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

Abstract

To provide a copolymer composition containing an ethylene / α - olefin / non-conjugated polyene copolymer which is excellent in physical properties, processability and the like of a molded article to be obtained, a method for producing the same, a foamed molded article obtained from the copolymer composition and a method for producing the same, and a crosslinked molded article and a method for producing the same.SOLUTION: A copolymer composition containing a copolymer (S) having a structural unit derived from ethylene (A), a structural unit derived from an α - olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a specific non-conjugated polyene (C) and satisfying requirements (i) and (ii), a hydrosilyl group-containing compound (Y) that is an organohydrogenpolysiloxane having at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in a molecule, and a platinum-based catalyst for hydrosilyl crosslinking.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin-non-conjugated polyene copolymer composition and a method for producing the same, a foamed molded article obtained from the 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 on January 12, 2022, and Japanese Patent Application No. 2022-142879 filed on September 8, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0002] Copolymer compositions obtained by hydrosilyl crosslinking of ethylene-α-olefin-non-conjugated polyene random copolymers (Patent Document 1) have excellent mechanical strength, heat aging resistance, compression set, and bloom resistance compared to sulfur vulcanization and peroxide crosslinking, and are capable of continuous crosslinking. These properties make them promising for use in sealing parts such as packings and gaskets.

[0003] Patent Document 1 proposes a copolymer composition that has a long scorch time so that crosslinking does not occur during kneading at a relatively low temperature of 50 to 130°C during kneading and molding, but can be crosslinked in a short time at a crosslinking temperature of 150 to 200°C. Patent Document 2 proposes crosslinking using a hydrosilyl-containing compound in combination with an organic peroxide, which is relatively inexpensive and easily available. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-131527 [Patent Document 1] Japanese Patent Application Publication No. 2019-156950 Summary of the Invention [Problem to be solved by the invention]

[0005] However, Patent Documents 1 and 2 do not fully consider the hydrosilyl group-containing compound used for crosslinking. In view of the above circumstances, an object of the present invention is 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, an expanded molded article obtained from the 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] In order to achieve the above object, the present invention has the following aspects. [1] Copolymer (S); A hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) has a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing, in the molecule, two or more partial structures in total, at least one of which is selected from the following formula (I) and the following formula (II), and satisfies the following requirements (i) and (ii): the hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule: the requirement (i) is that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin (B) having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; a copolymer composition in which the requirement (ii) is satisfied, the mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass% based on the total mass of the structural units constituting the copolymer (S); [ka] [ka] In formula (a), n and p are each independently 0 or a positive number, m is a number ranging from 1 to 20, the sum of n, m, and p is 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 ,R 2 , a hydrogen atom, and R a These structural units may be arranged in blocks or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms. [2] It further contains a sodium bicarbonate-based foaming agent that satisfies the following requirement (b): The requirement (b) is that the cumulative 10% unevenness in the cumulative distribution curve based on the number of unevenness is 0.9 or less, and the cumulative 90% equivalent circle diameter in the cumulative distribution curve based on the number of equivalent circle diameters is 43 μm or more, wherein the irregularity is a ratio of the envelope perimeter to the perimeter measured by dynamic image analysis using methyl ethyl ketone as a dispersion solvent, and the equivalent circle diameter is a 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 a dispersion solvent. [3] The copolymer composition according to [2], comprising, relative to 100 parts by mass of the copolymer (S), 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. [4] The copolymer composition according to [2] or [3], further comprising a reaction inhibitor in an amount of 0 to 2 parts by mass 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-based antioxidant per 100 parts by mass of the copolymer (S). [6] A foamed molded article comprising a foam obtained by crosslinking and foaming the copolymer composition according to any one of [2] to [5]. [7] A method for producing a foamed molded article, comprising melt-extruding and crosslinking the copolymer composition according to any one of [2] to [5]. [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: further containing 0.1 to 200 parts by mass of carbon black, 0.1 to 200 parts by mass of paraffinic process oil, and a reaction inhibitor as required, relative to 100 parts by mass of the copolymer (S); a composition obtained by mixing the hydrosilyl group-containing compound (Y), the platinum catalyst, and components other than the reaction inhibitor has a Mooney viscosity "ML(1+4)100°C" determined by the method described in JIS K 6300-1:2013 of 8 to 200; The requirement (iii) is calculated 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) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2) The requirement (v) is determined by the number of long chain branches (LCB) per 1,000 carbon atoms obtained using 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3): LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3). [9] A crosslinked molded article obtained by crosslinking the copolymer composition according to [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: further comprising 10 to 100 parts by mass of paraffinic process oil relative to 100 parts by mass of the copolymer (S); The Mooney viscosity "ML(1+4)100°C" determined by the method described in JIS K 6300-1:2013 is 0.1 to 8, The requirement (iii) is calculated 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) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2) The requirement (v) is determined by the number of long chain branches (LCB) per 1,000 carbon atoms obtained using 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3): LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3).

[11] A crosslinked molded article obtained by crosslinking the copolymer composition according to

[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: further containing 0.1 to 200 parts by mass of carbon black and 100 to 400 parts by mass of paraffinic process oil relative to 100 parts by mass of the copolymer (S), The Brookfield rotational viscosity at 25°C determined by the method described in JIS K 7117:1999 is 6000 Pa s or less, The requirement (iii) is calculated 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) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2) The requirement (v) is determined by the number of long chain branches (LCB) per 1,000 carbon atoms obtained using 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3): LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3).

[13] A crosslinked molded article obtained by crosslinking the copolymer composition according to

[12] .

[14] In addition, a reaction inhibitor and and an 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 requirement (iii) is calculated 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) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2) The requirement (v) is determined by the number of long chain branches (LCB) per 1,000 carbon atoms obtained using 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy 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 catalyst, and 0.001 to 5 parts by mass of the reaction inhibitor, relative to 100 parts by mass of the copolymer (S).

[16] A crosslinked molded article obtained by crosslinking the copolymer composition according to

[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 a first-stage blend; and

[0023] 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 blend and kneading the mixture at 10 to 130°C for 1 to 30 minutes to obtain a second-stage blend, The copolymer (S) has a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing, in the molecule, two or more partial structures in total, at least one of which is selected from the following formula (I) and the following formula (II), and satisfies the following requirements (i) and (ii): the hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule: the requirement (i) is that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin (B) having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; a production method in which the requirement (ii) is satisfied, wherein the mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass% based on the total mass of the structural units constituting the copolymer (S); [ka] [ka] In formula (a), n and p are each independently 0 or a positive number, m is a number ranging from 1 to 20, the sum of n, m, and p is 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 ,R 2 , a hydrogen atom, and R aThese structural units may be arranged in blocks or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

[18] The method for producing a copolymer composition according to

[17] , 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 catalyst are used relative to 100 parts by mass of the copolymer (S).

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

[17] or

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

[20] The method for producing a copolymer composition according to

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

[21] A crosslinked molded article obtained by crosslinking the copolymer composition obtained by the production method according to any one of

[17] to

[20] .

[22] The copolymer (S), the hydrosilyl group-containing compound (Y), and the platinum-based catalyst are melt-kneaded to obtain a kneaded product comprising the copolymer composition according to any one of [1] to [5], [8],

[10] ,

[12] ,

[14] , and

[15] ; The kneaded mixture is press-molded at 120 to 200°C for 1 to 20 minutes to perform primary crosslinking, thereby obtaining a primary molded body; and A method for producing a crosslinked molded body, comprising: heating the primary molded body in a heat medium at 120 to 160°C for 10 to 24 hours to perform secondary crosslinking; The copolymer (S) has a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing, in the molecule, two or more partial structures in total, at least one of which is selected from the following formula (I) and the following formula (II), and satisfies the following requirements (i) and (ii): the hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule: the requirement (i) is that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin (B) having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; a production method in which the requirement (ii) is satisfied, wherein the mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass% based on the total mass of the structural units constituting the copolymer (S); [ka] [ka] In formula (a), n and p are each independently 0 or a positive number, m is a number ranging from 1 to 20, the sum of n, m, and p is 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 ,R 2 , a hydrogen atom, and R a These structural units may be arranged in blocks or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

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

[22] , 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 catalyst are used relative to 100 parts by mass of the copolymer (S).

[24] The 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 the mixture.

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

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

[26] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[25] , wherein the content of the copolymer (S) is preferably 10 to 50 mass%, more preferably 15 to 45 mass%, and even more preferably 20 to 40 mass%, based on the total mass of the copolymer composition.

[27] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[26] , wherein the content of the structural units derived from ethylene (A) is preferably 50 to 80 mass%, more preferably 60 to 75 mass%, and even more preferably 65 to 72 mass%, relative to the total mass of the copolymer (S).

[28] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[27] , wherein the content of the structural units derived from the α-olefin (B) having 3 to 20 carbon atoms is preferably 20 to 50 mass%, more preferably 25 to 40 mass%, and even more preferably 28 to 35 mass%, relative to the total mass of the copolymer (S).

[29] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[28] , wherein the content of the structural units derived from the non-conjugated polyene (C) is preferably 0.1 to 8.0 mass%, more preferably 0.5 to 5.0 mass%, further preferably 1.0 to 3.0 mass%, and particularly preferably 1.2 to 2.0 mass%, relative to the total mass of the copolymer (S).

[30] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[29] , wherein 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.

[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.

[31] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[30] .

[32] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[31] , wherein the non-conjugated polyene (C) preferably contains at least one selected from the group consisting of 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene, more preferably contains VNB, and further preferably is VNB.

[33] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[32] , wherein the weight-average molecular weight of the copolymer (S) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, further preferably 50,000 to 400,000, and particularly preferably 60,000 to 200,000.

[34] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[33] , wherein the content of the hydrosilyl group-containing compound (Y) is preferably 0.3 to 5.0 mass%, more preferably 0.5 to 3.0 mass%, and even more preferably 0.7 to 2.5 mass%, relative to the total mass of the copolymer composition.

[35] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[34] , wherein the content of the aralkyl group is preferably 5 to 20 mass%, more preferably 8 to 18 mass%, and even more preferably 10 to 15 mass%, based on the total mass of the hydrosilyl group-containing compound (Y).

[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 still more preferably -CH2-CH(CH3)-C6H5. The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[35] .

[37] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[36] , wherein the content of the alkyl group is preferably 15 to 40 mass%, more preferably 20 to 38 mass%, and even more preferably 25 to 35 mass%, relative to the total mass of the hydrosilyl group-containing compound (Y).

[38] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[37] , wherein 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, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[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, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[38] .

[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, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[39] .

[41] In formula (a), p is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0. The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[40] .

[42] In formula (a), two R each independently represent preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0041] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[41] .

[43] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[42] , wherein the content of the platinum-based catalyst is preferably 0.01 to 1.0 mass%, more preferably 0.02 to 0.5 mass%, and even more preferably 0.03 to 0.1 mass%, relative to the total mass of the copolymer composition.

[44] The platinum catalyst is preferably at least one selected from the group consisting of platinum alone (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, and carrier-supported platinum catalysts, and more preferably at least one selected from the group consisting of a complex of chloroplatinic acid and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, and a complex of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane. The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[43] .

[45] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[44] , wherein the copolymer composition further contains a sodium bicarbonate-based blowing agent.

[46] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[45] , wherein the content of the sodium bicarbonate-based blowing agent is preferably 0.1 to 2.0 mass%, more preferably 0.3 to 1.5 mass%, and even more preferably 0.7 to 1.0 mass%, relative to the total mass of the copolymer composition.

[47] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[46] , wherein the copolymer composition further contains a reaction inhibitor.

[48] ​​The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[47] , wherein the content of the reaction inhibitor is preferably 0.005 to 0.3 mass%, more preferably 0.008 to 0.2 mass%, and even more preferably 0.01 to 0.15 mass%, relative to the total mass of the copolymer composition.

[49] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[48] , wherein the copolymer composition further contains a hindered phenol-based antioxidant.

[50] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[49] , wherein the content of the hindered phenol-based antioxidant is preferably 0.1 to 3.0 mass %, more preferably 0.3 to 2.0 mass %, and even more preferably 0.5 to 1.0 mass %, relative to the total mass of the copolymer composition.

[51] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[50] , wherein the copolymer composition further contains carbon black.

[52] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[51] , wherein the content of the carbon black is preferably 1 to 50 mass %, more preferably 3 to 45 mass %, and even more preferably 5 to 40 mass %, based on the total mass of the copolymer composition.

[53] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[52] , wherein the copolymer composition further contains a paraffinic process oil.

[54] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[53] , wherein the content of the paraffinic process oil is preferably 1 to 90 mass %, more preferably 3 to 50 mass %, and even more preferably 5 to 35 mass %, based on the total mass of the copolymer composition.

[55] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[54] , wherein the copolymer composition further contains an organic peroxide.

[56] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[55] , wherein the content of the organic peroxide is preferably 0.1 to 5.0 mass%, more preferably 0.3 to 4.0 mass%, and even more preferably 0.5 to 3.0 mass%, relative to the total mass of the copolymer composition.

[57] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[56] , wherein the copolymer composition further contains a reinforcing agent.

[58] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[57] , wherein the content of the reinforcing agent is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total mass of the copolymer composition.

[59] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[58] , wherein the copolymer composition further contains a moisture absorbent.

[60] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[59] , wherein the content of the moisture absorbent is preferably 0.5 to 3.0 mass %, more preferably 0.8 to 2.5 mass %, and even more preferably 1.0 to 2.0 mass %, relative to the total mass of the copolymer composition.

[61] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[60] , wherein the content of the solvent in the copolymer composition is preferably 0 to 5 mass %, more preferably 0 to 1 mass %, and even more preferably substantially 0 mass %, based on the total mass of the copolymer composition.

[62] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[61] , wherein the ratio [A] / [B] is preferably from 50 / 50 to 90 / 10, more preferably from 55 / 45 to 85 / 15, even more preferably from 55 / 45 to 78 / 22, and particularly preferably from 63 / 37 to 76 / 24.

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

[17] to

[20] and

[26] to

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

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

[17] to

[20] and

[26] to

[63] , wherein obtaining the second-stage blend is preferably carried out 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 under conditions of 30°C or higher but lower 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.

[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 kneaded product is obtained preferably at a temperature of 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.

[68] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[67] , wherein 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.

[69] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[68] , wherein in the copolymer composition, the number of silicon-bonded hydrogen atoms per 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.

[70] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the crosslinked molded product, or the method for producing a crosslinked molded product according to any one of [1] to

[69] , wherein the number of aralkyl groups in one molecule of the hydrosilyl group-containing compound (Y) in the copolymer composition is preferably 2 to 10, more preferably 3 to 8, and even more preferably 4 or 5.

[71] The copolymer composition, the method for producing a copolymer composition, the foamed molded product, the method for producing a foamed molded product, the cross-linked molded product, or the method for producing a cross-linked molded product according to any one of [1] to

[70] , wherein the copolymer (S) preferably has at least one, and more preferably has two or more, partial structures selected from the formula (I) and the formula (II) in the molecule. [Effects of the Invention]

[0007] According to the present invention, there are provided a copolymer composition containing an ethylene-α-olefin-non-conjugated polyene copolymer which is excellent in terms of the physical properties and processability of the resulting molded article, a method for producing the same, an expanded molded article obtained from the copolymer composition, a method for producing the same, and a crosslinked molded article, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0010] The total mass percent concentration of the structural units derived from ethylene (A), the structural units derived from the α-olefin (B) having 3 to 20 carbon atoms, and the structural units derived from the non-conjugated polyene (C) relative to all structural units constituting the copolymer (S) is preferably 100 mass%.

[0011] The copolymer (S) in this embodiment satisfies the following requirements (i) and (ii). (i) The ratio [A] / [B] of the number of moles [A] of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin (B) having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1. (ii) The mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass % based on the total mass of all structural units constituting the copolymer (S).

[0012] Examples of the α-olefin (B) having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as "α-olefin (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. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferred, with propylene being particularly preferred. Such α-olefins are preferred because they are relatively inexpensive as raw materials, the resulting copolymer (S) exhibits excellent mechanical properties, and a molded article having rubber elasticity can be obtained. These α-olefins may be used alone or in combination of two or more.

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

[0014] [ka]

[0015] Examples of the non-conjugated polyene (C) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene. Among these, it is preferable that the non-conjugated polyene (C) contains VNB, and it is more preferable that the non-conjugated polyene (C) is VNB, because it is easily available, exhibits good hydrosilyl crosslinking, and tends to improve the heat resistance of the polymer composition. The non-conjugated polyene (C) may be used alone or in combination of two or more.

[0016] The copolymer (S) in this embodiment may further contain a structural unit (CX) derived from a non-conjugated polyene (CX) containing only one partial structure selected from the group consisting of the general formulas (I) and (II) in the molecule, within a range that 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, 5-(2-ethyl-3-butenyl)-2-norbornene,

[0033] Examples of such methyl-5-hexenyl-2-norbornene 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] Among these, ENB is preferred because it is readily available, the crosslinking rate during hydrosilyl crosslinking is easily controlled, and good mechanical properties are easily obtained. The non-conjugated polyene (CX) may be used alone or in combination of two or more. When the copolymer (S) in this embodiment contains a structural unit derived from a non-conjugated polyene (CX), the mass percent concentration thereof is preferably 0 to 20 mass%, more preferably 0 to 8 mass%, and even more preferably 0.01 to 8 mass%, based on all structural units constituting the copolymer (S).

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

[0019] The ratio [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. When the copolymer (S) satisfies the requirement (i), the foam obtained by hydrosilyl crosslinking the copolymer (S) exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility, which is preferable. The ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles of structural units derived from α-olefin (B) in the copolymer (S) is 13 It can be determined by C-NMR.

[0020] Requirement (ii) specifies that the mass percent concentration of the structural units derived from the non-conjugated polyene (C) in the copolymer (S) is 0.07 to 10 mass % relative to all structural units constituting the copolymer (S). The mass percent concentration of the structural 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 the structural units derived from ethylene (A), the structural units derived from α-olefin (B), and the structural units derived from non-conjugated polyene (C) in the copolymer (S) does not exceed 100% by mass, based on the total mass of the copolymer (S).

[0021] The copolymer (S) is preferred because it satisfies requirement (ii), and therefore the foam obtained from the copolymer composition according to this embodiment has sufficient hardness and excellent mechanical properties. Furthermore, when the copolymer (S) is hydrosilyl crosslinked, it is preferred because it exhibits a fast crosslinking rate, allowing for efficient production of the foam. The mass percent concentration of the constitutional units derived from the non-conjugated polyene (C) in the copolymer (S) is 13 The content of the structural units derived from ethylene (A) and the content of the structural units derived from the α-olefin having 3 to 20 carbon atoms (B) in the copolymer (S) can be determined by the following method: 13 It can be determined by C-NMR.

[0022] In addition to the above requirements (i) and (ii), the copolymer (S) in this embodiment preferably further satisfies the following requirements (iii) to (v). Hereinafter, the copolymer (S) satisfying all of the requirements (i) to (v) may be referred to as the copolymer (S1). (iii) (n C ) is between 4.5 and 40. (n C ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative 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). (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 the complex viscosity η at frequency ω=100rad / 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2) (v) The number of long chain branches (LCB) per 1000 carbon atoms obtained using 3D-GPC 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3). LCB 1000C ≦1-0.07×Ln(Mw)...Equation (3)

[0023] Requirement (iii) is calculated by the following formula (1) (nC ) range is specified as 4.5 to 40. (n C ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative 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). Here, (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 ) is the number of constitutional units derived from the non-conjugated polyene (C) per weight average molecular weight (Mw) of the copolymer (S). (n C When the ratio (R) is equal to or greater than the lower limit, a sufficient crosslinking rate can be easily obtained during hydrosilyl crosslinking. When the ratio (R) is equal to or less than the upper limit, excessive crosslinking is unlikely to occur, and the resulting foam exhibits superior mechanical properties. When the requirement (iii) is satisfied, the copolymer (S) has a low content of long chain branches, and the crosslinking rate of hydroxy crosslinking is fast, and the obtained foam has an excellent balance of physical properties such as mechanical properties, and is less likely to undergo post-crosslinking, and is particularly excellent in heat aging resistance, which is preferable.

[0025] When the copolymer (S) contains the structural unit (CX), the (n C+cx ) 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 percent concentration of (C) / 100} / molecular weight of (C) + {mass percent concentration of (CX) / 100} / molecular weight of (CX)] (1') (n C+cx ) is the total number of constitutional units derived from the non-conjugated polyene (C) and the number of constitutional 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 of the copolymer (S) at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 °C) using a rheometer. * (ω=0.1) (Pa·sec) and the complex viscosity η at frequency ω=100rad / 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) (the content of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S): % by mass) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2)

[0027] The rheometer used was a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific), and measurements were carried out at 190° C., strain 1.0%, and varying frequency. The intrinsic viscosity [η] is a value measured in decalin at 135°C.

[0028] The copolymer (S) more preferably satisfies the following formula (2'). P / ([η] 2.9 ) ≦ (C) mass percent concentration × 5.7 Equation (2') ratio P(η * (ω=0.1) / η * (ω=100) ) represents the frequency dependence of viscosity, and is the left side of equation (2) and equation (2') P / ([η] 2.9) tends to show high values ​​when there are many long chain branches, although it is affected by factors such as short chain branches and molecular weight.

[0029] Generally, in an ethylene-α-olefin-non-conjugated polyene copolymer, the more structural units derived from the non-conjugated polyene the copolymer contains, the more long-chain branches it tends to contain. However, it is considered that the copolymer (S) in this embodiment has fewer long-chain branches than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, and therefore can satisfy the above formula (2).

[0030] Requirement (v) is the number of long chain branches (LCB) per 1,000 carbon atoms of the copolymer (S) obtained by 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3). LCB 1000C ≦1-0.07×Ln(Mw) Equation (3)

[0031] The upper limit of the content of long chain branches per unit carbon number of the copolymer (S) is determined by the above formula (3). That is, requirement (v) means that the proportion of long chain branches in the copolymer (S) is low. By satisfying the requirement (v), the copolymer (S) has excellent curing properties when subjected to hydrosilyl crosslinking, and the foam obtained using the copolymer has excellent heat aging resistance. The copolymer (S) more preferably satisfies the following formula (3'). LCB 1000C ≦1-0.071×Ln(Mw)...Equation (3')

[0032] Mw and (LCB 1000C ) is a value determined by structural analysis using 3D-GPC. Specifically, the absolute molecular weight distribution was determined using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was simultaneously determined 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 (Polymer Laboratories)

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

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

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

[0037]

number

[0038]

number

[0039] Furthermore, using g'w, the number of branch points per molecular chain, BrNo, and the number of long chain branches per 1000 carbon atoms, LCB, are calculated. 1000C The branching degree λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer formula (v-5). 1000C Equations (v-6) and (v-7) were used to calculate λ. g is the long-chain branching parameter calculated from the radius of gyration Rg, and the following simple correlation is established between g' calculated from the intrinsic viscosity. Various values ​​have been proposed for ε in the equation depending on the shape of the molecule. Here, calculations were performed assuming ε = 1 (i.e., g' = g).

[0040]

number

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

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

[0043] In this embodiment, the method for producing the copolymer (S) is not particularly limited, but it is preferably one obtained by copolymerizing monomers in the presence of a metallocene compound, and more preferably one obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound. Specifically, it can be produced by the method described in WO 2015 / 122495, for example.

[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-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule. The copolymer composition of this embodiment may contain two or more types of hydrosilyl group-containing compounds (Y).

[0045] [ka]

[0046] In formula (a), n and p are 0 or a positive number, m is a number ranging from 1 to 20, and the sum of n, m, and p is 5 to 50. 1 , R 2 are each independently a monovalent alkyl group, and may be the same or different. a is an aralkyl group and R is R 1 ,R 2 , hydrogen atom, R a However, when n=1, at least one of R is a hydrogen atom, and when n=0, both R are hydrogen atoms.

[0047] Such a hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane with a linear structure that has a relatively low degree of siloxane polymerization and has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule.

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

[0049] In formula (a), m is the number of diorganosiloxy units having silicon-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 in the side chain that have silicon-bonded hydrogen atoms and may be 0 or 1. When n=1, at least one of R is a hydrogen atom, and when n=0, both R are hydrogen atoms, resulting in a structure that has at least two silicon-bonded hydrogen atoms in the molecule.

[0051] Even if n is a number other than 0 or 1, one or both of the R at both molecular chain terminals may be a silicon-bonded hydrogen atom. Furthermore, n is preferably a number other than 0 or 1, and more preferably a number satisfying n≧m. More specifically, n may be a number in the range of 3 to 10, and is particularly preferably 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 a number within the range obtained by dividing the values ​​of n and m from the total degree of polymerization of diorganosiloxane units, which is represented by the sum of n, m, and p, as described below. For example, p may be a number within the range of 0 to 12, 0 to 10, 0 to 5, or 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 values ​​of n, m, and p is 5-50, preferably 5-20, or may be 5-15. In the hydrosilyl group-containing compound (Y) which is the crosslinking agent of the present invention, m is particularly preferably a number in the range of 3 to 6, n is a number in the range of 3 to 9, and p is a number in the range of 0 to 2.

[0054] In formula (a), R is R 1 ,R 2 , hydrogen atom, Ra However, when n=0 or 1, both or one of R is a hydrogen atom. R in the formula 1 ,R 2 are monovalent alkyl groups, which may be the same or different, and in which some of the carbon-carbon-bonded hydrogen atoms may be substituted with halogen atoms. Such alkyl groups may be alkyl groups having 1 to 20 carbon atoms, and industrially may be methyl groups.

[0055] In formula (a), R a is an aralkyl group, and may be an aralkyl group having 7 to 20 carbon atoms, preferably an aralkyl group having 7 to 15 carbon atoms. Examples of such aralkyl groups include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. In particular, an aralkyl group containing at least one branch unit represented by -CH(CH3)- in the alkylene group between the aryl group such as a phenyl group and the silicon atom is preferred. In the present invention, particularly preferred is an aralkyl group containing at least one branch unit represented by -CH(CH3)- in the alkylene group between the aryl group such as a phenyl group and the silicon atom. a is an aralkyl group represented by -CH2-CH(CH3)-C6H5.

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

[0057] [Platinum-based catalyst] Platinum catalysts for hydrosilyl crosslinking are widely used in the hydrosilylation crosslinking reaction, which involves the addition of silicon-bonded hydrogen atoms to carbon-carbon double bonds. Platinum catalysts for hydrosilyl crosslinking are addition reaction catalysts, and any catalyst can be used without particular limitations as long as it promotes the addition reaction (hydrosilylation reaction of alkenes) between the alkenyl groups in the copolymer (S) and the hydrosilyl groups in the hydrosilyl group-containing compound (Y).

[0058] Specific platinum catalysts may be known ones that are normally used in addition curing, such as the fine powder platinum metal catalyst described in U.S. Pat. No. 2,970,150, the chloroplatinic acid catalyst described in U.S. Pat. No. 2,823,218, the complex compounds of platinum and hydrocarbons described in U.S. Pat. Nos. 3,159,601 and 159,662, the complex compounds of chloroplatinic acid and olefins described in U.S. Pat. No. 3,516,946, and the complex compounds of platinum and vinylsiloxanes described in U.S. Pat. Nos. 3,775,452 and 3,814,780.

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

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

[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 alkene) between the alkenyl group of the copolymer (S) and the hydrosilyl group of the hydrosilyl group-containing compound (Y). The addition of a reaction inhibitor is preferred in terms of stabilizing the processability of the composition during kneading and molding.

[0062] Specific examples of the reaction inhibitor include benzotriazole; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1-ethynylcyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; acrylonitrile; N,N-diallylacetamide; N,N-diallylacetamide; arylbenzamide, N,N,N',N'-tetraallyl-o-phthalic acid diamide, N,N,N',N'-tetraallyl-m-phthalic acid diamide, N,N,N',N'-tetraallyl-p-phthalic acid diamide, and other amide compounds); and other compounds containing sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, organic peroxides such as hydroperoxide, and the like. Among these compounds, 3,5-dimethyl-1-hexyn-3-ol is particularly preferred. The copolymer composition of this embodiment may contain two or more types of reaction inhibitors.

[0063] [Antioxidants] The copolymer composition of this embodiment may contain an antioxidant, preferably a hindered phenol-based antioxidant. By including a hindered phenol-based antioxidant, the copolymer composition of this embodiment can give a foamed molded article having a high water absorption rate and excellent compression set. The copolymer composition of this embodiment may contain two or more antioxidants.

[0064] Examples of hindered phenol-based antioxidants include 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene (manufactured by ADEKA Corporation, trade name: Adekastab AO-330, melting point: 243 to 245°C), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by ADEKA Corporation, trade name: Adekastab AO-330, melting point: 243 to 245°C), 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 ADEKA Corporation, trade name: Adekastab AO-330, melting point: 243 to 245°C). DEKA Corporation, trade name: Adeka Stab AO-20, melting point: 220-222°C), 4,4'-butylidenebis(6-tert-butyl-m-cresol) (ADEKA Corporation, trade name: Adeka Stab AO-40, melting point: 210-214°C), N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine (BASF Japan Ltd., trade name: Irganox Examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Ltd., trade name: Irganox 1010, 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 the antioxidant, known antioxidants used in general rubber compositions can be used, specifically sulfur-based antioxidants and amine-based antioxidants. The antioxidants may be used alone, but are preferably used in combination of two or more kinds in order to maintain heat aging resistance for a long period of time 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, relative to 100 parts by mass of the copolymer (S). Use of the sulfur-based antioxidant in the above range is preferred because it has a significant effect of improving heat aging resistance and does not inhibit crosslinking of the copolymer composition.

[0067] The amine-based antiaging agent is used in an amount of preferably 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, relative to 100 parts by mass of the copolymer (S). Use of the amine-based antiaging agent in this range is preferred because it has a significant effect of improving heat aging resistance and does not inhibit crosslinking of the copolymer composition.

[0068] [Reinforcing agent] The copolymer composition of this embodiment may contain a reinforcing agent to improve physical properties such as tensile stress at break and tensile elongation at break. The reinforcing agent is a known rubber reinforcing agent that is compounded into a rubber composition, and specific examples thereof include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, finely divided talc, and differential silicic acid. The copolymer composition of this embodiment may contain two or more types of reinforcing agents.

[0069] [Softener] The copolymer composition of this embodiment may contain a softening agent. The softener is a known softener that is compounded in rubber compositions.Specific examples include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymers such as terpene resin, petroleum resin, and coumarone-indene resin; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factice).Among these, petroleum-based softeners are preferred, and paraffin-based process oil is particularly preferred. The copolymer composition of this embodiment may contain two or more types of softeners.

[0070] [Moisture absorbent] The copolymer composition of this embodiment may contain a moisture absorbent. Examples of moisture absorbents include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. Of these, calcium oxide is preferred. The amount of moisture absorbent 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 of this embodiment may contain two or more types of moisture absorbents.

[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)hexyne-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-butyl peroxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0072] [Crosslinking aid] The copolymer composition of this embodiment may contain a crosslinking aid together with the organic peroxide. Specific examples of the crosslinking aid 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, divinylbenzene, etc. Such a crosslinking aid is used in an amount of preferably 0.5 to 2 moles, more preferably about equimolar, per mole of the organic peroxide used.

[0073] [Filler] The copolymer composition of this embodiment may contain a filler to reduce compounding costs. Examples of fillers include talc and clay. These fillers may be used alone or in combination of two or more. Such fillers are used in an amount of preferably 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 aids] The copolymer composition of this embodiment may also contain a processing aid. As the processing aid, a wide variety of processing aids that are generally compounded into rubbers can be used. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters. These processing aids may be used alone or in combination of two or more. The processing aid may be appropriately compounded 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 the copolymer (S). When the amount of the processing aid is within the above range, excellent processability, such as kneading processability, extrusion processability, and injection moldability, is achieved.

[0075] [Activator] The copolymer composition of this embodiment may contain an active agent. Examples of the activator include glycols such as polyethylene glycol and diethylene glycol; and amines such as di-n-butylamine and triethanolamine. These activators may be used alone or in combination with one another. The activator may 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 the copolymer (S).

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

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

[0078] Examples of resins other than the copolymer (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 the hydrosilyl group-containing compound (Y) blended per 100 parts by mass of the 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, still 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 the platinum-based catalyst to be 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, still more preferably 0.02 to 1.0 parts by mass, still 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] [Action and effect] The copolymer composition of this embodiment suppresses the crosslinking reaction at relatively low temperatures (e.g., 50 to 130°C) during kneading and molding, thereby preventing scorching (burning or early, unexpected crosslinking reaction) caused by heat during processing or storage. Furthermore, it has excellent crosslinking properties, allowing crosslinking in a short time at crosslinking temperatures (e.g., 150 to 200°C). Therefore, by employing various known molding methods, it can be molded at a higher speed than conventional copolymer compositions.

[0082] <Second aspect> The copolymer composition according to the 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 and may also contain a hindered phenol-based antioxidant.

[0083] The foamed molded article according to the second aspect of the present invention is a foamed molded article obtained by crosslinking and foaming the copolymer composition according to the second aspect. A method for producing a foamed molded article according to a second aspect of the present invention is characterized in that the copolymer composition according to the second aspect is melt-extruded and crosslinked in a hot-air vulcanization tank.

[0084] [Copolymer (S)] The copolymer (S) in this embodiment is the same as the copolymer (S) in the first embodiment, and the preferred embodiments are also the same as those in the first embodiment. That is, it has a structural unit derived from ethylene (A) as explained 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), and satisfies the above requirements (i) and (ii). The copolymer composition of this embodiment may contain two or more types of 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. That is, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural features as those explained in the first embodiment. The preferred embodiments of the hydrosilyl 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 types of hydrosilyl group-containing compounds (Y).

[0086] [Platinum catalyst] The platinum catalyst for hydrosilyl crosslinking in this embodiment is the same as the platinum catalyst for hydrosilyl crosslinking in the first embodiment, and preferred embodiments are also the same. The copolymer composition of this embodiment may contain two or more platinum 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 10% irregularity in the cumulative distribution curve based on the number of irregularities is 0.9 or less, and the cumulative 90% equivalent circle diameter in the cumulative distribution curve based on the number of equivalent circle diameters is 43 μm or more. The copolymer composition of this embodiment may contain two or more types of sodium bicarbonate-based blowing agents.

[0088] The roughness in requirement (b) 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 outline of the particle, and the envelope perimeter is the perimeter of the shape connecting the convex parts of the particle at the shortest distance. The equivalent circle diameter is the diameter of a circle having an area equal to the projected area of ​​the grain.

[0089] A cumulative 10% irregularity of 0.9 or less means that a certain amount of particles with a small irregularity (large irregularity) are contained. A cumulative 90% equivalent circle diameter of 43 μm or more means that a certain amount of particles with large equivalent circle diameters are included.

[0090] The perimeter and envelope perimeter for determining the degree of unevenness, as well as the projected area of ​​the particle for determining the equivalent circle diameter, were measured by dynamic image analysis (wet, observation magnification 4x) using MEK as the dispersion solvent with a particle shape image analyzer PITA3 (manufactured by Seishin Enterprise Co., Ltd.). An example of a commercially available sodium bicarbonate foaming agent that satisfies the requirement (b) is Celbon FE-507R (trade name) manufactured by Eiwa Chemical Industry Co., Ltd.

[0091] [Combined ingredients, etc.] Reaction inhibitors, antioxidants, antiaging agents, reinforcing agents, softeners, moisture absorbents, organic peroxides, crosslinking aids, fillers, processing aids, activators, 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 the hydrosilyl group-containing compound (Y) per 100 parts by mass of the copolymer (S) is the same as in the first embodiment. In the copolymer composition of this embodiment, the preferred amount of platinum catalyst to be blended 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 the 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, still more preferably 0.5 to 7.5 parts by mass, still 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 the reaction inhibitor to be 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, still more preferably 0 to 1.4 parts by mass, still more preferably 0 to 1.2 parts by mass, particularly preferably 0 to 1.0 part by mass, and most preferably 0 to 0.8 parts by mass.

[0095] In the copolymer composition of this embodiment, the amount of the hindered phenol-based antioxidant blended per 100 parts by mass of the 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 the reinforcing agent to be blended per 100 parts by mass of the copolymer (S) is preferably 70 to 200 parts by mass, more preferably 70 to 150 parts by mass. In the copolymer composition of this embodiment, the amount of the softener to be blended per 100 parts by mass of the copolymer (S) is preferably 60 to 120 parts by mass, more preferably 60 to 110 parts by mass.

[0097] [Foam molded body] To obtain a molded article made of a foam obtained by crosslinking and foaming the copolymer composition of this embodiment, a known general processing method (molding method) for rubber compounds can be used. Specifically, it is as follows. For example, the copolymer (S) and other components are kneaded for 3 to 10 minutes at a temperature of 80 to 170°C using an internal mixer such as a Banbury mixer, kneader, or intermix, followed by adding the hydrosilyl group-containing compound (Y), platinum catalyst, reaction inhibitor, reinforcing agent, softener, and sodium bicarbonate blowing agent in the amounts specified above, as well as other compounding ingredients and other rubbers and resins, if necessary, and kneading the mixture for 5 to 30 minutes at a roll temperature of 50 to 130°C using rolls such as open rolls or a kneader, followed by dispensing. A ribbon- or sheet-like composition is usually obtained in this manner.

[0098] The obtained composition is preformed into a desired shape by various molding methods such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then, or simultaneously with molding, the molded product is introduced into a vulcanization tank and heated to crosslink, thereby obtaining a foamed molded article consisting of a foam obtained by crosslinking and foaming the copolymer composition.

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

[0100] The foamed molded article obtained from the copolymer composition of this embodiment can be used in a variety of applications. Specifically, it can be suitably used in applications such as highly expanded sealants, automotive sealants, sealants for civil engineering and construction, and various industrial sealants. It is particularly suitable for weatherstrip sponge materials (expansion ratio preferably 1.3 to 4.0 times), and also for highly expanded sponge materials (expansion ratio preferably more than 3.0 times but not more than 30 times) used for sponges, dam rubbers, etc. Specific examples of such foamed molded articles 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] [Action and effect] The foamed molded article obtained from the copolymer composition of this embodiment exhibits excellent sponge properties, such as low specific gravity and high water absorption, and also has low compression set. Although the reason for this is unclear, it is thought that the copolymer composition of this embodiment contains a sodium bicarbonate-based blowing agent that satisfies requirement (b), which allows the crosslinking reaction and the blowing agent decomposition reaction to proceed simultaneously, and also makes it easier for the crosslink density to increase.

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

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

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

[0105] 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 specified. The copolymer composition of this embodiment may contain two or more copolymers (S1) having an intrinsic viscosity [η] within the above range.

[0106] [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. That is, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural features as those explained in the first embodiment. The preferred embodiments of the hydrosilyl 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 types of hydrosilyl group-containing compounds (Y).

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

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

[0109] [Softener] The copolymer composition of this embodiment contains paraffinic process oil as a softener. The copolymer composition of this embodiment preferably contains 5% by mass or more of paraffinic process oil relative to the total amount of softener contained, more preferably 10% by mass or more, and particularly preferably contains only paraffinic process oil.

[0110] Examples of softeners other than paraffin-based process oils include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic polymeric substances 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 lubricating oils, tall oil, and sub(factice).

[0111] [Combined ingredients, etc.] Reaction inhibitors, antioxidants, antiaging agents, reinforcing agents other than carbon black, softeners other than paraffin-based process oils, moisture absorbents, organic peroxides, crosslinking aids, fillers, processing aids, activators, 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 the hydrosilyl group-containing compound (Y) per 100 parts by mass of the copolymer (S) is the same as in the first embodiment. In the copolymer composition of this embodiment, the preferred amount of platinum catalyst to be blended 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. When the blending amount of carbon black is equal to or greater than the lower limit, the mechanical strength is excellent, and when the blending amount of carbon black is equal to or less than the upper limit, the processability is excellent.

[0114] In the copolymer composition of this embodiment, the amount of paraffinic process oil blended per 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. When the blending amount of paraffin-based process oil is equal to or greater than the lower limit, the processability is excellent. When the blending amount of paraffin-based process oil is equal to or less than the upper limit, the mechanical strength is excellent.

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

[0116] [Crosslinked molded product] The copolymer composition of this embodiment can be preformed into a desired shape by various molding methods, such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then, simultaneously with molding, the molded product can be introduced into a vulcanization tank and heated to crosslink, thereby obtaining a crosslinked molded product obtained by crosslinking the copolymer composition.

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

[0118] The crosslinked molded article obtained from the copolymer composition of this embodiment can be used for various purposes, specifically, it is suitable for use as a weatherstrip sponge, etc.

[0119] [Action and effect] The copolymer composition of this embodiment has excellent moldability, such as extrusion moldability, press moldability, and injection moldability, and excellent processability, such as roll processability. Furthermore, the crosslinked molded article obtained by crosslinking this copolymer composition has excellent low-temperature properties (flexibility at low temperatures, rubber elasticity, etc.), mechanical properties, heat resistance stability, etc. The reason for this is not clear, but it is thought that the high crosslink density and the uniform crosslink structure are the main reasons.

[0120] <Fourth aspect> The copolymer composition according to the fourth aspect of the present invention comprises the copolymer (S1) shown as a preferred embodiment of the copolymer (S) in the first aspect and 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. In addition, the "Mooney viscosity ML(1+4)100°C" determined by the method described in JIS K 6300-1:2013 is 0.1 to 8. A crosslinked molded article according to a fourth aspect of the present invention is characterized in that it is obtained by crosslinking the copolymer composition according to 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, the copolymer (S) has structural units derived from ethylene (A), structural units derived from an α-olefin (B) having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene (C), as described in the first embodiment, and satisfies the above requirements (iii) to (v) in addition to the above requirements (i) and (ii), and has an intrinsic viscosity [η] of 0.5 dL / g or more and less than 2.0 dL / g.

[0122] When 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, determined by the method described in JIS K 6300-1:2013, to 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, 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 specified. The copolymer composition of this embodiment may contain two or more copolymers (S1) having an intrinsic viscosity [η] within the above range.

[0124] [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. That is, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural features as those explained in the first embodiment. The preferred embodiments of the hydrosilyl 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 types of hydrosilyl group-containing compounds (Y).

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

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

[0127] Examples of softeners other than paraffin-based process oils include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic polymeric substances 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 lubricating oils, tall oil, and sub(factice).

[0128] [Combined ingredients, etc.] Reaction inhibitors, antioxidants, antiaging agents, reinforcing agents, softeners other than paraffin-based process oils, moisture absorbents, organic peroxides, crosslinking aids, fillers, processing aids, activators, 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 the hydrosilyl group-containing compound (Y) per 100 parts by mass of the copolymer (S) is the same as in the first embodiment. In the copolymer composition of this embodiment, the preferred amount of platinum catalyst to be blended 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 is within the above range, an excellent balance between processability and mechanical strength is achieved.

[0131] In the copolymer composition of this embodiment, the amount of paraffinic process oil blended per 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. When the blending amount of oil is equal to or greater than the lower limit, excellent processability is achieved. When the blending amount of paraffin-based process oil is equal to or less than the upper limit, excellent mechanical strength is achieved.

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

[0133] [Crosslinked molded product] The copolymer composition of this embodiment can be preformed into a desired shape by various molding methods, such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then, simultaneously with molding, the molded product can be introduced into a vulcanization tank and heated to crosslink, thereby obtaining a crosslinked molded product obtained by crosslinking the copolymer composition.

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

[0135] The crosslinked molded article obtained from the copolymer composition of this embodiment can be used for various purposes, specifically, golf club grips, walking stick grips, toothbrush grips, tableware (spoon, fork, chopstick) grips, broom grips, teacup and rice bowl grips, etc.

[0136] [Action and effect] 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, so that handmade molding is possible. The reason for the small compression set is not clear, but it is thought that this is due to the high crosslink density and the uniform crosslink structure.

[0137] <Fifth aspect> The copolymer composition according to the fifth aspect of the present invention comprises the copolymer (S1) shown as a preferred embodiment of the copolymer (S) in the first aspect and 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 catalyst, carbon black, and a paraffinic process oil. In addition, the Brookfield rotational viscosity at 25°C determined by the method described in JIS K 7117:1999 is 6000 Pa·s or less. A crosslinked molded article according to a fifth aspect of the present invention is characterized in that it is obtained by crosslinking the copolymer composition according to the fifth aspect.

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

[0139] When 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 Brookfield rotational viscosity at 25°C of the copolymer composition, determined by the method described in JIS K 7117:1999, to 6000 Pa s or less. The intrinsic viscosity [η] of the copolymer (S) in this embodiment is preferably 0.6 to 1.5 dL / g, more preferably 0.7 to 1.3 dL / g.

[0140] 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 specified. 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. That is, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural features as those explained in the first embodiment. The preferred embodiments of the hydrosilyl 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 types of hydrosilyl group-containing compounds (Y).

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

[0143] [Reinforcing agent] The copolymer composition of this embodiment contains carbon black as a reinforcing agent. The copolymer composition of this embodiment preferably contains 5 mass or more of carbon black relative to the total amount of reinforcing agents contained, more preferably 10 mass or more of carbon black, and particularly preferably contains only carbon black. 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 softener. The copolymer composition of this embodiment preferably contains 5% by mass or more of paraffinic process oil relative to the total amount of softener contained, more preferably 10% by mass or more, and particularly preferably contains only paraffinic process oil. Examples of softeners other than paraffin-based process oils include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic polymeric substances 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 lubricating oils, tall oil, and sub(factice).

[0145] [Combined ingredients, etc.] Reaction inhibitors, antioxidants, antiaging agents, reinforcing agents other than carbon black, softeners other than paraffin-based process oils, moisture absorbents, organic peroxides, crosslinking aids, fillers, processing aids, activators, 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 the hydrosilyl group-containing compound (Y) per 100 parts by mass of the copolymer (S) is the same as in the first embodiment. In the copolymer composition of this embodiment, the preferred amount of platinum catalyst to be blended 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 is within the above range, the balance between fluidity, mechanical strength and compression set is excellent.

[0148] In the copolymer composition of this embodiment, the amount of paraffinic process oil blended per 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 blending amount of the paraffinic process oil is within the above range, an excellent balance of fluidity, mechanical strength and compression set is achieved.

[0149] [Brookfield rotational viscosity] The copolymer composition of this embodiment has a Brookfield rotational viscosity (B-type viscosity) at 25° C. determined by the method described in JIS K 7117:1999 of 6000 Pa·s or less. The Brookfield rotational viscosity is preferably 50 to 5800 Pa·s, more preferably 50 to 5600 Pa·s. When the Brookfield rotational viscosity is in the above range, the fluidity is excellent. For the measurement, a Brookfield rotational viscometer Model DV-II (manufactured by Brookfield Engineering Laboratories, Inc.) was used.

[0150] [Crosslinked molded product] The copolymer composition of this embodiment can be preformed into a desired shape by various molding methods, such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then, simultaneously with molding, the molded product can be introduced into a vulcanization tank and heated to crosslink, thereby obtaining a crosslinked molded product obtained by crosslinking the copolymer composition.

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

[0152] The crosslinked molded article obtained from the copolymer composition of this embodiment can be used in a variety of applications, specifically, it is suitable for use as a potting material, rubber coating, etc.

[0153] [Action and effect] According to the copolymer composition of this embodiment, excellent rubber physical properties can be obtained in the crosslinked molded article obtained by crosslinking this copolymer composition. The reason for this is unclear, but it is thought that the uniformity of the cross-linked structure is a factor.

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

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

[0156] The total mass percent concentration of the structural units derived from ethylene (A), the structural units derived from the α-olefin (B) having 3 to 20 carbon atoms, and the structural units derived from the non-conjugated polyene (C) relative to all structural units constituting the copolymer (S) is preferably 80 mass% or more, more preferably 90 mass% or more, even more preferably 92 mass% or more, and particularly preferably 100 mass%.

[0157] Examples of the α-olefin (B) having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as "α-olefin (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. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferred, with propylene being particularly preferred. Such α-olefins are preferred because they are relatively inexpensive as raw materials, the resulting copolymer (S) exhibits excellent mechanical properties, and a molded article having rubber elasticity can be obtained. These α-olefins may be used alone or in combination of two or more.

[0158] The non-conjugated polyene (C) is a non-conjugated polyene containing, in the molecule, two or more partial structures in total, each of which is at least one of the partial structures represented by the following formula (I) and the following formula (II).

[0159] [ka]

[0160] Examples of the non-conjugated polyene (C) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene. Among these, it is preferable that the non-conjugated polyene (C) contains VNB, and it is more preferable that the non-conjugated polyene (C) is VNB, because it is easily available, exhibits good hydrosilyl crosslinking, and tends to improve the heat resistance of the polymer composition. The non-conjugated polyene (C) may be used alone or in combination of two or more.

[0161] The copolymer (S) in this embodiment may further contain a structural unit (CX) derived from a non-conjugated polyene (CX) containing only one partial structure selected from the group consisting of the general formulas (I) and (II) in the molecule, within the range that does not impair the effects of this embodiment. 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, 5-(2-ethyl-3-butenyl)-2-norbornene,

[0033] Examples of such methyl-5-hexenyl-2-norbornene 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] Among these, ENB is preferred because it is readily available, the crosslinking rate during hydrosilyl crosslinking is easily controlled, and good mechanical properties are easily obtained. The non-conjugated polyene (CX) may be used alone or in combination of two or more. When the copolymer (S) in this embodiment contains a structural unit derived from a non-conjugated polyene (CX), the mass percent concentration thereof is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0.01 to 8 mass%, based on all structural units constituting the copolymer (S).

[0163] The copolymer (S) in this embodiment satisfies the following requirements (i) to (v). (i) The ratio [A] / [B] of the number of moles [A] of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin (B) having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1. (ii) The mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass % based on the total mass of all structural units constituting the copolymer (S).

[0164] (iii) (n C ) is between 4.5 and 40. (n C ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative 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).

[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 the complex viscosity η at frequency ω=100rad / 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] 2.9 ) ≦ (C) mass percent concentration × 6 Equation (2)

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

[0167] Requirement (i) specifies that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from α-olefin (B) in the copolymer (S) in this embodiment 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. When the copolymer (S) satisfies the requirement (i), the molded article obtained by hydrosilyl crosslinking the copolymer (S) exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility, which is preferable. The ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles of structural units derived from α-olefin (B) in the copolymer (S) is 13 It can be determined by C-NMR.

[0169] Requirement (ii) specifies that the mass percent concentration of the structural units derived from the non-conjugated polyene (C) in the copolymer (S) is 0.07 to 10 mass % relative to all structural units constituting the copolymer (S). The mass percent concentration of the structural 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] The copolymer (S) is preferred because it satisfies requirement (ii), and therefore the crosslinked molded article obtained from the copolymer composition according to this embodiment has sufficient hardness and excellent mechanical properties. Furthermore, when the copolymer (S) is hydrosilyl crosslinked, it is preferred because it exhibits a fast crosslinking rate, allowing for efficient production of the crosslinked molded article. The mass percent concentration of the constitutional units derived from the non-conjugated polyene (C) in the copolymer (S) is 13 It can be determined by C-NMR.

[0171] The mass percent concentration of the constitutional units derived from the non-conjugated polyene (C) and the weight average molecular weight (Mw) of the copolymer (S) preferably satisfies the following formula (4). 6 - 0.45 × Ln(Mw) ≦ (C) mass percent concentration... Equation (4)

[0172] Requirement (iii) is calculated by the following formula (1) (n C ) range is specified as 4.5 to 40. (n C ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). Here, (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.

[0173] (n C ) is the number of constitutional units derived from the non-conjugated polyene (C) per weight average molecular weight (Mw) of the copolymer (S). (n C When the ratio (R) is equal to or greater than the lower limit, a sufficient crosslinking rate can be easily obtained during hydrosilyl crosslinking. When the ratio (R) is equal to or less than the upper limit, excessive crosslinking is unlikely to occur, and the resulting crosslinked molded article exhibits superior mechanical properties. When the requirement (iii) is satisfied, the copolymer (S) has a low content of long chain branches, a high crosslinking rate of hydroxy crosslinking, and an excellent balance of physical properties such as mechanical properties of the obtained crosslinked molded article, and is also less likely to undergo post-crosslinking and has excellent heat aging resistance, which is preferable.

[0174] When the copolymer (S) contains the structural unit (CX), the (n C+cx ) 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 percent concentration of (C) / 100} / molecular weight of (C) + {mass percent concentration of (CX) / 100} / molecular weight of (CX)] (1') (n C+cx ) is the total number of constitutional units derived from the non-conjugated polyene (C) and the number of constitutional units derived from the non-conjugated polyene (CX) per weight average molecular weight (Mw) of the copolymer (S).

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

[0176] The rheometer used was a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific), and measurements were carried out at 190° C., strain 1.0%, and varying 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 ) ≦ (C) mass percent concentration × 5.7 Equation (2') ratio P(η * (ω=0.1) / η * (ω=100) ) represents the frequency dependence of viscosity, and is the left side of equation (2) and equation (2') P / ([η] 2.9 ) tends to show high values ​​when there are many long chain branches, although it is affected by factors such as short chain branches and molecular weight.

[0178] Generally, in an ethylene-α-olefin-non-conjugated polyene copolymer, the more structural units derived from the non-conjugated polyene the copolymer contains, the more long-chain branches it tends to contain. However, it is considered that the copolymer (S) in this embodiment has fewer long-chain branches than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, and therefore can satisfy the above formula (2).

[0179] Requirement (v) is the number of long chain branches (LCB) per 1,000 carbon atoms of the copolymer (S) obtained by 3D-GPC. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3). LCB 1000C ≦1-0.07×Ln(Mw) Equation (3)

[0180] The upper limit of the content of long chain branches per unit carbon number of the copolymer (S) is determined by the above formula (3). That is, requirement (v) means that the proportion of long chain branches in the copolymer (S) is low. By satisfying the requirement (v), the copolymer (S) has excellent curing properties when subjected to hydrosilyl crosslinking, and the crosslinked molded article obtained using the copolymer has excellent heat aging resistance. The copolymer (S) more preferably satisfies the following formula (3'). LCB 1000C ≦1-0.071×Ln(Mw)...Equation (3')

[0181] Mw and (LCB 1000C) is a value determined by structural analysis using 3D-GPC. Specifically, the absolute molecular weight distribution was determined using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was simultaneously determined 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 (Polymer Laboratories)

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

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

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

[0186]

number

[0187]

number

[0188] Furthermore, using g'w, the number of branch points per molecular chain, BrNo, and the number of long chain branches per 1000 carbon atoms, LCB, are calculated. 1000C The branching degree λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer formula (v-5). 1000C Equations (v-6) and (v-7) were used to calculate λ. g is the long-chain branching parameter calculated from the radius of gyration Rg, and the following simple correlation is established between g' calculated from the intrinsic viscosity. Various values ​​have been proposed for ε in the equation depending on the shape of the molecule. Here, calculations were performed assuming ε = 1 (i.e., g' = g).

[0189]

number

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

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

[0192] The copolymer (S) in this embodiment also preferably satisfies the 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 non-conjugated polyene (C)}+1.42 … Equation (5)

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

[0194] In the formula (5), the apparent iodine value derived from the non-conjugated 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 the above formula (5), the left side represents the shear rate dependency, which is an index of the amount of long chain branches, and the right side represents an index of the content of non-conjugated polyene (C) that is not consumed as long chain branches during polymerization. If requirement (vi) is satisfied, the degree of long chain branching is not too high, which is preferable. If requirement (vi) is not satisfied, a large proportion of the copolymerized non-conjugated polyene (C) is consumed in the formation of long chain branches.

[0196] The copolymer composition of this embodiment may contain two or more types of copolymers (S). For example, two or more types of the copolymers (S) differing in (a) the molar ratio of ethylene / α-olefin having 3 to 20 carbon atoms, (b) the iodine value, or (c) the intrinsic viscosity [η] may be mixed and used. In particular, in the case of (c), a mixture of a low intrinsic viscosity component and a high intrinsic viscosity component may be used.

[0197] In this embodiment, the method for producing the copolymer (S) is not particularly limited, but it is preferably one obtained by copolymerizing monomers in the presence of a metallocene compound, and more preferably one obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound. Specifically, it can be produced by the method described in WO 2015 / 122495, for example.

[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-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule. The copolymer composition of this embodiment may contain two or more types of hydrosilyl group-containing compounds (Y).

[0199] [ka]

[0200] In formula (a), n and p are 0 or a positive number, m is a number ranging from 1 to 20, and the sum of n, m, and p is 5 to 50. 1 , R 2 are each independently a monovalent alkyl group, and may be the same or different. a is an aralkyl group and R is R 1 ,R 2 , hydrogen atom, R aHowever, when n=1, at least one of R is a hydrogen atom, and when n=0, both R are hydrogen atoms.

[0201] Such a hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane with a linear structure that has a relatively low degree of siloxane polymerization and has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule.

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

[0203] In formula (a), m is the number of diorganosiloxy units having silicon-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 in the side chain that have silicon-bonded hydrogen atoms and may be 0 or 1. When n=1, at least one of R is a hydrogen atom, and when n=0, both R are hydrogen atoms, resulting in a structure that has at least two silicon-bonded hydrogen atoms in the molecule.

[0205] Even if n is a number other than 0 or 1, one or both of the R at both molecular chain terminals may be a silicon-bonded hydrogen atom. Furthermore, n is preferably a number other than 0 or 1, and more preferably a number satisfying n≧m. More specifically, n may be a number in the range of 3 to 10, and is particularly preferably 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 a number within the range obtained by dividing the values ​​of n and m from the total degree of polymerization of diorganosiloxane units, which is represented by the sum of n, m, and p, as described below. For example, p may be a number within the range of 0 to 12, 0 to 10, 0 to 5, or 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 values ​​of n, m, and p is 5-50, preferably 5-20, or may be 5-15. In the hydrosilyl group-containing compound (Y) which is the crosslinking agent of the present invention, m is particularly preferably a number in the range of 3 to 6, n is a number in the range of 3 to 9, and p is a number in the range of 0 to 2.

[0208] In formula (a), R is R 1 ,R 2 , hydrogen atom, R a However, when n=0 or 1, both or one of R is a hydrogen atom. R in the formula 1 ,R 2 are monovalent alkyl groups, which may be the same or different, and in which some of the carbon-carbon-bonded hydrogen atoms may be substituted with halogen atoms. Such alkyl groups may be alkyl groups having 1 to 20 carbon atoms, and industrially may be methyl groups.

[0209] In formula (a), R a is an aralkyl group, and may be an aralkyl group having 7 to 20 carbon atoms, 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 preferred that the alkylene structure between the aryl group, such as a phenyl group, and the silicon atom contains at least one branching unit represented by -CH(CH3)-. In the present invention, it is particularly preferred that R ais an aralkyl group represented by -CH2-CH(CH3)-C6H5.

[0210] The aralkyl group is a characteristic functional group that confers usefulness as a crosslinking agent to the hydrosilyl group-containing compound (Y). In particular, the presence of an aralkyl group together with a silicon-bonded hydrogen atom in this component, where n, m, and p fall 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 the hydrosilyl group-containing compound (Y) blended per 100 parts by mass of the 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] The platinum catalyst for hydrosilyl crosslinking is an addition reaction catalyst, and any catalyst can be used without particular limitation, as long as it promotes the addition reaction (hydrosilylation reaction of alkene) between the alkenyl group in the copolymer (S) and the hydrosilyl group in the hydrosilyl group-containing compound (Y).

[0213] Specific platinum catalysts may be known ones that are normally used in addition curing, such as the fine powder platinum metal catalyst described in U.S. Pat. No. 2,970,150, the chloroplatinic acid catalyst described in U.S. Pat. No. 2,823,218, the complex compounds of platinum and hydrocarbons described in U.S. Pat. Nos. 3,159,601 and 159,662, the complex compounds of chloroplatinic acid and olefins described in U.S. Pat. No. 3,516,946, and the complex compounds of platinum and vinylsiloxanes described in U.S. Pat. Nos. 3,775,452 and 3,814,780.

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

[0215] In the copolymer composition of this embodiment, the amount of the platinum catalyst blended per 100 parts by mass of the 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 the organic peroxide (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)hexyne-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-butyl peroxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0217] The organic peroxide (Z) is preferably one whose decomposition products produced during crosslinking are low molecular weight compounds with sufficiently high vapor pressures, since the use of such organic peroxide (Z) makes it difficult for odors to remain in the resulting crosslinked molded article. In this specification and claims, the amount of organic peroxide (Z) is the amount converted to a purity of 100% by mass. For ease of handling, organic peroxides are usually sold with a purity of about 40% by mass. In the case of a product with a purity of 40% by mass, the amount of organic peroxide is calculated 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, 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 the 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 amounts of the hydrosilyl group-containing compound (Y) and the organic peroxide (Z) is preferably 23 / 77 to 99 / 1, 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 alkene) between the alkenyl groups of the copolymer (S) and the hydrosilyl groups of the hydrosilyl group-containing compound (Y). The addition of a reaction inhibitor is preferred in that it stabilizes the processability of the composition during kneading and molding.

[0222] Specific examples of the reaction inhibitor include benzotriazole; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1-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-phthalic acid diamide, N,N,N',N'-tetraallyl-m-phthalic acid diamide, and N,N,N',N'-tetraallyl-p-phthalic acid diamide; and others, sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, and tetramethyltetravinylcyclotetrasiloxane. Among these compounds, 3,5-dimethyl-1-hexyn-3-ol is particularly preferred. The copolymer composition of this embodiment may contain two or more types of reaction inhibitors.

[0223] In the copolymer composition of this embodiment, the amount of the reaction inhibitor to be added per 100 parts by mass of the 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] [Antioxidants] The copolymer composition of this embodiment may contain an antioxidant, preferably a hindered phenol-based antioxidant. By including a hindered phenol-based antioxidant, the copolymer composition of this embodiment can give a crosslinked molded article having a high water absorption rate and excellent compression set. The copolymer composition of this embodiment may contain two or more antioxidants.

[0225] Examples of the hindered phenol antioxidant include 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene (manufactured by ADEKA Corporation, trade name: Adekastab AO-330, melting point: 243 to 245°C), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by ADEKA Corporation, trade name: Adekastab AO-330, melting point: 243 to 245°C), and ADEKA Corporation, trade name: ADK STAB AO-20, melting point: 220-222°C), 4,4'-butylidenebis(6-tert-butyl-m-cresol) (ADEKA Corporation, trade name: ADK STAB AO-40, melting point: 210-214°C), N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine (BASF Japan Ltd., trade name: Irganox Examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Ltd., trade name: Irganox 1010, 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] When the copolymer composition of this embodiment contains an antioxidant, the amount of the 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 the antioxidant, known antioxidants used in general rubber compositions can be used, such as sulfur-based antioxidants, phenol-based antioxidants, and amine-based antioxidants. The antioxidants may be used alone, but are preferably used in combination of two or more kinds in order to maintain heat aging resistance for a long period of time 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 the copolymer (S). When the sulfur-based antioxidant is used in the above range, the effect of improving heat aging resistance is significant.

[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). When the phenolic antioxidant is used in the above range, the effect of improving heat aging resistance is significant.

[0230] When the copolymer composition of this embodiment contains an amine-based antioxidant, it is used in an amount of preferably 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). When the amine-based antioxidant is used in the above range, the effect of improving heat aging resistance is significant.

[0231] [Reinforcing agent] The copolymer composition of this embodiment may contain a reinforcing agent to improve physical properties such as tensile stress at break and tensile elongation at break. The reinforcing agent is a known rubber reinforcing agent that is compounded into a rubber composition, and specific examples thereof include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, finely divided talc, and differential silicic acid. The copolymer composition of this embodiment may contain two or more types of reinforcing agents.

[0232] Among these, it is preferable to contain carbon black. When carbon black is contained, the processability of the copolymer composition can be improved, and the copolymer composition can have improved mechanical properties such as tensile strength, tear strength, and abrasion resistance.

[0233] Examples of carbon black that can be used include known products such as Asahi #50HG, Asahi #55G, and Asahi #60UG (all manufactured by Asahi Carbon Co., Ltd.), Seast SVH, Seast V, and Seast G-SO (all manufactured by Tokai Carbon Co., Ltd.). These can be used alone or in combination. Carbon blacks that have been surface-treated with a silane coupling agent or the like can also be used.

[0234] When the copolymer composition of this embodiment contains carbon black, it is used in an amount of preferably 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). When the amount of carbon black is within the above range, a copolymer composition excellent in dynamic magnification (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 compounded in rubber compositions.Specific examples include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymers such as terpene resin, petroleum resin, and coumarone-indene resin; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factice).Among these, petroleum-based softeners are preferred, and paraffin-based process oil is particularly preferred. The copolymer composition of this embodiment may contain two or more types of softeners.

[0236] When the copolymer composition of this embodiment contains a softener, it is used in an amount of preferably 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). When the amount of softener is within the above range, a copolymer composition can be obtained that has little tack and is excellent in processability, heat aging resistance, mechanical properties, etc.

[0237] [Moisture absorbent] The copolymer composition of this embodiment may contain a moisture absorbent. Examples of moisture absorbents include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. Of these, calcium oxide is preferred. The amount of moisture absorbent 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 of this embodiment may contain two or more types of moisture absorbents.

[0238] [Crosslinking aid] The copolymer composition of this embodiment may contain a crosslinking aid. Specific examples of the crosslinking aid 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, divinylbenzene, etc. Such a crosslinking aid is used in an amount of preferably 0.5 to 2 moles, more preferably about equimolar, per mole of the organic peroxide used.

[0239] [Filler] The copolymer composition of this embodiment may contain a filler to reduce compounding costs. Examples of fillers include talc and clay. These fillers may be used alone or in combination of two or more. Such fillers are used in an amount of preferably 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 aids] The copolymer composition of this embodiment may also contain a processing aid. As the processing aid, a wide variety of processing aids that are generally compounded with rubber can be used. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters. These processing aids may be used alone or in combination.

[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 blending amount of the processing aid is within the above range, excellent processability such as kneading processability, extrusion processability, and injection moldability is achieved.

[0242] [Activator] The copolymer composition of this embodiment may contain an active agent. Examples of the activator include glycols such as polyethylene glycol and diethylene glycol; and amines such as di-n-butylamine and triethanolamine. These activators may be used alone or in combination with one another. The activator may 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 the copolymer (S).

[0243] [Foaming agent] The copolymer composition of this embodiment may contain a foaming agent. Examples of the blowing agent include sodium bicarbonate blowing agents, ADCA (azodicarbonamide), DPT (N,N'-dinitropentamethylenetetramine), and OBSH (4,4'-oxybisbenzenesulfonylhydrazide). Among these, sodium bicarbonate blowing agents are preferred because they can lower the specific gravity of the foamed molded article and increase the crosslink density.

[0244] When the copolymer composition of this embodiment contains a foaming agent, the amount of the foaming 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 known rubber compounding agents, such as metal salts of α,β-unsaturated organic acids, crosslinking accelerators, plasticizers, and tackifiers, as long as the object of this embodiment is not impaired.

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

[0247] Examples of resins other than the copolymer (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] [Production of copolymer composition] The copolymer composition of this embodiment can be obtained by the same method as that used for known general rubber compositions. Specifically, the method is as follows. For example, the copolymer (S) and other components are kneaded for 3 to 10 minutes at a temperature of 80 to 170°C using an internal mixer such as a Banbury mixer, kneader, or intermix, and then the hydrosilyl group-containing compound (Y), platinum catalyst, and, if necessary, other compounding agents such as a reaction inhibitor, reinforcing agent, or softener, as well as other rubbers or resins, are added, and the mixture is kneaded for 5 to 30 minutes at a roll temperature of 50 to 130°C using rolls such as open rolls or a kneader, followed by dispensing. In this manner, a copolymer composition is usually obtained in the form of a ribbon or sheet.

[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, if necessary, other components (first kneading), and then add a platinum-based catalyst for hydrosilyl crosslinking, a reaction inhibitor, an organic peroxide, and, if necessary, other components to the resulting kneaded mixture and knead them together (second kneading). The organic peroxide may be added during either the first kneading or the second kneading.

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

[0251] When a reinforcing agent, softener, etc. is added, it may be added during either the first kneading or the second kneading, but it is preferable to add it during the first kneading. When other rubber compounding agents, such as metal salts of α,β-unsaturated organic acids, moisture absorbents, antioxidants, fillers, processing aids, activators, plasticizers, and tackifiers, are added, they are preferably added during the first kneading, and crosslinking aids, crosslinking accelerators, and foaming agents are preferably added during the second kneading.

[0252] The kneading device used in the first kneading may be any known kneading device capable of high-temperature processing, such as a Banbury mixer, a kneader, or an extruder. Examples of the kneading device used in the second kneading include a roll, a kneader, and an extruder, which are easy to control the temperature of.

[0253] By kneading in two stages, the first kneading and the second kneading, the copolymer (S) and the hydrosilyl group-containing compound (Y) can be kneaded at a high temperature in the first kneading, so that moisture contained in the hydrosilyl group-containing compound (Y), which acts as a crosslinking inhibitor, can be removed in a short time. Therefore, the copolymer composition can be obtained without increasing the amount of the hydrosilyl group-containing compound (Y), thereby reducing production costs.

[0254] Furthermore, by dividing the kneading of each component into the first kneading and the second kneading, the kneading time can be shortened compared to when all components are kneaded without being divided. Furthermore, by adding a platinum catalyst and a reaction inhibitor for hydrosilyl crosslinking and an organic peroxide during the second kneading, the progress of crosslinking during the first kneading can be suppressed, so the temperature during the first kneading can be increased and moisture can be removed in a shorter time.

[0255] [Action and effect] In the copolymer composition of this embodiment, the crosslinking reaction is suppressed at a relatively low temperature (for example, 50 to 130°C) during kneading and molding, and therefore scorching (burning or early unexpected crosslinking reaction) caused by heat during processing or storage can be suppressed. On the other hand, crosslinking can be achieved in a sufficiently short time at a crosslinking temperature (for example, 150 to 200° C.), and therefore the copolymer composition of this embodiment has excellent storage stability and productivity.

[0256] <Crosslinked molded body> A crosslinked molded article according to one embodiment of the present invention is a crosslinked molded article obtained by crosslinking the copolymer composition of the present invention. The crosslinked molded article can be obtained by preforming the copolymer composition of the present invention into a desired shape by a molding method using various molding machines such as an extruder, a calendar roll, a press molding machine, an injection molding machine, a transfer molding machine, etc., and then, simultaneously with molding, introducing the molded article into a vulcanization tank and heating it to crosslink it. When the copolymer composition of the present invention contains a foaming agent, foaming also proceeds along with crosslinking, and a foamed crosslinked molded article (foamed molded article) is obtained.

[0257] Any known heating method can be used without limitation, but it is particularly preferred to heat at a temperature of 150 to 200°C for 1 to 30 minutes using a heating bath such as a far-infrared heating furnace, hot air, a glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, or LCM (molten salt bath). Molding and crosslinking may or may not require the use of a mold. When a mold is not used, the rubber composition is usually molded and crosslinked continuously.

[0258] It is also preferred that the copolymer composition of the present invention is press-molded to carry out primary crosslinking, and then removed from the mold to obtain a primary molded article, which is then subjected to secondary crosslinking in a heat medium. Specifically, the copolymer composition of the present invention is press-molded at 120 to 200°C for 1 to 20 minutes, preferably at 150 to 200°C for 10 to 18 minutes, to perform primary crosslinking, and then removed from the mold to obtain a primary molded article, and the obtained primary molded article is then subjected to secondary crosslinking in a heat medium at 120 to 160°C for 10 to 24 hours, preferably at 140 to 160°C for 15 to 20 minutes. The heat medium used for the secondary crosslinking is air, steam, paraffin-based process oil, molten salt, or the like.

[0259] When primary crosslinking is performed by press molding, the crosslinked body does not reach high temperatures due to shear heating, which makes it possible to suppress the generation of low-molecular-weight siloxanes and polymer degradation. Furthermore, in press molding in which crosslinking is performed in a sealed state, a certain amount of generated low molecular weight siloxane remains inside the crosslinked body, but by subsequently performing secondary crosslinking in a heat medium, the low molecular weight siloxane can be volatilized, making it possible to obtain a crosslinked body with a low amount of low molecular weight siloxane.

[0260] The crosslinked molded article of this embodiment can be used in a variety of applications, including tire rubber, O-rings, industrial rolls, packing (e.g., condenser packing), gaskets, belts (e.g., heat insulating belts, copier belts, and conveyor belts), hoses such as automotive hoses (e.g., water hoses, brake reservoir hoses, radiator hoses, and air hoses), vibration-isolating rubber, vibration-isolating or vibration-damping materials (e.g., engine mounts and motor mounts), muffler hangers, sponges (e.g., weatherstrip sponges, heat insulating sponges, protective sponges, and micro-foam sponges), cables (ignition cables, cab tire cables, and high-tension cables), electric wire coating materials (high-voltage electric wire coating materials, low-voltage electric wire coating materials, and marine electric wire coating materials), glass run channels, color skin materials, paper feed rolls, and roofing sheets.

[0261] [Action and effect] The crosslinked molded article obtained from the copolymer composition of the present invention has a large tensile elongation at break and excellent rubber physical properties.

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

[0263] [Copolymer (S)] The copolymer (S) used in the production method of this embodiment is the same as the copolymer (S) in the first embodiment. That is, the copolymer (S) in this embodiment has structural units derived from ethylene (A) as described in the first embodiment, structural units derived from an α-olefin (B) having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene (C), and satisfies the above requirements (i) and (ii). The preferred embodiments of the copolymer (S) in this embodiment are the same as those in the first embodiment. In the method for producing the copolymer composition of this embodiment, two or more types of copolymers (S) may be used.

[0264] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) used in the production method of this embodiment is the same as the hydrosilyl group-containing compound (Y) in the first embodiment. That is, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural features as those explained in the first embodiment. The preferred embodiments of the hydrosilyl group-containing compound (Y) in this embodiment are the same as those in the first embodiment. In the method for producing the copolymer composition of this embodiment, two or more hydrosilyl group-containing compounds (Y) may be used.

[0265] [Platinum catalyst] The platinum catalyst for hydrosilyl crosslinking used in the production method of this embodiment is the same as the platinum catalyst for hydrosilyl crosslinking in the first embodiment, and preferred embodiments are also the same. In the production method of this embodiment, two or more platinum-based catalysts may be used.

[0266] [Reaction inhibitor] The reaction inhibitor used in the production method of this embodiment is the same as the reaction inhibitor in the first embodiment, and the preferred embodiments are also the same. In the production method of this embodiment, two or more types of reaction inhibitors may be used.

[0267] [Combined ingredients, etc.] Antioxidants, antiaging agents, reinforcing agents, softeners, moisture absorbents, organic peroxides, crosslinking aids, fillers, processing aids, activators, 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 the 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, still more preferably 0.1 to 15 parts by mass, still more preferably 0.1 to 10 parts by mass, still more preferably 1 to 10 parts by mass, particularly preferably 2 to 10 parts by mass, and most preferably 3 to 10 parts by mass, relative to 100 parts by mass of the copolymer (S).

[0269] The platinum 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, still more preferably 0.02 to 1.0 parts by mass, still 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, relative to 100 parts by mass of copolymer (S).

[0270] The amount of 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, still 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, relative to 100 parts by mass of the copolymer (S).

[0271] [Kneading] The kneading device used in the first kneading may be any known kneading device capable of high-temperature processing, such as a Banbury mixer, a kneader, or an extruder. Examples of the kneading device used in the second kneading include a roll, a kneader, and an extruder, which are easy to control the temperature of.

[0272] When a reinforcing agent, softener, etc. is added, it may be added during either the first kneading or the second kneading, but it is preferable to add it during the first kneading. When other rubber compounding agents, such as organic peroxides, metal salts of α,β-unsaturated organic acids, moisture absorbents, antioxidants, crosslinking aids, crosslinking accelerators, fillers, processing aids, activators, plasticizers, tackifiers, and foaming agents, are added, they may be added during either the first kneading or the second kneading.

[0273] [Crosslinked molded product] The copolymer composition obtained by the production method of this embodiment can be preformed into a desired shape by various molding methods, such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then, simultaneously with molding, the molded product can be introduced into a vulcanization tank and heated to crosslink, thereby obtaining a crosslinked molded article obtained by crosslinking the copolymer composition.

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

[0275] The crosslinked molded article obtained from the copolymer composition obtained by the production method of this embodiment can be used in a variety of applications, including tire rubber, O-rings, industrial rolls, packing (e.g., condenser packing), gaskets, belts (e.g., heat-insulating belts, copier belts, and conveyor belts), hoses such as automotive hoses (e.g., water hoses, brake reservoir hoses, radiator hoses, and air hoses), vibration-isolating rubber, vibration-insulating or vibration-damping materials (e.g., engine mounts and motor mounts), muffler hangers, sponges (e.g., weatherstrip sponges, heat-insulating sponges, protective sponges, and micro-foam sponges), cables (ignition cables, cab-tire cables, and high-tension cables), electric wire coating materials (high-voltage electric wire coating materials, low-voltage electric wire coating materials, and marine electric wire coating materials), glass run channels, colored skin materials, paper feed rolls, and roofing sheets.

[0276] [Action and effect] In the crosslinked molded article of this embodiment, the copolymer (S) and the hydrosilyl group-containing compound (Y) are kneaded at high temperature in the first kneading, so that moisture contained in the hydrosilyl group-containing compound (Y), which acts as a crosslinking inhibitor, can be removed in a short time, and therefore the copolymer composition can be obtained without increasing the amount of the hydrosilyl group-containing compound (Y), thereby reducing production costs.

[0277] In the production method of this embodiment, the kneading of each component is divided into a first kneading and a second kneading, which allows for a shorter kneading time than when the first kneading and the second kneading are not divided. Furthermore, by adding a platinum catalyst for hydrosilyl crosslinking and a reaction inhibitor during the second kneading, the progress of crosslinking during the first kneading can be suppressed, which allows for an increase in the temperature during the first kneading and enables moisture to be removed in a shorter time.

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

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

[0280] [Copolymer (S)] The copolymer (S) used in the production method of this embodiment is the same as the copolymer (S) in the first embodiment. That is, the copolymer (S) in this embodiment has structural units derived from ethylene (A) as described in the first embodiment, structural units derived from an α-olefin (B) having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene (C), and satisfies the above requirements (i) and (ii). The preferred embodiments of the copolymer (S) in this embodiment are the same as those in the first embodiment. In the method for producing the copolymer composition of this embodiment, two or more types of copolymers (S) may be used.

[0281] [Hydrosilyl group-containing compound (Y)] The hydrosilyl group-containing compound (Y) used in the production method of this embodiment is the same as the hydrosilyl group-containing compound (Y) in the first embodiment. That is, the hydrosilyl group-containing compound (Y) in this embodiment has the same structural features as those explained in the first embodiment. The preferred embodiments of the hydrosilyl group-containing compound (Y) in this embodiment are the same as those in the first embodiment. In the method for producing the copolymer composition of this embodiment, two or more hydrosilyl group-containing compounds (Y) may be used.

[0282] [Platinum catalyst] The platinum catalyst for hydrosilyl crosslinking used in the production method of this embodiment is the same as the platinum catalyst for hydrosilyl crosslinking in the first embodiment, and preferred embodiments are also the same. In the production method of this embodiment, two or more platinum-based catalysts may be used.

[0283] [Reaction inhibitor] The reaction inhibitor used in the production method of this embodiment is the same as the reaction inhibitor in the first embodiment, and the preferred embodiments are also the same. In the production method of this embodiment, two or more types of reaction inhibitors may be used.

[0284] [Combined ingredients, etc.] Antioxidants, antiaging agents, reinforcing agents, softeners, moisture absorbents, organic peroxides, crosslinking aids, fillers, processing aids, activators, 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 amount of the hydrosilyl group-containing compound (Y) used in the method for producing a crosslinked molded article of this embodiment is preferably 0.1 to 30 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of the copolymer (S). The amount of the platinum catalyst is preferably 0.001 to 10 parts by mass, more preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the copolymer (S). The reaction inhibitor is preferably used in an amount of 0 to 2 parts by mass, more preferably 0 to 0.8 parts by mass, per 100 parts by mass of the copolymer (S).

[0286] [Kneading] In the method for producing a crosslinked molded article of this embodiment, any known kneading device can be used for kneading as long as it is capable of performing high-temperature processing. Specific examples include a Banbury mixer, a kneader, and internal mixers such as an intermix.

[0287] [Crosslinked molded product] The crosslinked molded article obtained by the production method of this embodiment can be used in a variety of applications, including tire rubber, O-rings, industrial rolls, packing (e.g., condenser packing), gaskets, belts (e.g., heat insulating belts, copier belts, and conveyor belts), hoses such as automotive hoses (e.g., water hoses, brake reservoir hoses, radiator hoses, and air hoses), vibration-isolating rubber, vibration-isolating or vibration-damping materials (e.g., engine mounts and motor mounts), muffler hangers, sponges (e.g., weatherstrip sponges, heat insulating sponges, protective sponges, and micro-foam sponges), cables (ignition cables, cab tire cables, and high-tension cables), electric wire coating materials (high-voltage electric wire coating materials, low-voltage electric wire coating materials, and marine electric wire coating materials), glass run channels, colored skin materials, paper feed rolls, and roofing sheets.

[0288] [Action and effect] In the manufacturing method of this embodiment, the primary crosslinking is performed by press molding, so the crosslinked body does not reach a high temperature due to shear heating, which makes it possible to suppress the generation of low-molecular-weight siloxanes and degradation of the polymer. Furthermore, if primary crosslinking is performed by injection molding, the crosslinked body will reach extremely high temperatures due to shear heating caused by the high speed injection of the material into the mold from the nozzle, which can easily lead to the generation of low-molecular-weight siloxanes and accelerate the degradation of the polymer.

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

[0290] The crosslinked molded article obtained by the manufacturing method of this embodiment has a small compression set, and although the reason for this is not clear, it is thought to be due to the high crosslink density and the uniform crosslinked structure.

[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 the present invention of 600% or less, more preferably 100 to 600%, and even more preferably 150 to 500%. The copolymer composition of the present invention preferably has a tensile stress at break TB (MPa) measured by the method described in the Examples of the copolymer composition of the present invention of 15 MPa or less, more preferably 0.5 to 15 MPa, and even more preferably 0.7 to 13 MPa. The copolymer composition of the present invention preferably has a resistance to deformation of 5,000 or less, more preferably 100 to 5,000, and even more preferably 200 to 4,500, 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 preferably has a CS of 60% or less, more preferably 3 to 55%, and even more preferably 5 to 50%, when heat-treated at 150°C for 22 hours at a compressibility of 25%, as measured by the method described in the Examples. The copolymer composition of the present invention preferably has a CS of 20% or less, more preferably 3 to 18%, and even more preferably 5 to 15%, when heat-treated at 120°C for 72 hours at a compressibility of 25%, as measured by the method described in the Examples. 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 at a compressibility of 50%, as measured by the method described in the Examples. The copolymer composition of the present invention preferably has a CS of 30% or less, more preferably 1 to 25%, and even more preferably 3 to 20%, when heat-treated at 70°C for 22 hours at a compressibility of 50%, as measured by the method described in the Examples. The copolymer composition of the present invention has a specific gravity (Mg (megagrams / m)) measured by the method described in the Examples. 3 ) is 0.65Mg / m 3 Preferably, it is 0.1 to 0.60 Mg / m or less. 3 is preferred, and 0.2 to 0.55 Mg / m 3 is more preferred. The copolymer composition of the present invention preferably has a water absorption rate of 10% or more, more preferably 15 to 70%, and even more preferably 20 to 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) measured by the method described in the Examples of 10 ppm or less, more preferably 5 ppm or less, and even more preferably 3 ppm or less. The copolymer composition of the present invention has a crosslink density of 0.1×10 19 ~20×10 19 pcs / cc is preferable, 0.3 x 10 19 ~15×10 19 pcs / cc is more preferable, 0.5 x 10 19 ~13×10 19 Pieces / cc is more preferred. The copolymer composition of the present invention has a Brookfield viscosity measured by the method described in the Examples of preferably from 500 to 7000 Pa·s, more preferably from 800 to 6500 Pa·s, and even more preferably from 1000 to 6000 Pa·s. [Example]

[0292] The present invention will be explained 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 composition and molded article obtained in each example were evaluated by the following measurement methods.

[0294] [Crosslinking behavior of copolymer composition] Using the uncrosslinked copolymer composition in each example, the following values ​​were determined from the crosslinking curve measured at the crosslinking temperature and crosslinking time shown in each table in accordance with JIS K6300-2. MDR2000 (manufactured by Alpha Technologies) was used for the measurement.

[0295] "S' max " (dNm): Maximum torque value S' max is. "S' min " (dNm): Minimum torque value S' min is. "S' max -S' min " (dNm): Maximum torque value S' max and minimum torque value S' min This is the difference. "tcx1" (min): Minimum torque value S' min From "S' max -S'min " and the minimum torque value S' min The time it takes to reach the torque value corresponding to the sum of the minimum torque value S'. For example, "tc10" is the time it takes to reach the minimum torque value S'. min From "S' max -S' min " and the minimum torque value S' min The time required to reach a torque value corresponding to the sum of "tsx2" (min): Minimum torque value S' min For example, "ts1" is the time it takes for the torque value to increase by x2 (dNm) from the minimum torque value S'. min This is the time it takes for the torque value to increase by 1 (dNm). "MCR" (dNm / min): The maximum rate of change of torque in the crosslinking curve.

[0296] [Hardness test (Duro-A hardness)] In accordance with JIS K 6253-3, the hardness (Type A durometer, HA) of the sheet-shaped molded product was measured using six 2mm sheet-shaped rubber molded products with smooth surfaces, stacked on their flat surfaces to a thickness of approximately 12mm. However, test specimens containing foreign matter, air bubbles, or scratches were not used. The dimensions of the measurement surface of the test specimen were such that measurements could be made with the tip of the indenter at least 12mm away from the edge of the specimen.

[0297] [Hardness test (Duro-C hardness)] In accordance with JIS K 7312, the test was carried out using six 2mm sheet-shaped rubber molded specimens with smooth surfaces, stacked on top of each other on the flat side at a thickness of approximately 6mm, with a spindle No. 7, 1 rpm, and 25°C. However, specimens containing foreign matter, air bubbles, or scratches were not used. The dimensions of the measurement surface of the specimen were such that measurements could be made with the tip of the indenter at least 12mm away from the edge of the specimen.

[0298] [Tensile test] The molded articles of each example were punched out to prepare No. 3 dumbbell test pieces as specified in JIS K 6251 (1993). Using these test pieces, tensile tests were carried out according to the method specified in JIS K 6251, paragraph 3, at a measurement temperature of 25°C and a tensile speed of 500 mm / min to measure the modulus (MPa), tensile stress at break TB (MPa), and tensile elongation at break EB (%). The product of TB and EB was taken as the resistance to deformation. The number after M indicating the modulus is the elongation percentage; for example, "M25" means the modulus when the elongation percentage is 25% (25% modulus).

[0299] [Compression set (CS) of tubular molded body] The tubular molded article was cut into 30 mm lengths in the lengthwise direction, and the resulting test specimens were attached to a compression set measurement mold. The test specimens were compressed to half their height before the load was applied (compression rate: 50%), and the mold was placed in a Geer oven at the temperature shown in each table and heat-treated for the time shown in each table. The test specimens were then removed from the mold and allowed to cool for 30 minutes. The height of the test specimens was then measured, and the compression set (CS) (%) was calculated using the following formula: Compression set (CS) (%) = {(t0-t1) / (t0-t2)} x 100 t0: Height of the specimen before the test. t1: Height after heat treatment of the test piece and cooling for 30 minutes. t2: Height of the test specimen when attached to the measuring mold.

[0300] [Compression set (CS) of sheet-shaped molded product] Five 2mm thick sheet-like molded articles were stacked and attached to a compression set measurement mold. The test pieces were compressed to 3 / 4 of their original height (25% compression) and then placed in a Geer oven at the temperature shown in each table, followed by heat treatment for the time shown in each table. The test pieces were then removed from the mold and allowed to cool for 30 minutes. The height of the test pieces was then measured, and the compression set (CS) (%) was calculated using the following formula: Compression set (CS) (%) = {(t0-t1) / (t0-t2)} x 100 t0: Height of the specimen before the test. t1: Height after heat treatment of the test piece and cooling for 30 minutes. t2: Height of the test specimen when attached to the measuring mold.

[0301] [Specific gravity of foam molded product] The specific gravity of the foam molded article was measured in accordance with the underwater displacement method (JIS K 6268) using a 20 mm x 20 mm test piece from the hot-air crosslinked tubular foam molded article.

[0302] [Water absorption rate of foam molded body] A 20mm x 20mm test piece was punched out from the hot-air crosslinked tubular foam molded article, and surface dirt was wiped off with alcohol. The test piece was then placed 50mm below the water surface, the pressure was reduced to -625mmHg, and held there for 3 minutes. The pressure was then returned to atmospheric pressure, and after 3 minutes, the weight of the water-absorbed test piece 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] 1.0 g of a sample taken from the molded article of each example was precisely weighed into a 10 mL headspace vial, which was then sealed and subjected to measurement of low molecular weight components under the following headspace GC / MS conditions. Static headspace GC / MS Heating temperature / time: 190°C x 5 minutes, Quantitative analysis: Quantitative analysis converted using toluene Analytical equipment (Agilent Technologies) Headspace sampler: G1888 (Agilent Technologies) GC / MS:HP6890N / NP5973 Column: HP-3MS 0.25mm 30mm film thickness 0.25μm

[0304] [Crosslink density] The crosslink density ν was calculated from the Flory-Rehner equation (I) using the equilibrium swelling: Rwas determined by extracting a crosslinked 2 mm sheet with toluene at 37°C for 72 hours.

[0305]

number

[0306] [Crosslinking rate of copolymer composition] The uncrosslinked copolymer composition in each example was heated at a predetermined crosslinking temperature in accordance with JIS K6300-2, and the following values ​​were determined from the crosslinking curve measured using an MDR2000 (manufactured by Alpha Technologies).

[0307] "S' max " (dNm): Maximum torque value S' max is. "S' min " (dNm): Minimum torque value S' min is. "S' max -S' min " (dNm): Maximum torque value S' max and minimum torque value S' min This is the difference. "125°C (TS1) minutes": The time it takes for the torque value to increase by 1 (dNm) from the minimum torque value S'min, based on the start of measurement, under the condition of a temperature of 125°C. "180°C (tc90) minutes": The time required to reach a torque value equivalent to 90% of "S'max - S'min" based on the start of measurement under the condition of a temperature of 180°C.

[0308] [Odor] The uncrosslinked copolymer composition in each example was press-molded at 50°C for 10 minutes to obtain a sheet-like molded product having a smooth surface and a thickness of 3 mm. This was then crosslinked by heating in a Geer oven at 240°C for 6 minutes to obtain a crosslinked molded product of each example. The odor of the crosslinked molded article obtained in each example was evaluated according to the following criteria. ○: No unpleasant odor. ×: Unpleasant odor.

[0309] [Surface stickiness] The uncrosslinked copolymer composition in each example was press-molded at 50°C for 10 minutes to obtain a sheet-like molded product having a smooth surface and a thickness of 3 mm. This was then crosslinked by heating in a Geer oven at 240°C for 6 minutes to obtain a crosslinked molded product of each example. The surface of the crosslinked molded article obtained in each example was touched with a finger and evaluated according to the following criteria. ○: No stickiness when touched with hands. ×: Sticky when touched with hand.

[0310] [Scratch resistance] The uncrosslinked copolymer composition in each example was press-molded at 50°C for 10 minutes to obtain a sheet-like molded product having a smooth surface and a thickness of 3 mm. This was then crosslinked by heating in a Geer oven at 240°C for 6 minutes to obtain a crosslinked molded product of each example. The surface of each crosslinked molded article obtained was scratched with a brass rod with a circular, flat tip having a diameter of 3 mm immediately after removal from the gear oven, and evaluated according to the following criteria. The evaluation was carried out by three panelists, and the average of the results was calculated.

[0311] 5: No scratches. 4: Very slight scratches. 3: Slight scratches. 2: Scratches. 1: Clear scratches.

[0312] [Hardness test (Duro-A hardness)] The uncrosslinked copolymer composition of each example was press-molded at 180°C for 10 minutes to obtain a sheet-like molded article having a thickness of 2 mm. Six of the obtained crosslinked molded articles of each example were stacked to obtain a test piece having a thickness of 12 mm, and the hardness (Duro-A) was measured in accordance with JIS K 6253-3. The dimensions of the measurement surface of the test piece were such that the tip of the indenter could be measured at a position at least 12 mm away from the end of the test piece.

[0313] [Tensile test] The uncrosslinked copolymer composition in each example was press-molded at 180°C for 10 minutes to obtain a sheet-like molded article having a thickness of 2 mm. The crosslinked molded article obtained in each example was punched out to prepare a No. 3 dumbbell test piece described in JIS K 6251 (1993). Using this test piece, a tensile test was performed according to the method specified in JIS K 6251, paragraph 3, at a measurement temperature of 23°C and a tensile speed of 500 mm / min, and the tensile stress at break TB (MPa) and tensile elongation at break EB (%) were measured.

[0314] [Compression set (CS) of sheet-shaped molded product] The uncrosslinked copolymer composition in each example was crosslinked by heating at 180°C for 15 minutes using a press molding machine equipped with a cylindrical mold, and 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 test specimen was compressed by 25% of its height (12.5 mm) before applying a load, and placed together with the spacer in a gear oven at 120°C for 72 hours for heat treatment. The test specimen was then removed and left at room temperature for 30 minutes, after which the height of the test specimen was measured and the compression set (%) was calculated using the following formula: Compression set (%) = {(t0-t1) / (t0-t2)} x 100 t0: Height of the specimen before the test. t1: Height after treating the test piece under the above conditions and leaving it at room temperature for 30 minutes. t2: Height of the test specimen when attached to the measuring mold.

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

[0316] [Production Example 1: Production of Copolymer (S-1)] Copolymer (S-1) was produced in the same manner as in Production Example 1 of JP 2018-131527 A.

[0317] [Production Example 2: Production of Copolymer (S-2)] Copolymer (S-2) was produced by the method for producing an ethylene-propylene-VNB copolymer described in Example 1 (paragraphs

[0386] to

[0391] ) of WO 2019 / 180802, except that the hydrogen feed rate was changed to 50 liters / hr.

[0318] [Production Example 3: Production of Copolymer (A-1)] Terpolymerization of ethylene, propylene, and 5-vinyl-2-norbornene was carried out continuously in a 100-liter stainless steel polymerization vessel equipped with an impeller (stirring speed: 250 rpm). Hexane, 3.0 kg ethylene, 9.0 kg propylene, and 550 g VNB were fed into the liquid phase from the side of the vessel at rates of 60 liters per hour, 50 liters of hydrogen, and 95 mmol of VOCl3, 443 mmol of Al(Et)2Cl, and 500 mmol of Al(Et)2Cl as catalysts. 1.5 Cl 1.5 was fed continuously at a rate of 127 mmol.

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

[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 placed in a reactor and heated to 40°C while stirring under a nitrogen stream. 0.4 g of a toluene solution of platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex (Pt concentration 0.3 wt %) was added, and 265 g of α-methylstyrene was added dropwise while maintaining the reaction temperature at 40 to 90°C.

[0323] [ka]

[0324] After the dropwise addition, stirring was continued for 2 hours at 85°C, and then 0.5 g of the reaction solution was sampled and confirmed to be about 36% by alkali decomposition gas generation method (residual Si-H groups were decomposed with an ethanol / aqueous solution of KOH, and the reaction rate of Si-H groups was calculated from the volume of generated hydrogen gas). The reaction solution was then heated to 135°C under reduced pressure for 2 hours to distill off low boiling points, yielding 673 g of crosslinker (Y-1-1).

[0325] The resulting crosslinking agent (Y-1-1) was 29 It was confirmed by Si-NMR that the compound was the compound 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 viscometer according to JIS-Z-8803. 2 / s.

[0326] [ka]

[0327] [Crosslinking agent (Y-1-2)] A reactor was charged with 370 g of methylhydrogenpolysiloxane represented by the following formula (a-2-1), and the mixture was heated to 80°C while stirring under a nitrogen stream. 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 to 120°C.

[0328] [ka]

[0329] After the dropwise addition, stirring was continued for 1 hour at 145°C, and then 0.5 g of the reaction solution was sampled and confirmed to be about 50% by alkali decomposition gas generation method (the remaining Si-H groups were decomposed with an ethanol / aqueous solution of KOH, and the reaction rate of the Si-H groups was calculated from the volume of hydrogen gas generated). The reaction solution was then heated to 145°C under reduced pressure for 1 hour to distill off low boiling points, yielding 600 g of crosslinker (Y-1-2).

[0330] The resulting crosslinking agent (Y-1-2) was 29 It was confirmed by Si-NMR that the compound was the compound represented by the following formula (a-2). The viscosity of the obtained crosslinking agent (Y-1-2) was measured at 25°C using an Ubbelohde viscometer according to JIS-Z-8803. 2 / s.

[0331] [ka]

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

[0333] [ka]

[0334] <Other ingredients> 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), 1-minute half-life temperature 179.8°C Organic peroxide (Z-2): NOF Corporation, Percumyl (registered trademark) D-40, dicumyl peroxide (purity 40% by mass), 1-minute half-life temperature 175.2°C

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

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

[0338] Carbon black 1: Asahi #60G, manufactured by Asahi Carbon Co., Ltd. Carbon black 2: Asahi #50HG, manufactured by Asahi Carbon Co., Ltd. Carbon black 3: Asahi #60UG, FEF carbon black, manufactured by Asahi Carbon Co., Ltd. Heavy calcium carbonate: Whiten SB, manufactured by Shiraishi Calcium Co., Ltd. Calcium carbonate: Shiraishi Kogyo Co., Ltd., Hakuenka CC Precipitated silica: Tosoh Silica Corporation, Nipsil VN3 Calcium oxide 1: Vesta PP, manufactured by Inoue Lime Industry Co., Ltd. Calcium oxide 2: Vesta BS, manufactured by Inoue Lime Industry Co., Ltd.

[0339] Antioxidant: Irganox 1010, manufactured by BASF Japan Ltd. Titanium oxide: Ishihara Sangyo Kaisha, Ltd., R-820 Blue complex oxide pigment: Dipyroxide Blue, manufactured by Dainichiseika Chemicals Co., Ltd. Red pigment: PIGMOTEX RED 102 ET, manufactured by Sanyo Pigment Co., Ltd. Yellow pigment: PIGMOTEX YELLOW 83 ET, manufactured by Sanyo Pigment Co., Ltd. Calcined kaolin: BASF Japan Ltd., TRANSLINK-37

[0340] Baking soda 1: FE-507R, manufactured by Eiwa Chemical Industry Co., Ltd. Baking soda 2: FE-507, manufactured by Eiwa Chemical Industry Co., Ltd. Table 2 shows the values ​​obtained from the cumulative distribution curve of the number of irregularities and the cumulative distribution curve of the number of equivalent circle diameters for sodium bicarbonate 1 and sodium bicarbonate 2.

[0341] [Table 2]

[0342] <Examples 1-1 to 1-7> [Preparation of Uncrosslinked Composition] In the first stage, the raw materials shown in raw material 1 in Tables 3 and 4 were mixed for 2 minutes at 140°C using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.). The ram was then raised and cleaned, and the mixture was mixed for another minute and discharged at approximately 150°C to obtain the first-stage compound. The Mooney viscosity of the first-stage compound is shown in Tables 3 and 4.

[0343] Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; surface temperature of front roll: 50°C; surface temperature of rear roll: 50°C; rotation speed of front roll: 16 rpm; rotation speed of rear roll: 18 rpm), and the raw material shown in raw material 2 in Tables 3 and 4 was added thereto and kneaded for 10 minutes to obtain the uncrosslinked composition of each example.

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

[0345] [evaluation] For the uncrosslinked compositions of each example, 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 in Examples 1-1 to 1-7, the molded articles obtained were excellent in physical properties and processability.

[0346] As shown in Tables 3 and 4, Examples 1-1 to 1-7, which used crosslinking agent (Y-1-1) or (Y-1-2), had larger ts values ​​in low-temperature crosslinking than Example 1-8, which used crosslinking agent (Y-2), and thus had excellent scorch resistance. Furthermore, Examples 1-1 to 1-7 had tc90 of 10 minutes or less in high-temperature crosslinking, demonstrating that a sufficient crosslinking rate was obtained during crosslinking. Furthermore, in Examples 1-1 to 1-7, the crosslinked molded articles had a larger resistance to deformation than Example 1-8, and were excellent in elongation properties.

[0347] [Table 3]

[0348] [Table 4]

[0349] <Examples 2-1 to 2-4> [Preparation of Uncrosslinked Composition] In the first stage, the raw materials shown in Raw Material 1 in Table 5 were mixed for 2 minutes at 140°C using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.). After that, the ram was raised and cleaned, and the mixture was mixed for another minute and then discharged at approximately 150°C to obtain the first stage compound.

[0350] Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; surface temperature of front roll: 50°C; surface temperature of rear roll: 50°C; rotation speed of front roll: 16 rpm; rotation speed of rear roll: 18 rpm), and the raw material shown in raw material 2 in Table 5 was added thereto and kneaded for 10 minutes to obtain the uncrosslinked composition of each example.

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

[0352] [evaluation] The crosslinking behavior of the uncrosslinked composition of each example was measured at a crosslinking temperature of 180°C for a crosslinking time of 15 minutes. The results are shown in Table 5. As shown in Table 5, the molded articles obtained in all examples were found to have excellent physical properties and processability. As shown in Table 5, in all examples, the tc90 was 10 minutes or less, indicating that a sufficient crosslinking rate was obtained during crosslinking.

[0353] Table 5 also shows the results of evaluating the sponge properties of the sheet-like foamed molded products of each example. As shown in Table 5, Examples 2-1 and 2-2, which used sodium bicarbonate 1, had a lower specific gravity than Examples 2-3 and 2-4, which used sodium bicarbonate 2. The water absorption rate was also higher than that of Example 2-3. The results of evaluating the compression set (CS) of the tubular foam molded articles of each example are shown in Table 5. 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 Uncrosslinked Composition of Example 3-1] In the first stage, the raw materials shown in Raw Material 1 in Table 5 were mixed 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 the mixture was mixed for another minute and then discharged at approximately 150°C to obtain the first stage compound.

[0356] Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and the raw material shown in raw material 2 in Table 6 was added thereto. After kneading for 5 minutes, the mixture was separated into ribbons to obtain an uncrosslinked composition.

[0357] [Preparation of Uncrosslinked Compositions of Examples 3-2 and 3-3] In the first stage, the raw materials shown in Raw Material 1 in Table 5 were mixed 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 the mixture was mixed for another minute and then discharged at approximately 150°C to obtain the first stage compound.

[0358] Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and the raw material shown in raw material 2 in Table 6 was added thereto. After kneading for 10 minutes, the mixture was separated into ribbons to obtain the uncrosslinked composition of each example.

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

[0360] [evaluation] For the uncrosslinked composition of each example, the crosslinking behavior (high temperature crosslinking) was measured at a crosslinking temperature of 180°C for a crosslinking time of 15 minutes. The results are shown in Table 6. As shown in Table 6, it was found that the physical properties and processability of the molded articles obtained in all examples were excellent. As shown in Table 6, in all examples, tc90 was 10 minutes or less, indicating that a sufficient crosslinking rate was obtained during crosslinking. The results of evaluating the physical properties of the crosslinked molded body of each example are shown in Table 6. 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 Composition] In the first stage, the raw materials shown in Raw Material 1 in Table 7 were kneaded at 120°C for 5 minutes using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.) to obtain a first stage blend.

[0363] Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; surface temperature of front roll: 50°C; surface temperature of rear roll: 50°C; rotation speed of front roll: 16 rpm; rotation speed of rear roll: 18 rpm), and the raw material shown in raw material 2 in Table 7 was added thereto and kneaded for 5 minutes to obtain the uncrosslinked composition of each example.

[0364] [Preparation of crosslinked molded article of Example 4-1] The uncrosslinked composition was pressed in a mold using a press molding machine at 180°C for 15 minutes to obtain a sheet-like primary crosslinked body having a thickness of 2 mm. The primary crosslinked body was then subjected to secondary crosslinking at 150°C for 16 hours in a high-temperature incubator (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 crosslinked molded article of Example 4-2] The primary crosslinked body obtained in Example 4-1 was used as a crosslinked molded body in Example 4-2.

[0366] [Preparation of crosslinked molded article of Example 4-3] The primary crosslinked body obtained in Example 4-1 was subjected to secondary crosslinking at 180°C for 2 hours in a high-temperature incubator (product name: Horizontal High-Temperature Oven PHH-202, manufactured by Espec Corporation) to obtain a crosslinked molded body of Example 4-3.

[0367] [Preparation of crosslinked molded article of 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 incubator (product name: Horizontal High-Temperature Oven PHH-202, manufactured by Espec Corporation) to obtain a crosslinked molded body of Example 4-4.

[0368] [evaluation] The compression set (CS) and the content of low molecular weight components of the crosslinked molded article of each example were measured. The results are shown in Table 7. As shown in Table 7, the molded articles obtained in all examples were found to have excellent physical properties and processability. In particular, as shown in Table 7, the crosslinked molded body of Example 4-1, which was obtained by carrying out secondary crosslinking for 16 hours in a heat medium maintained at a relatively low temperature of 150°C, had a small compression set and an extremely small content of low molecular weight components.

[0369] [Table 7]

[0370] <Examples 5-1 to 5-6> [Preparation of Uncrosslinked Composition] In the first stage, the raw materials shown in Raw Material 1 in Tables 8 and 9 were kneaded for 10 minutes using an 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm). Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and the raw materials shown as raw material 2 in Tables 8 and 9 were added thereto and kneaded for 10 minutes to obtain the uncrosslinked composition of each example. The Mooney viscosity of the uncrosslinked composition of each example is shown in Tables 8 and 9.

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

[0372] [evaluation] The crosslinking behavior of the uncrosslinked composition of each example was measured at a crosslinking temperature of 170° C. for 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, and it was found that a sufficient crosslinking rate was obtained during crosslinking.

[0373] The physical properties of the crosslinked molded articles of each example were evaluated, and the results are shown in Tables 8 and 9. As shown in Tables 8 and 9, the molded articles obtained in all examples were found to have 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 smaller compression set (CS) than Example 5-6, in which the Mooney viscosity of the uncrosslinked composition was high. The compression set (CS) was evaluated for a sheet-like crosslinked molded product.

[0374] [Table 8]

[0375] [Table 9]

[0376] <Examples 6-1 to 6-7> [Preparation of Uncrosslinked Composition] In the first step, the raw materials shown in Raw Material 1 in Table 10 were kneaded at room temperature for 10 minutes using a defoaming conditioning mixer, Awatori Neritaro (AR-250, manufactured by Thinky Corporation, rotation / revolution propeller-less mixing method). Next, in the second step, the compound obtained in the first step was wound around a three-roll mill (BR-230BV, manufactured by Imex Co., Ltd., roll dimensions: φ86.5 × 230 mmL), and the raw material shown as raw material 2 in Table 10 was added thereto and kneaded at room temperature for 10 minutes to obtain the uncrosslinked composition of each example. The Brookfield viscosity of the uncrosslinked composition of each example is shown in Table 10.

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

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

[0379] The physical properties of the crosslinked molded articles of each example were evaluated, and the results are shown in Table 13. As shown in Table 13, it was found that the molded articles obtained in Examples 6-1 to 6-6 were excellent in physical properties and processability. As shown in Table 13, it was found that Examples 6-1 to 6-6, which used copolymer (S-2), had lower hardness and larger EB than Example 6-7, which used copolymer (A-1).

[0380] [Table 10]

[0381] [Table 11]

[0382] [Table 12]

[0383] [Table 13]

[0384] <Examples 1 to 4> The copolymer compositions of each example were prepared as follows. In the first stage, the raw materials shown in Raw Material 1 in Table 14 were mixed using a BB-4 mixer (manufactured by Kobe Steel, Ltd.). The mixing conditions were a rotor rotation speed of 50 rpm and a floating weight pressure of 3 kg / cm. 2 The kneading time was 5 minutes, and the discharge temperature was 150°C to obtain a first-stage compound.

[0385] Next, in the second step, the compound obtained in the first step was wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd.; front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 18 rpm, rear roll rotation speed 15 rpm), and the raw material shown in raw material 2 in Table 14 was added thereto and kneaded for 5 minutes to obtain an uncrosslinked copolymer composition.

[0386] [evaluation] The copolymer composition of each example was evaluated for odor. In addition, the crosslinking rate and the physical properties of the crosslinked molded article were measured and evaluated. The results are shown in Table 14. As shown in Table 14, it was found that the molded articles obtained in all examples had excellent physical properties and processability. As shown in Table 14, in Examples 1 to 4 in which the hydrosilyl group-containing compound (Y-1-1) was used, the "180°C (tc90) min" was not excessively large, and the "125°C (TS1) min" was approximately 20 minutes or more, and sufficient scorch resistance was obtained while maintaining a moderate crosslinking rate.

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

[0388] [Table 14] [Industrial Applicability]

[0389] According to the present invention, there are provided an ethylene-α-olefin-non-conjugated polyene copolymer composition which is excellent in terms of the physical properties and processability of the resulting molded article, an expanded 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); a hydrosilyl group-containing compound (Y); and A copolymer composition comprising a platinum-based catalyst, The copolymer (S) has a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing, in the molecule, two or more partial structures in total, at least one of which is selected from the following formula (I) and the following formula (II), and satisfies the following requirements (i) and (ii): The hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule: the requirement (i) being that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; a copolymer composition in which the requirement (ii) is satisfied, the mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass % based on the total mass of the structural units constituting the copolymer (S); 【Chemistry 1】 【Chemistry 2】 In formula (a), n and p are each independently 0 or a positive number, m is a number ranging from 1 to 20, the sum of n, m, and p is 5 to 50, and a plurality of R １ and R ２ are each independently a monovalent alkyl group, and R ａ is an aralkyl group, and two R are each independently R １ , R ２ , a hydrogen atom, and R ａ These structural units may be arranged in blocks or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

2. Further, the composition contains a sodium bicarbonate-based foaming agent that satisfies the following requirement (b): The requirement (b) is that the cumulative 10% unevenness in a cumulative distribution curve based on the number of unevenness is 0.9 or less, and the cumulative 90% equivalent circle diameter in a cumulative distribution curve based on the number of equivalent circle diameters is 43 μm or more, wherein the irregularity is a ratio of the envelope perimeter to the perimeter measured by dynamic image analysis using methyl ethyl ketone as a dispersion solvent, and the equivalent circle diameter is a 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 a dispersion solvent.

3. 3. The copolymer composition according to claim 2, comprising, relative to 100 parts by mass of the copolymer (S), 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.

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

5. The copolymer composition according to any one of claims 2 to 4, further comprising 0.07 to 10 parts by mass of a hindered phenol-based antioxidant per 100 parts by mass of the copolymer (S).

6. A foamed molded article comprising a foam obtained by crosslinking and foaming the copolymer composition according to any one of claims 2 to 5.

7. A method for producing a foamed molded article, comprising melt-extruding the copolymer composition according to any one of claims 2 to 5 and crosslinking the composition.

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: Further, the copolymer (S) 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, relative to 100 parts by mass of the copolymer (S), a composition obtained by mixing the hydrosilyl group-containing compound (Y), the platinum-based catalyst, and components other than the reaction inhibitor has a Mooney viscosity "ML(1+4)100°C" of 8 to 200 as determined by the method described in JIS K 6300-1:2013; The requirement (iii) is calculated by the following formula (1) (n Ｃ ) is 4.5 or more and 40 or less, (n Ｃ ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω=0.1 rad / s obtained by linear viscoelasticity measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa sec) and the complex viscosity η at a frequency ω = 100 rad / s ＊ （ω＝１００） (Pa sec) 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] ２．９ ) ≦ mass percent concentration of (C) × 6 Equation (2) The requirement (v) is satisfied by the number of long chain branches (LCB) per 1,000 carbon atoms obtained by 3D-GPC. １０００Ｃ 2. The copolymer composition according to claim 1, wherein the weight average molecular weight (Mw) of the copolymer (1) satisfies the following formula (3): LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3).

9. A crosslinked molded article obtained by crosslinking the copolymer composition according to claim 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: further comprising 10 to 100 parts by mass of a paraffinic process oil relative to 100 parts by mass of the copolymer (S); The Mooney viscosity "ML(1+4)100°C" determined by the method described in JIS K 6300-1:2013 is 0.1 to 8, The requirement (iii) is calculated by the following formula (1) (n Ｃ ) is 4.5 or more and 40 or less, (n Ｃ ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω=0.1 rad / s obtained by linear viscoelasticity measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa sec) and the complex viscosity η at a frequency ω = 100 rad / s ＊ （ω＝１００） (Pa sec) 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] ２．９ ) ≦ mass percent concentration of (C) × 6 Equation (2) The requirement (v) is satisfied by the number of long chain branches (LCB) per 1,000 carbon atoms obtained by 3D-GPC. １０００Ｃ 2. The copolymer composition according to claim 1, wherein the weight average molecular weight (Mw) of the copolymer (1) satisfies the following formula (3): LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3).

11. A crosslinked molded article obtained by crosslinking the copolymer composition according to claim 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: further comprising 0.1 to 200 parts by mass of carbon black and 100 to 400 parts by mass of paraffinic process oil relative to 100 parts by mass of the copolymer (S); The Brookfield rotational viscosity at 25°C determined by the method described in JIS K 7117:1999 is 6000 Pa s or less, The requirement (iii) is calculated by the following formula (1) (n Ｃ ) is 4.5 or more and 40 or less, (n Ｃ ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω=0.1 rad / s obtained by linear viscoelasticity measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa sec) and the complex viscosity η at a frequency ω = 100 rad / s ＊ （ω＝１００） (Pa sec) 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] ２．９ ) ≦ mass percent concentration of (C) × 6 Equation (2) The requirement (v) is satisfied by the number of long chain branches (LCB) per 1,000 carbon atoms obtained by 3D-GPC. １０００Ｃ 2. The copolymer composition according to claim 1, wherein the weight average molecular weight (Mw) of the copolymer (1) satisfies the following formula (3): LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3).

13. A crosslinked molded article obtained by crosslinking the copolymer composition according to claim 12.

14. Furthermore, a reaction inhibitor, and an 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 requirement (iii) is calculated by the following formula (1) (n Ｃ ) is 4.5 or more and 40 or less, (n Ｃ ) = (Mw) × {mass percent concentration of (C) / 100} / molecular weight of (C) (1) In formula (1), (Mw) is the weight average molecular weight of the copolymer (S), the mass percent concentration of (C) is the content (mass%) of structural units derived from the non-conjugated polyene (C) relative to the total mass of structural units constituting the copolymer (S), and the molecular weight of (C) is the molecular weight of the non-conjugated polyene (C). The requirement (iv) is a complex viscosity η at a frequency ω=0.1 rad / s obtained by linear viscoelasticity measurement (190°C) using a rheometer. ＊ （ω＝０．１） (Pa sec) and the complex viscosity η at a frequency ω = 100 rad / s ＊ （ω＝１００） (Pa sec) 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) (the content (mass%) of the structural units derived from the non-conjugated polyene (C) relative to the total mass of the structural units constituting the copolymer (S)) satisfy the following formula (2): P / ([η] ２．９ ) ≦ mass percent concentration of (C) × 6 Equation (2) The requirement (v) is satisfied by the number of long chain branches (LCB) per 1,000 carbon atoms obtained by 3D-GPC. １０００Ｃ 2. The copolymer composition according to claim 1, wherein the weight average molecular weight (Mw) of the copolymer (1) satisfies the following formula (3): LCB １０００Ｃ ≦1-0.07×Ln(Mw)・・・Equation (3).

15. 15. The copolymer composition according to claim 14, comprising, relative to 100 parts by mass of the copolymer (S), 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.

16. A crosslinked molded article obtained by crosslinking the copolymer composition according to claim 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 a first-stage blend; and 16. A method for producing the copolymer composition according to any one of claims 1 to 5, 8, 10, 12, 14 and 15, comprising adding a platinum-based catalyst to the first-stage blend and kneading the mixture at 10 to 130°C for 1 to 30 minutes to obtain a second-stage blend, The copolymer (S) has a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing, in the molecule, two or more partial structures in total, at least one of which is selected from the following formula (I) and the following formula (II), and satisfies the following requirements (i) and (ii): The hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule: the requirement (i) being that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; a production method in which the requirement (ii) is satisfied, wherein the mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass% based on the total mass of the structural units constituting 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 ranging from 1 to 20, the sum of n, m, and p is 5 to 50, and a plurality of R １ and R ２ are each independently a monovalent alkyl group, and R ａ is an aralkyl group, and two R are each independently R １ , R ２ , a hydrogen atom, and R ａ These structural units may be arranged in blocks or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

18. The method for producing a copolymer composition according to claim 17, 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 relative to 100 parts by mass of the copolymer (S).

19. A crosslinked molded article obtained by crosslinking the copolymer composition obtained by the production method according to claim 17 or 18.

20. obtaining a kneaded product comprising the copolymer composition according to any one of claims 1 to 5, 8, 10, 12, 14, and 15 by melt-kneading the copolymer (S), the hydrosilyl group-containing compound (Y), and the platinum-based catalyst; The kneaded mixture is press-molded at 120 to 200°C for 1 to 20 minutes to perform primary crosslinking, thereby obtaining a primary molded body; and A method for producing a crosslinked molded body, comprising: heating the primary molded body in a heat medium at 120 to 160°C for 10 to 24 hours to perform secondary crosslinking; The copolymer (S) has a structural unit derived from ethylene (A), a structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (C) containing, in the molecule, two or more partial structures in total, at least one of which is selected from the following formula (I) and the following formula (II), and satisfies the following requirements (i) and (ii): The hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane represented by the following formula (a) and having at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in the molecule: the requirement (i) being that the ratio [A] / [B] of the number of moles of structural units derived from ethylene (A) to the number of moles [B] of structural units derived from an α-olefin having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; a production method in which the requirement (ii) is satisfied, wherein the mass percent concentration of the structural units derived from the non-conjugated polyene (C) is 0.07 to 10 mass% based on the total mass of the structural units constituting 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 ranging from 1 to 20, the sum of n, m, and p is 5 to 50, and a plurality of R １ and R ２ are each independently a monovalent alkyl group, and R ａ is an aralkyl group, and two R are each independently R １ , R ２ , a hydrogen atom, and R ａ These structural units may be arranged in blocks or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

21. The method for producing a crosslinked molded article according to claim 20, 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 relative to 100 parts by mass of the copolymer (S).

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