage formulation and kneading it at 10 to 130°C for 1 to 30 minutes to obtain a second-stage formulation, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The manufacturing method wherein requirement (ii) is that the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S); 【Chemistry 15】 【Chemistry 16】 In equation (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, and multiple R １ and R ２ Each is independently a monovalent alkyl group, and Ra is -CH in the alkylene group between the aryl group and the silicon atom. ２ -CH(CH ３ An aralkyl group containing at least one branched unit represented by ), where the two Rs are each independently R １ , R ２ , hydrogen atom, and R ａ The group is selected from the group consisting of the following, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

16. A method for producing the copolymer composition according to claim 15, wherein 0.1 to 100 parts by mass of the hydrosilyl group-containing compound (Y) and 0.001 to 10 parts by mass of the platinum-based catalyst are used per 100 parts by mass of the copolymer (S).

17. A crosslinked molded article obtained by crosslinking a copolymer composition obtained by the manufacturing method described in claim 15.

18. A kneaded product comprising the copolymer composition according to any one of claims 1 to 4, 6, 8, 10, 12, and 13 is obtained by melt-kneading the copolymer (S), the hydrosilyl group-containing compound (Y), and the platinum-based catalyst; A primary molded body is obtained by press-molding the aforementioned kneaded material at 120 to 200°C for 1 to 20 minutes to perform primary crosslinking; and A method for producing a crosslinked molded article, comprising heating the primary molded article in a heat transfer medium at 120 to 160°C for 10 to 24 hours to perform secondary crosslinking, The copolymer (S) comprises a constituent unit derived from ethylene (A), a constituent unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a constituent unit derived from a non-conjugated polyene (C) containing a total of two or more substructures selected from the following formulas (I) and (II) in the molecule, and satisfies the following requirements (i) and (ii). The hydrosilyl group-containing compound (Y) is represented by the following formula (a) and is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in the molecule. The requirement (i) is that the ratio [A] / [B], which is the ratio of the number of moles [A] of constituent units derived from ethylene (A) to the number of moles [B] of constituent units derived from α-olefin (B) having 3 to 20 carbon atoms, is 40 / 60 to 99.9 / 0.

1. The above requirement (ii) is a manufacturing method in which the mass percentage concentration of the constituent units derived from the non-conjugated polyene (C) is 0.07 to 5.0% by mass relative to the total constituent units of the copolymer (S); 【Chemistry 17】 [Chemistry 18] In equation (a), n and p are each independently 0 or a positive number, m is a number in the range of 1 to 20, the sum of n, m and p is between 5 and 50, and multiple R １ and R ２ Each is independently a monovalent alkyl group, and Ra is -CH in the alkylene group between the aryl group and the silicon atom. ２ -CH(CH ３ An aralkyl group containing at least one branched unit represented by ), where the two Rs are each independently R １ , R ２ , hydrogen atom, and R ａ The group is selected from the group consisting of the following, and these constituent units may be arranged in a block-like manner or randomly, provided that 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.

19. A method for producing a crosslinked molded article according to claim 18, wherein 0.1 to 100 parts by mass of the hydrosilyl group-containing compound (Y) and 0.001 to 10 parts by mass of the platinum-based catalyst are used per 100 parts by mass of the copolymer (S).

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