Silane-modified hydrogenated block copolymer, polymer composition, and crosslinked product

Abstract

The present invention provides a silane-modified hydrogenated block copolymer which has a silane-containing functional group, and which is obtained by modifying a hydrogenated block copolymer (A) represented by general formula (A) with an unsaturated silane modifier.　(A): Ar1a-HDa-Ar2a (In general formula (A), the ratio (Mw(Ar2a) / Mw(Ar1a)) of the weight average molecular weight (Mw(Ar2a)) of Ar2a to the weight average molecular weight (Mw(Ar1a)) of Ar1a is 3.0 to 20.)

Description

Silane-modified hydrogenated block copolymer, polymer composition and crosslinked product

[0001] The present invention relates to a silane-modified hydrogenated block copolymer, a polymer composition, and a crosslinked product.

[0002] Aromatic vinyl-conjugated diene-aromatic vinyl block copolymers, such as styrene-isoprene-styrene block copolymer (SIS) and styrene-butadiene-styrene block copolymer (SBS), are thermoplastic elastomers with characteristic properties in various aspects and are therefore used in a variety of applications.

[0003] For example, Patent Document 1 discloses a hydrogenated block copolymer having, in its molecule, a polymer block (C) mainly composed of a conjugated diene compound, a polymer block (B) mainly composed of a conjugated diene compound, and a polymer block (S) mainly composed of an aromatic vinyl compound, wherein the polymer block (B) comprises polymer blocks (B1) and (B2), the content of the polymer block (C) in the hydrogenated block copolymer is 1 to 20% by mass, the content of the polymer block (B) is 73 to 97% by mass, and the content of the polymer block (S) is 1 to 15% by mass, the vinyl bond content of the polymer block (C) before hydrogenation is 1 to 25 mol%, the vinyl bond content of the polymer block (B1) is 40 to 60 mol%, and the vinyl bond content of the polymer block (B2) is 60 to 100 mol%, and the hydrogenation rate is 80 mol% or more. However, the hydrogenated block copolymer obtained by the technology of Patent Document 1 is required to have improved compression recovery.

[0004] International Publication No. 2017 / 188190

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a block copolymer having excellent compression recovery properties.

[0006] The present inventors have conducted studies to achieve the above-mentioned object, and have found that the above-mentioned object can be achieved by a block copolymer having a skeleton derived from a hydrogenated block copolymer (A) represented by a specific general formula (A) and having a silane-containing functional group, thereby completing the present invention.

[0007] That is, according to the present invention, there is provided the following silane-modified hydrogenated block copolymer.

[0008] [1] A silane-modified hydrogenated block copolymer having a silane-containing functional group, obtained by modifying a hydrogenated block copolymer (A) represented by the following general formula (A) with an unsaturated silane modifier: Ar1 ａ -HD ａ -Ar2 ａ (A) (In the above general formula (A), Ar1 ａ and Ar2 ａ is an aromatic vinyl polymer block, and HD ａ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 ａ Weight average molecular weight (Mw(Ar1 ａ )) with respect to Ar2 ａ Weight average molecular weight (Mw(Ar2 ａ )) ratio (Mw(Ar2 ａ ) / Mw(Ar1 ａ [2] The silane-modified hydrogenated block copolymer according to [1], wherein the hydrogenation rate of olefin in the hydrogenated block copolymer (A) is 10 to 100%. [3] The silane-containing functional group is added to the hydrogenated polymer block HD of the conjugated diene polymer. ａ The silane-modified hydrogenated block copolymer according to [1] or [2], wherein Ar1 has, as a side chain, a silane-modified hydrogenated block copolymer. [4] The silane-modified hydrogenated block copolymer according to any one of [1] to [3], wherein the content of aromatic vinyl monomer units in the hydrogenated block copolymer (A) is 20 to 90% by weight based on the total monomer units. [5] The silane-modified hydrogenated block copolymer according to any one of [1] to [4], wherein the weight-average molecular weight of the hydrogenated block copolymer (A) is 20,000 to 500,000. [6] In the above general formula (A), Ar1 ａThe weight average molecular weight of Ar2 is 1,000 to 40,000. ａ The weight average molecular weight of HD is 5,000 to 250,000. ａ [7] The silane-modified hydrogenated block copolymer according to any one of [1] to [6], wherein the unsaturated silane modifier is a compound (1) represented by the following general formula (1): (In the above general formula (1), R １ ~R ３ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R ４ is a hydrocarbon group having a carbon-carbon unsaturated bond. [8] In the above general formula (1), R １ ~R ３ [8] The silane-modified hydrogenated block copolymer according to [7], wherein at least one of the groups is an alkoxy group having 1 to 6 carbon atoms.

[0009] The present invention also provides the following polymer composition and crosslinked product: [9] A polymer composition comprising: the silane-modified hydrogenated block copolymer (A-Si) according to any one of [1] to [8]; and a silane-modified hydrogenated block copolymer (B-Si) having a silane-containing functional group, which is obtained by modifying a hydrogenated block copolymer (B) represented by the following general formula (B) with an unsaturated silane modifier. Ar1 ｂ -HD ｂ -Ar2 ｂ (B) (In the above general formula (B), Ar1 ｂ and Ar2 ｂ is an aromatic vinyl polymer block, and HD ｂ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 ｂ Weight average molecular weight (Mw(Ar1 ｂ )) with respect to Ar2 ｂ Weight average molecular weight (Mw(Ar2 ｂ )) ratio (Mw(Ar2 ｂ ) / Mw(Ar1 ｂ)) is 0.95 to 1.05.

[10] The polymer composition according to [9], obtained by modifying a hydrogenated block copolymer composition containing the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) with the unsaturated silane modifier.

[11] A crosslinked product obtained by crosslinking the silane-modified hydrogenated block copolymer according to any one of [1] to [8] or the polymer composition according to any one of [9] to

[10] .

[12] The crosslinked product according to

[11] , having a crosslinked structure derived from the silane-containing functional group.

[13] The crosslinked product according to

[11] or

[12] , wherein the crosslinked structure contains a —Si—O—Si— bond.

[14] The crosslinked product according to any one of

[11] to

[13] , having a melt flow rate of 0.05 to 100 g / 10 min as measured in accordance with ISO 1133 (G condition, 200°C, 5 kg).

[15] The crosslinked product according to any one of

[11] to

[14] , which is a cushioning material, a weather strip, an impact absorbing material, a glass interlayer film, a shoe sole, or a sealing material.

[0010] According to the present invention, a block copolymer having excellent compression recovery properties can be provided.

[0011] <Silane-Modified Hydrogenated Block Copolymer (A-Si)> The silane-modified hydrogenated block copolymer (A-Si) of the present invention is a block copolymer obtained by modifying the hydrogenated block copolymer (A) described below with an unsaturated silane modifier, and is a block copolymer having a silane-containing functional group. The silane-modified hydrogenated block copolymer (A-Si) of the present invention has a skeleton derived from the hydrogenated block copolymer (A) represented by specific general formula (A) and has a silane-containing functional group, thereby enabling it to exhibit excellent compression recovery. Furthermore, the silane-modified hydrogenated block copolymer (A-Si) of the present invention also has excellent moldability and transparency.

[0012] (Hydrogenated Block Copolymer (A)) The hydrogenated block copolymer (A) is a block copolymer represented by the following general formula (A): ａ -HD ａ -Ar2 ａ (A) (In the above general formula (A), Ar1 ａ and Ar2 ａis an aromatic vinyl polymer block, and HD ａ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 ａ Weight average molecular weight (Mw(Ar1 ａ )) with respect to Ar2 ａ Weight average molecular weight (Mw(Ar2 ａ )) ratio (Mw(Ar2 ａ ) / Mw(Ar1 ａ )) is 3.0 to 20.

[0013] Aromatic vinyl polymer block Ar1 of hydrogenated block copolymer (A) ａ and Ar2 ａ is a polymer block composed of aromatic vinyl monomer units.

[0014] The aromatic vinyl monomer used to form the aromatic vinyl monomer unit is not particularly limited as long as it is an aromatic vinyl compound. Examples of aromatic vinyl compounds include styrene; alkyl-substituted styrenes such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, and 5-t-butyl-2-methylstyrene; halogen-substituted styrenes such as 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl-4,6-dichlorostyrene, and 2,4-dibromostyrene; and vinylnaphthalene. Among these, styrene is preferred. These aromatic vinyl monomers can be used alone or in combination of two or more in each aromatic vinyl polymer block. Furthermore, the same aromatic vinyl monomer may be used in each aromatic vinyl polymer block, or different aromatic vinyl monomers may be used.

[0015] The content of aromatic vinyl monomer units in each aromatic vinyl polymer block is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably substantially 100% by weight, based on the total weight of the aromatic vinyl polymer block.

[0016] Aromatic vinyl polymer block Ar1 ａ and Ar2 ａ may each contain a monomer unit other than an aromatic vinyl monomer unit. Examples of monomers constituting the monomer units other than aromatic vinyl monomer units include conjugated diene monomers such as 1,3-butadiene and isoprene (2-methyl-1,3-butadiene); α,β-unsaturated nitrile monomers; unsaturated carboxylic acid or acid anhydride monomers; unsaturated carboxylic acid ester monomers; and non-conjugated diene monomers. The content of monomer units other than aromatic vinyl monomer units in each aromatic vinyl polymer block is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably substantially 0% by weight, based on the total weight of the aromatic vinyl polymer block.

[0017] Hydrogenated polymer block HD of conjugated diene polymer in hydrogenated block copolymer (A) ａ is a polymer block constituted by conjugated diene monomer units, and at least a portion of the conjugated diene monomer units constituting the polymer block are hydrogenated.

[0018] The conjugated diene monomer used to form the conjugated diene monomer unit is not particularly limited as long as it is a conjugated diene compound. Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Among these, from the viewpoint of polymerization reactivity, it is preferable to use 1,3-butadiene and / or isoprene, and it is particularly preferable to use isoprene. These conjugated diene monomers can be used alone or in combination of two or more.

[0019] Hydrogenated polymer block HD of conjugated diene polymer ａ The content of the conjugated diene monomer unit (including the hydrogenated conjugated diene monomer unit) in the hydrogenated polymer block HD of the conjugated diene polymer ａ It is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably substantially 100% by weight, based on the total weight.

[0020] Hydrogenated polymer block HD of conjugated diene polymer ａ may contain a monomer unit other than the conjugated diene monomer unit. Examples of the monomer constituting the monomer unit other than the conjugated diene monomer unit include aromatic vinyl monomers such as styrene and α-methylstyrene; α,β-unsaturated nitrile monomers; unsaturated carboxylic acid or acid anhydride monomers; unsaturated carboxylic acid ester monomers; and non-conjugated diene monomers. The hydrogenated polymer block HD of the conjugated diene polymer ａ The content of monomer units other than conjugated diene monomer units (including hydrogenated conjugated diene monomer units) in the hydrogenated polymer block HD of the conjugated diene polymer is ａ The content is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably substantially 0% by weight, based on the total weight.

[0021] The hydrogenated block copolymer (A) is Ar1 ａ Weight average molecular weight (Mw(Ar1 ａ )) with respect to Ar2 ａ Weight average molecular weight (Mw(Ar2 ａ )) ratio (Mw(Ar2 ａ ) / Mw(Ar1 ａ )) is in the range of 3.0 to 20. Therefore, the hydrogenated block copolymer (A) contains an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight. ａ , hydrogenated polymer block HD of conjugated diene polymer ａ and an aromatic vinyl polymer block Ar2 having a relatively large weight average molecular weight ａ It is a hydrogenated product of an asymmetric aromatic vinyl-conjugated diene-aromatic vinyl block copolymer composed of these units linked in this order.

[0022] In the hydrogenated block copolymer (A), Mw(Ar2 ａ ) / Mw(Ar1 ａ ) is in the range of 3.0 to 20. ａ ) / Mw(Ar1 ａ ) is preferably in the range of 4.0 to 16, more preferably in the range of 5.0 to 13. ａ ) / Mw(Ar1 ａ By setting the molecular weight (Mw) and number average molecular weight (Mn) of the polymer or polymer block to the above range, the compression recovery can be further improved, and the moldability, transparency, and compression set resistance can also be improved. In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer or polymer block are determined as polystyrene-equivalent values ​​measured by high performance liquid chromatography.

[0023] The hydrogenation rate of the olefin in the hydrogenated block copolymer (A) is preferably 10 to 100%, more preferably 50 to 100%, even more preferably 80 to 100%, particularly preferably 90 to 100%, and most preferably 95 to 100%. By setting the hydrogenation rate of the olefin within the above range, the silane-modified hydrogenated block copolymer (A-Si) can be made to have excellent compression recovery and compression set resistance. Here, the hydrogenation rate of the olefin specifically refers to the proportion (mol %) of hydrogenated non-aromatic carbon-carbon double bonds contained in the hydrogenated block copolymer (A) before hydrogenation. The hydrogenation rate of the olefin can be determined by the following method: １ It can be determined by H-NMR spectrum measurement.

[0024] The content of aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (A) is not particularly limited, but is preferably 20 to 90% by weight, more preferably 30 to 90% by weight, even more preferably 40 to 85% by weight, and particularly preferably 45 to 85% by weight. By setting the content of aromatic vinyl monomer units within the above range, compression recovery can be further improved, and moldability, transparency, and compression set resistance can also be improved. The content of aromatic vinyl monomer units can be determined based on the detection intensity ratio between a differential refractometer and an ultraviolet detector in high-performance liquid chromatography measurements.

[0025] The weight-average molecular weight of the hydrogenated block copolymer (A) is not particularly limited, but is preferably 20,000 to 500,000, more preferably 25,000 to 300,000, and even more preferably 30,000 to 150,000. By setting the weight-average molecular weight within the above range, it is possible to further improve compression recovery, and also to improve moldability, transparency, and compression set resistance.

[0026] Aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight, which constitutes the hydrogenated block copolymer (A) ａ Weight average molecular weight (Mw(Ar1 ａ )) is preferably 1,000 to 40,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 8,000. ａ By setting the value of (a) to be within the above range, the compression recovery can be further improved, and the moldability, transparency and resistance to compression set can also be improved.

[0027] The aromatic vinyl polymer block Ar2 having a relatively large weight average molecular weight that constitutes the hydrogenated block copolymer (A) ａ Weight average molecular weight (Mw(Ar2 ａ )) is preferably 5,000 to 250,000, more preferably 10,000 to 120,000, and even more preferably 20,000 to 80,000. ａBy setting the value of (a) to be within the above range, the compression recovery can be further improved, and the moldability, transparency and resistance to compression set can also be improved.

[0028] The hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (A) ａ Weight average molecular weight (Mw(HD ａ )) is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, even more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000. ａ By setting the value of (a) to be within the above range, the compression recovery can be further improved, and the moldability, transparency and resistance to compression set can also be improved.

[0029] The hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (A) ａ The vinyl bond content (the proportion of 1,2-vinyl bonds and 3,4-vinyl bonds in all conjugated diene monomer units) is preferably 1 to 80 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 12 mol %. By setting the vinyl bond content within the above range, it is possible to further improve the compression recovery, and also to improve the moldability, transparency, and compression set resistance. The vinyl bond content of the hydrogenated polymer block of the conjugated diene polymer can be determined by the following method: １ It can be determined by H-NMR.

[0030] The molecular weight distribution of the hydrogenated block copolymer (A) and of each polymer block constituting the hydrogenated block copolymer (A), expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) [(Mw) / (Mn)], is not particularly limited, but is preferably 1.1 or less, and more preferably 1.05 or less.

[0031] (Silane-Containing Functional Group) The silane-modified hydrogenated block copolymer (A-Si) of the present invention is a block copolymer obtained by modifying the hydrogenated block copolymer (A) with an unsaturated silane modifier. The silane-modified hydrogenated block copolymer (A-Si) of the present invention has a silane-containing functional group as a modifying group derived from the unsaturated silane modifier. The silane-modified hydrogenated block copolymer (A-Si) of the present invention may have one type of silane-containing functional group, or may have two or more types of silane-containing functional groups.

[0032] Here, when the hydrogenated block copolymer (A) is modified with an unsaturated silane modifier, the hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (A) is usually ａ The carbon atoms in the polymer and the unsaturated silane modifier act to form a hydrogenated polymer block HD of the conjugated diene polymer. ａ In this case, the silane-modified hydrogenated block copolymer (A-Si) of the present invention has a silane-containing functional group introduced as a side chain between the hydrogenated polymer block HD of the conjugated diene polymer and the ... ａ It has it as a side chain.

[0033] The unsaturated silane modifier used in the present invention is not particularly limited as long as it is a silane compound containing a carbon-carbon unsaturated bond in the molecule, but is preferably a compound (1) represented by the following general formula (1): (In the above general formula (1), R １ ~R ３ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R ４ is a hydrocarbon group having a carbon-carbon unsaturated bond.

[0034] In general formula (1), R １ ~R ３ are not particularly limited as long as they are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. １ ~R ３ The alkyl group and alkoxy group represented by R may be linear, branched, or may contain a cyclic structure. ２ ~R ４may be the same or different.

[0035] R １ ~R ３ As R, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms are preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred. １ ~R ３ The number of carbon atoms in each of R may be independently 0 to 6, preferably 0 to 4, more preferably 0 to 2, and even more preferably 1 (methyl group or methoxy group). １ ~R ３ By having the above structure, the compression recovery can be further improved, and the moldability, transparency, and resistance to compression set can also be improved.

[0036] In general formula (1), R １ ~R ３ At least one of R is preferably an alkoxy group having 1 to 6 carbon atoms, １ ~R ３ It is more preferable that at least two of R are alkoxy groups having 1 to 6 carbon atoms. １ ~R ３ It is more preferable that all of the groups are alkoxy groups having 1 to 6 carbon atoms.

[0037] In general formula (1), R ４ is not particularly limited as long as it is a hydrocarbon group having a carbon-carbon unsaturated bond. ４ R may be linear, branched, or may contain a cyclic structure. ４ Examples of R include vinyl group-containing hydrocarbon groups such as vinyl group, allyl group, 1-methylethenyl group, and 3-butenyl group; and alkynyl groups such as propynyl group, with vinyl group-containing hydrocarbon groups being preferred. ４ The number of carbon atoms in R is not particularly limited, but is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 (vinyl group). ４ By having the above structure, the compression recovery can be further improved, and the moldability, transparency, and resistance to compression set can also be improved.

[0038] For example, R４ is a vinyl group-containing hydrocarbon group, the compound (1) is a compound (2) represented by the following general formula (2):

[0039] In the above general formula (2), R １ ~R ３ are the groups described above, and R ５ is a single bond or a divalent hydrocarbon group. ５ The hydrocarbon group as -R in general formula (2) may be linear, branched, or may contain a cyclic structure. ５ -CH=CH ２ represents -R in general formula (1). ４ Corresponds to.

[0040] For example, when compound (2) is used as the unsaturated silane modifier, the silane-modified hydrogenated block copolymer (A-Si) of the present invention has a group (3) (silane-containing functional group) represented by the following general formula (3) as a modifying group derived from compound (2):

[0041] The unsaturated silane modifier is preferably a compound (4) represented by the following general formula (4).

[0042] In general formula (4), R ６ ~R ８ are each independently an alkyl group having 1 to 6 carbon atoms, and R ９ is a single bond or an alkylene group having 1 to 4 carbon atoms. ６ , -OR ７ , and -OR ８ represents -R in the general formulas (1) to (3), respectively. １ , -R ２ , and -R ３ corresponds to R in general formula (4) ９ represents R in general formulas (2) and (3). ５ Corresponds to.

[0043] R ６ ~R ８ Each of R may be linear, branched, or may contain a cyclic structure.６ ~R ８ may be the same or different. ６ ~R ８ may each independently have 1 to 6 carbon atoms, preferably 1 to 4, more preferably 1 or 2 (methyl group, ethyl group), and even more preferably 1 (methyl group).

[0044] R ９ R may be linear, branched, or may contain a cyclic structure. ９ The number of carbon atoms may be 0 to 4, preferably 0 to 2, more preferably 0 or 1, and even more preferably 0 (single bond).

[0045] The amount of silane-containing functional groups in the silane-modified hydrogenated block copolymer (A-Si) of the present invention is not particularly limited. The amount of silane-containing functional groups per 100 g of the silane-modified hydrogenated block copolymer (A-Si) of the present invention is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and even more preferably 1 to 30 mmol. By setting the amount of silane-containing functional groups within the above range, compression recovery can be further improved, and moldability, transparency, and compression set resistance can also be improved.

[0046] (Method for Producing Silane-Modified Hydrogenated Block Copolymer (A-Si)) The silane-modified hydrogenated block copolymer (A-Si) of the present invention can be produced by a production method including a modification step of reacting the hydrogenated block copolymer (A) with an unsaturated silane modifier.

[0047] The hydrogenated block copolymer (A) used in the present invention can be produced, for example, by combining a conventional method for producing a block copolymer and a hydrogenation method. The method for producing the hydrogenated block copolymer (A) used in the present invention is preferably a production method comprising the following steps (1A) to (5A): (1A): A step of polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active end. (2A): A step of adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having an active end obtained in the step (1A) above and polymerizing the conjugated diene monomer to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having an active end. (3A): A step of adding an aromatic vinyl monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active end obtained in the step (2A) above and polymerizing the aromatic vinyl monomer to obtain a solution containing a block copolymer (A'). (4A): A step of hydrogenating the solution containing the block copolymer (A') obtained in the step (3A) above to obtain a solution containing a hydrogenated block copolymer (A). (5A): A step of recovering the hydrogenated block copolymer (A) from the solution containing the hydrogenated block copolymer (A) obtained in the step (4A).

[0048] <Step (1A)> In the above production method, first, in step (1A), an aromatic vinyl monomer is polymerized in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active end.

[0049] The polymerization initiator may be any polymerization initiator known to have anionic polymerization activity for aromatic vinyl monomers and conjugated diene monomers, such as organic alkali metal compounds, organic alkaline earth metal compounds, and organic lanthanoid series rare earth metal compounds.

[0050] As the organic alkali metal compound, an organic lithium compound having one or more lithium atoms in the molecule is particularly preferably used. Specific examples of the organic alkali metal compound include organic monolithium compounds such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dialkylaminolithium, diphenylaminolithium, and ditrimethylsilylaminolithium; organic dilithium compounds such as methylenedilithium, tetramethylenedilithium, hexamethylenedilithium, isoprenyldilithium, and 1,4-dilithio-ethylcyclohexane; and organic trilithium compounds such as 1,3,5-trilithiobenzene. Among these, organic monolithium compounds are particularly preferably used.

[0051] Examples of organic alkaline earth metal compounds include n-butyl magnesium bromide, n-hexyl magnesium bromide, ethoxy calcium, calcium stearate, t-butoxy strontium, ethoxy barium, isopropoxy barium, ethylmercapto barium, t-butoxy barium, phenoxy barium, diethylamino barium, barium stearate, and ethyl barium.

[0052] In addition to the above, a catalyst that forms a homogeneous system in an organic solvent and has living polymerizability, such as a composite catalyst comprising a lanthanoid series rare earth metal compound containing neodymium, samarium, gadolinium, etc. / alkylaluminum / alkylaluminum halide / alkylaluminum hydride, or a metallocene catalyst containing titanium, vanadium, samarium, gadolinium, etc., can also be used.

[0053] The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited and may be determined depending on the target molecular weight, but is preferably 0.01 to 20 mmol, more preferably 0.05 to 15 mmol, and even more preferably 0.1 to 10 mmol, per 100 g of the total monomers used in the polymerization.

[0054] The solvent used in the polymerization is not particularly limited as long as it is inert to the polymerization initiator, and examples thereof include chain hydrocarbon solvents, cyclic hydrocarbon solvents, and mixed solvents thereof. Examples of chain hydrocarbon solvents include chain alkanes and alkenes having 4 to 6 carbon atoms, such as n-butane, isobutane, 1-butene, isobutylene, trans-2-butene, cis-2-butene, 1-pentene, trans-2-pentene, cis-2-pentene, n-pentane, isopentane, neo-pentane, and n-hexane. Examples of cyclic hydrocarbon solvents include aromatic compounds such as benzene, toluene, and xylene; alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane; and the like. These solvents may be used alone or in combination of two or more.

[0055] The amount of the solvent used is not particularly limited, but is preferably an amount such that the concentration of the total block copolymer in the solution after the polymerization reaction is 5 to 60% by weight, more preferably 10 to 55% by weight, and even more preferably 20 to 50% by weight.

[0056] Furthermore, when producing the hydrogenated block copolymer (A), a Lewis base compound may be added to the reaction system in order to control the structure of each polymer block. Examples of the Lewis base compound include ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; tertiary amines such as tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxides such as potassium t-amyl oxide and potassium t-butyl oxide; and phosphines such as triphenylphosphine. These Lewis base compounds may be used alone or in combination of two or more.

[0057] In producing the hydrogenated block copolymer (A), the timing of adding the Lewis base compound is not particularly limited and may be appropriately determined depending on the desired structure. For example, the Lewis base compound may be added in advance before the start of polymerization.

[0058] The polymerization reaction temperature is preferably 10 to 150° C., more preferably 30 to 130° C., and even more preferably 40 to 90° C. The polymerization time is preferably 48 hours or less, more preferably 0.5 to 10 hours. The polymerization pressure is not particularly limited as long as it is within a pressure range sufficient to maintain the monomer and solvent in a liquid phase at the polymerization temperature.

[0059] Under the above conditions, an aromatic vinyl monomer is polymerized in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active end. The aromatic vinyl polymer having an active end obtained in step (1A) in this manner is obtained by polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator under the above conditions. The aromatic vinyl polymer having an active end obtained in step (1A) is obtained by polymerizing an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight of the hydrogenated block copolymer (A). ａ or Ar2 ａ Therefore, the polymerization conditions in step (1A), including the amount of the aromatic vinyl monomer, may be determined depending on the target weight average molecular weight of these polymer blocks, etc.

[0060] <Step (2A)> Next, in step (2A), a conjugated diene monomer is added to the solution containing the aromatic vinyl polymer having active ends obtained in step (1A), and the conjugated diene monomer is polymerized to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends.

[0061] According to the step (2A), by adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having active ends obtained in the step (1A), a conjugated diene polymer chain is formed starting from the active ends, thereby obtaining a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends.

[0062] The conjugated diene polymer chain formed in step (2A) (the conjugated diene block constituting the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2A)) is a hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (A). ａ Therefore, the polymerization conditions in step (2A), including the amount of the conjugated diene polymer, may be determined depending on the target weight average molecular weight of the polymer block, etc. (For example, the polymerization conditions may be determined within the ranges explained in step (1A) above).

[0063] <Step (3A)> Next, in step (3A), an aromatic vinyl monomer is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2A), and the aromatic vinyl monomer is polymerized to obtain a solution containing block copolymer (A').

[0064] According to the step (3A), by adding an aromatic vinyl monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active end obtained in the step (2A), an aromatic vinyl polymer chain is formed starting from the active end, thereby obtaining a solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end.

[0065] The aromatic vinyl polymer chain formed in step (3A) (the aromatic vinyl block constituting the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end obtained in step (3A)) is the aromatic vinyl polymer block Ar1 of the hydrogenated block copolymer (A). ａ , Ar2 ａ One of (i.e., Ar1 ａ or Ar2 ａ is a block different from the block formed in step (1A), for example, Ar1 ａ When the compound is formed, Ar2 ａTherefore, the polymerization conditions in step (3A), including the amount of aromatic vinyl monomer, may be determined depending on the target weight-average molecular weight of the polymer block, etc. (for example, the polymerization conditions may be determined within the ranges explained in step (1A) above).

[0066] A polymerization terminator is added to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends obtained as described above to deactivate the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer, thereby obtaining a solution containing block copolymer (A'). Note that block copolymer (A') obtained in step (3A) is the block copolymer before hydrogenation for obtaining hydrogenated block copolymer (A).

[0067] The polymerization terminator can react with an active terminal to deactivate the active terminal, and after reacting with one active terminal, it does not react with another active terminal, and is not particularly limited, but is preferably a compound that does not contain a halogen atom, and among them, a polymerization terminator that generates a metal alkoxide, a metal aryloxide, or a metal hydroxide when reacting with an active terminal is particularly preferred. Specific examples of the polymerization terminator include water; monohydric alcohols such as methanol and ethanol; monohydric phenols such as phenol and cresol; etc. The amount of the polymerization terminator used can be selected appropriately.

[0068] <Step (4A)> Next, in step (4A), the solution containing the block copolymer (A′) obtained in step (3A) is subjected to a hydrogenation reaction to obtain a solution containing the hydrogenated block copolymer (A).

[0069] The method for hydrogenating the solution containing the block copolymer (A′) is not particularly limited, and examples thereof include a method in which the solution containing the block copolymer (A′) is brought into contact with hydrogen in the presence of a hydrogenation catalyst.

[0070] The hydrogenation catalyst is not particularly limited, but examples thereof include supported heterogeneous catalysts in which a metal such as Ni, Pt, Pd, or Ru is supported on a carrier such as carbon, silica, alumina, or diatomaceous earth; Ziegler-type catalysts that use an organic salt or acetylacetone salt of Ni, Co, Fe, Cr, or the like and a reducing agent such as organoaluminum; organic complex catalysts such as organometallic compounds of Ru, Rh, etc.; and homogeneous catalysts that use a titanocene compound and a reducing agent such as organolithium, organoaluminum, or organomagnesium; among these, Ziegler-type catalysts are preferred.

[0071] The hydrogenation reaction can be carried out according to the methods disclosed in, for example, Japanese Patent Publication Nos. 42-8704, 43-6636, Japanese Patent Laid-Open Nos. 59-133203 and 60-220147.

[0072] The hydrogenation reaction conditions may be selected depending on the hydrogenation rate of the target olefin, and the hydrogenation reaction temperature is preferably 0 to 200°C, more preferably 30 to 150°C. The hydrogen pressure used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa, and the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction may be carried out by a batch process, a continuous process, or a combination thereof.

[0073] <Step (5A)> Next, in step (5A), the target hydrogenated block copolymer (A) is recovered from the solution containing the hydrogenated block copolymer (A) obtained in step (4A).

[0074] The recovery method may be any conventional method and is not particularly limited. For example, the target polymer can be recovered by adding an additive such as an antioxidant as needed, and then applying a known solvent method such as direct drying or steam stripping to the solution.

[0075] When the hydrogenated block copolymer (A) is recovered as a slurry by steam stripping or the like, it is preferable to dehydrate it using an arbitrary dehydrator such as an extruder-type squeezer to recover the hydrogenated block copolymer (A) in the form of crumbs, and then dry the obtained crumbs using an arbitrary dryer such as a band dryer or an expansion extrusion dryer. The hydrogenated block copolymer (A) thus obtained may be processed into pellets or the like according to a conventional method before use.

[0076] The solid (pellet-like, crumb-like, etc.) hydrogenated block copolymer (A) thus obtained is preferably used after reducing the water content in the solid hydrogenated block copolymer (A) using a dryer such as a hopper dryer, a hot air circulation tray dryer, a tray vacuum dryer, an agitation vacuum dryer, etc. The drying conditions are not particularly limited as long as the target water content can be achieved, and may be set depending on the amount of water to be reduced and the type of dryer, etc., but are usually set at a drying temperature of 40 to 90°C for a drying time of 1 to 24 hours.

[0077] <Modification Step> The silane-modified hydrogenated block copolymer (A-Si) of the present invention can be produced by a production method including a modification step of reacting the hydrogenated block copolymer (A) with an unsaturated silane modifier. Preferably, the silane-modified hydrogenated block copolymer (A-Si) of the present invention can be produced by melt-kneading the hydrogenated block copolymer (A), the unsaturated silane modifier, and a peroxide.

[0078] The unsaturated silane modifier may be used alone or in combination of two or more. The amount of the unsaturated silane modifier used is not particularly limited, but is preferably 0.1 to 20 g, more preferably 0.5 to 15 g, and even more preferably 1 to 10 g per 100 g of the polymer component to be modified with the unsaturated silane modifier.

[0079] Examples of peroxides include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-t-butylperoxyhexane, 2,5-dimethyl-t-butylperoxyhexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, p-chlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t-butylbenzoate, and 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. These can be used alone or in combination of two or more.

[0080] The amount of peroxide used is not particularly limited, but is preferably 0.01 to 1 g, more preferably 0.02 to 0.5 g, and even more preferably 0.05 to 0.2 g per 1 g of the unsaturated silane modifier used.

[0081] The method for melt-kneading the hydrogenated block copolymer (A), the unsaturated silane modifier, and the peroxide is not particularly limited, and examples thereof include a method in which the components are heated, melt-mixed using a kneading device such as a roll, a Banbury mixer, a kneader, a Labo Plastomill, a single-screw extruder, or a twin-screw extruder. The conditions for the heated, melt-mixed components are preferably conditions that can prevent excessive decomposition of the components or the progression of unexpected reactions. For example, the mixing temperature is preferably 180 to 260°C, more preferably 200 to 240°C. The mixing time is preferably 0.5 to 20 minutes, more preferably 1 to 10 minutes.

[0082] <Polymer Composition> The present invention also relates to a polymer composition containing the above-mentioned silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) described below.

[0083] [Silane-Modified Hydrogenated Block Copolymer (B-Si)] The silane-modified hydrogenated block copolymer (B-Si) used in the present invention is a block copolymer obtained by modifying the hydrogenated block copolymer (B) described below with an unsaturated silane modifier, and is a block copolymer having a silane-containing functional group.

[0084] (Hydrogenated Block Copolymer (B)) The hydrogenated block copolymer (B) is a block copolymer represented by the following general formula (B): ｂ -HD ｂ -Ar2 ｂ (B) (In the above general formula (B), Ar1 ｂ and Ar2 ｂ is an aromatic vinyl polymer block, and HD ｂ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 ｂ Weight average molecular weight (Mw(Ar1 ｂ )) with respect to Ar2 ｂ Weight average molecular weight (Mw(Ar2 ｂ )) ratio (Mw(Ar2 ｂ ) / Mw(Ar1 ｂ )) is 0.95 to 1.05.

[0085] The hydrogenated block copolymer (B) is a conjugated diene polymer block HD. ｂ At both ends of each of the two aromatic vinyl polymer blocks Ar1 ｂ , Ar2 ｂ It is a hydrogenated aromatic vinyl-conjugated diene-aromatic vinyl block copolymer composed of the following:

[0086] Aromatic vinyl polymer block Ar1 of hydrogenated block copolymer (B) ｂ and Ar2 ｂ is a polymer block composed of aromatic vinyl monomer units. ｂ and Ar2 ｂ The aromatic vinyl polymer block Ar1 of the hydrogenated block copolymer (A) can be used as a monomer for constituting the aromatic vinyl polymer block Ar1. ａ and Ar2 ａThe monomers used to form the aromatic vinyl polymer block Ar1 of the hydrogenated block copolymer (A) include the monomers described above. The preferred type and content of each monomer are ａ and Ar2 ａ The preferred types and contents are the same as those of the above.

[0087] Hydrogenated block copolymer (B) of conjugated diene polymer block HD ｂ is a polymer block composed of conjugated diene monomer units, and at least a portion of the conjugated diene monomer units constituting the polymer block are hydrogenated. ｂ The monomers used to form the hydrogenated block copolymer (A) include the hydrogenated polymer block HD of the conjugated diene polymer. ａ The monomers used to form the hydrogenated block copolymer (A) include the above-mentioned monomers. The preferred type and content of each monomer are determined by the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (A). ａ The preferred types and contents are the same as those of the above.

[0088] The hydrogenated block copolymer (B) is ｂ Weight average molecular weight (Mw(Ar1 ｂ )) with respect to Ar2 ｂ Weight average molecular weight (Mw(Ar2 ｂ )) ratio (Mw(Ar2 ｂ ) / Mw(Ar1 ｂ )) is in the range of 0.95 to 1.05. ｂ ) / Mw(Ar1 ｂ ) is preferably in the range of 0.98 to 1.02. ｂ ) / Mw(Ar1 ｂ By setting the value of (a) to be within the above range, the compression recovery can be further improved, and the moldability, transparency, and resistance to compression set can also be improved.

[0089] The hydrogenation rate of the olefin in the hydrogenated block copolymer (B) is preferably 10 to 100%, more preferably 50 to 100%, even more preferably 80 to 100%, particularly preferably 90 to 100%, and most preferably 95 to 100%. Specifically, the hydrogenation rate of the olefin refers to the proportion (mol %) of hydrogenated carbon-carbon double bonds in the total non-aromatic carbon-carbon double bonds contained in the hydrogenated block copolymer (B) before hydrogenation. The hydrogenation rate of the olefin can be determined by the following method: １ It can be determined by H-NMR spectrum measurement.

[0090] The content of aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (B) is not particularly limited, but is preferably 7 to 60% by weight, more preferably 10 to 50% by weight, and even more preferably 15 to 40% by weight. The content of aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (B) can be determined based on the detection intensity ratio between a differential refractometer and an ultraviolet detector in high performance liquid chromatography measurement.

[0091] The weight-average molecular weight of the hydrogenated block copolymer (B) is not particularly limited, but is preferably 20,000 to 500,000, more preferably 25,000 to 300,000, and even more preferably 30,000 to 150,000. By setting the weight-average molecular weight within the above range, it is possible to further improve compression recovery, and also to improve moldability, transparency, and compression set resistance.

[0092] Two aromatic vinyl polymer blocks Ar1 constituting the hydrogenated block copolymer (B) ｂ , Ar2 ｂ Weight average molecular weight (Mw(Ar1 ｂ ), Mw(Ar2 ｂ )) are each preferably 1,000 to 40,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 8,000. ｂ ) and Mw(Ar2 ｂBy setting the ratio of the two aromatic vinyl polymer blocks Ar1 to Ar2 in the above range, the compression recovery can be further improved, and the moldability, transparency, and resistance to compression set can also be improved. ｂ , Ar2 ｂ Weight average molecular weight (Mw(Ar1 ｂ ), Mw(Ar2 ｂ )) may be the same as or different from each other, but are preferably substantially the same. ｂ Weight average molecular weight (Mw(Ar1 ｂ )) with respect to Ar2 ｂ Weight average molecular weight (Mw(Ar2 ｂ )) ratio (Mw(Ar2 ｂ ) / Mw(Ar1 ｂ )) may be in the range of 0.95 to 1.05, and preferably in the range of 0.97 to 1.03.

[0093] In addition, these two aromatic vinyl polymer blocks Ar1 ｂ , Ar2 ｂ At least one polymer block of the ｂ ), Mw(Ar2 ｂ )) is an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight, which constitutes the hydrogenated block copolymer (A). ａ Weight average molecular weight (Mw(Ar1 ａ )) may be equal to or different from Ar1), but it is more preferable that they are substantially equal to each other. ａ Weight average molecular weight (Mw(Ar1 ａ )) with respect to Ar1 ｂ Weight average molecular weight (Mw(Ar1 ｂ )) ratio (Mw(Ar1 ｂ ) / Mw(Ar1 ａ )) is in the range of 0.95 to 1.05, or Ar1 ａ Weight average molecular weight (Mw(Ar1 ａ )) with respect to Ar2 ｂ Weight average molecular weight (Mw(Ar2 ｂ )) ratio (Mw(Ar2 ｂ ) / Mw(Ar1ａ )) is preferably in the range of 0.95 to 1.05.

[0094] The hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (B) ｂ Weight average molecular weight (Mw(HD ｂ )) is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, even more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000. ｂ is its weight average molecular weight (Mw(HD ｂ ) is a hydrogenated polymer block HD of a conjugated diene polymer constituting the hydrogenated block copolymer (A). ａ Weight average molecular weight (Mw(HD ａ )) may be equal to or different from, but it is more preferable that they are substantially equal to. ａ Weight average molecular weight (Mw(HD ａ )) against HD ｂ Weight average molecular weight (Mw(HD ｂ )) ratio (Mw(HD ｂ ) / Mw(HD ａ )) is preferably in the range of 0.95 to 1.05.

[0095] The hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (B) ｂ The vinyl bond content of the hydrogenated polymer block of the diolefin polymer is preferably 1 to 80 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 12 mol %. １ The hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (B) can be determined by H-NMR. ｂ The vinyl bond content of the hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (A) is ａ For example, the vinyl bond content of the hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (A) is preferably substantially equal toａ The hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (B) relative to the vinyl bond content of ｂ It is preferable that the ratio of the vinyl bond content of the copolymer to the vinyl bond content of the copolymer is in the range of 0.95 to 1.05.

[0096] The molecular weight distribution of the hydrogenated block copolymer (B) and of each polymer block constituting the hydrogenated block copolymer (B), expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) [(Mw) / (Mn)], is not particularly limited, but is preferably 1.1 or less, and more preferably 1.05 or less.

[0097] In producing the silane-modified hydrogenated block copolymer (B-Si) used in the present invention, for example, when a production method using a coupling agent is adopted, such as when a production method for the hydrogenated block copolymer (B) having the steps (1a) to (6a) described below is adopted, the hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (B) is used. ｂ However, Ar1 may contain a residue of a coupling agent. Specifically, the hydrogenated block copolymer (B) may be a compound represented by the following formula: ｂ - (HD ｂ’ -X-HD ｂ’’ ) -Ar2 ｂ That is, as shown in the above formula, the hydrogenated polymer block HD of the conjugated diene polymer ｂ is coupled to HD via the residue X of the coupling agent. ｂ’ , H.D. ｂ’’ Examples of the residue X of the coupling agent include residues of bifunctional coupling agents exemplified in the method for producing the hydrogenated block copolymer (B) having steps (1a) to (6a) described below.

[0098] (Silane-Containing Functional Group) The silane-modified hydrogenated block copolymer (B-Si) used in the present invention is a block copolymer obtained by modifying the hydrogenated block copolymer (B) with an unsaturated silane modifier. The silane-modified hydrogenated block copolymer (B-Si) used in the present invention has a silane-containing functional group as a modifying group derived from the unsaturated silane modifier. The silane-modified hydrogenated block copolymer (B-Si) used in the present invention may have one type of silane-containing functional group, or may have two or more types of silane-containing functional groups.

[0099] Here, when the hydrogenated block copolymer (B) is modified with an unsaturated silane modifier, the hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (B) is usually ｂ The carbon atoms in the polymer and the unsaturated silane modifier act to form a hydrogenated polymer block HD of the conjugated diene polymer. ｂ In this case, the silane-modified hydrogenated block copolymer (B-Si) used in the present invention has a silane-containing functional group introduced as a side chain between the hydrogenated polymer block HD of the conjugated diene polymer and the silane-containing functional group. ｂ It has it as a side chain.

[0100] The unsaturated silane modifier used in the present invention is not particularly limited as long as it is a silane compound containing a carbon-carbon unsaturated bond in the molecule, but is preferably the above-mentioned compound (1).

[0101] The amount of silane-containing functional groups in the silane-modified hydrogenated block copolymer (B-Si) used in the present invention is not particularly limited. The amount of silane-containing functional groups per 100 g of the silane-modified hydrogenated block copolymer (B-Si) used in the present invention is preferably 1 to 100 mmol, more preferably 2 to 50 mmol, and even more preferably 3 to 30 mmol. By setting the amount of silane-containing functional groups within the above range, it is possible to further improve compression recovery, and also to improve moldability, transparency, and compression set resistance.

[0102] (Other Components) The polymer composition of the present invention may contain other polymer components in addition to the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si), as long as the effects of the present invention are not impaired, or may contain only the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) as polymer components.

[0103] Examples of other polymer components include aromatic vinyl-conjugated diene-aromatic vinyl block copolymers other than the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si), aromatic vinyl-conjugated diene block copolymers, aromatic vinyl homopolymers, conjugated diene homopolymers, aromatic vinyl-conjugated diene random copolymers, and branched polymers thereof; thermoplastic elastomers such as polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyester-based thermoplastic elastomers; thermoplastic resins such as polyvinyl chloride, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and polyphenylene ether; and the like. These may be used alone or in combination of two or more. The timing of addition of these polymer components is not particularly limited, and may be before or after the modification step with the unsaturated silane modifier.

[0104] In the polymer composition of the present invention, the content of polymer components other than the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, even more preferably 0 to 5 parts by weight, particularly preferably 0 to 1 part by weight, and most preferably substantially 0 part by weight, relative to 100 parts by mass of the total content of the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) in the polymer composition of the present invention.

[0105] The polymer composition of the present invention may further contain, as necessary, antioxidants, zinc oxide, foaming agents, foaming assistants, fillers, tackifying resins, softeners, antibacterial agents, light stabilizers, ultraviolet absorbers, dyes, lubricants, etc. The timing of adding these components is not particularly limited, and they may be added before or after the modification step with the unsaturated silane modifier.

[0106] (Method for Producing Polymer Composition) The method for producing the polymer composition of the present invention is not particularly limited. For example, the polymer composition can be produced by separately producing a silane-modified hydrogenated block copolymer (A-Si) and a silane-modified hydrogenated block copolymer (B-Si) and then mixing them according to a conventional method such as kneading or solution mixing. The silane-modified hydrogenated block copolymer (B-Si) can be produced by a production method comprising a step of obtaining a hydrogenated block copolymer (B) according to a conventional block copolymer production method and hydrogenation method, and a modification step of reacting the obtained hydrogenated block copolymer (B) with an unsaturated silane modifier. The conditions for the modification step can be similar to those for the modification step of reacting the hydrogenated block copolymer (A) with an unsaturated silane modifier.

[0107] On the other hand, in the present invention, from the viewpoint of enabling the polymer composition of the present invention to be produced with high productivity, it is preferable to produce the polymer composition of the present invention by a production method including a step of obtaining a hydrogenated block copolymer composition containing hydrogenated block copolymer (A) and hydrogenated block copolymer (B) and a modification step of reacting the obtained hydrogenated block copolymer composition with an unsaturated silane modifier. That is, the polymer composition of the present invention is preferably obtained by modifying a hydrogenated block copolymer composition containing hydrogenated block copolymer (A) and hydrogenated block copolymer (B) with an unsaturated silane modifier.

[0108] The weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) contained in the hydrogenated block copolymer composition is not particularly limited, but is preferably 10 / 90 to 80 / 20, more preferably 20 / 80 to 60 / 40, and even more preferably 25 / 75 to 50 / 50. By setting the weight ratio (A / B) within the above range, compression recovery can be further improved, and moldability, transparency, and compression set resistance can also be improved. The weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) can be determined from the area ratio of the peaks corresponding to each block copolymer in a chart obtained by high-performance liquid chromatography.

[0109] The proportion of aromatic vinyl monomer units in the entire polymer components in the hydrogenated block copolymer composition (total monomer units constituting the polymer components) (hereinafter sometimes referred to as "total aromatic vinyl monomer unit content") is preferably 20 to 70% by weight, more preferably 25 to 60% by weight, and even more preferably 30 to 55% by weight. By setting the total aromatic vinyl monomer unit content within the above range, it is possible to further improve compression recovery, and also to improve moldability, transparency, and compression set resistance. The total aromatic vinyl monomer unit content can be determined by the following formula: １ It can be determined by H-NMR measurement.

[0110] In addition, when all polymer components constituting the hydrogenated block copolymer composition are composed only of aromatic vinyl monomer units and conjugated diene monomer units, the polymer components in the hydrogenated block copolymer composition can be decomposed by ozonolysis and then reduced with lithium aluminum hydride according to the method described in Rubber Chem. Technol., 45, 1295 (1972), whereby the conjugated diene monomer unit portions (including hydrogenated portions) can be decomposed and only the aromatic vinyl monomer unit portions can be isolated, thereby easily measuring the total aromatic vinyl monomer unit content. The aromatic vinyl monomer unit content and the conjugated diene monomer unit content in each block copolymer can be determined by the same method.

[0111] The weight average molecular weight of all the polymer components constituting the hydrogenated block copolymer composition is not particularly limited, but is preferably 30,000 to 400,000, more preferably 35,000 to 150,000, and even more preferably 40,000 to 100,000. By setting the weight average molecular weight of all the polymer components within the above range, it is possible to further improve compression recovery, and it is also possible to improve moldability, transparency, and compression set resistance.

[0112] Furthermore, the molecular weight distribution, which is expressed as the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of all the polymer components constituting the hydrogenated block copolymer composition, is not particularly limited, but is preferably 1 to 5, more preferably 1.01 to 3, and even more preferably 1.02 to 1.5.

[0113] The method for producing the hydrogenated block copolymer composition is not particularly limited, and the composition can be produced, for example, by separately producing the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) according to conventional block copolymer production methods and hydrogenation methods, and then mixing them according to a conventional method such as kneading, solution mixing, etc. On the other hand, from the viewpoint of being able to produce the hydrogenated block copolymer composition with high productivity, the production method described below is preferred.

[0114] That is, the method for producing the hydrogenated block copolymer composition is preferably a production method comprising the following steps (1) to (7): (1): A step of polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having active ends. (2): A step of adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having active ends obtained in the step (1) above and polymerizing the conjugated diene monomer to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends. (3): A step of adding an aromatic vinyl monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having active ends obtained in the step (2) above and polymerizing the aromatic vinyl monomer to obtain a solution containing an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends. (4): A step of adding a polymerization terminator to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends obtained in the step (3) above in an amount of less than 1 molar equivalent relative to the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer to deactivate a portion of the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends to obtain a solution containing block copolymer (B'). (5): A step of adding an aromatic vinyl monomer to the solution containing the block copolymer (B') obtained in the step (4) above to polymerize the aromatic vinyl monomer, thereby obtaining a solution containing the block copolymer (B') and the block copolymer (A'). (6): A step of subjecting the solution containing the block copolymer (B') and the block copolymer (A') obtained in the step (5) above to a hydrogenation reaction, thereby obtaining a solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A). (7): A step of recovering a hydrogenated block copolymer composition from the solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A) obtained in the step (6).

[0115] <Steps (1) and (2)> Steps (1) and (2) are similar to the above-described steps (1A) and (2A), and similar conditions can be employed.

[0116] The aromatic vinyl polymer having an active end obtained in step (1) is an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight of the hydrogenated block copolymer (A). ａ and the aromatic vinyl polymer block Ar1 of the hydrogenated block copolymer (B) ｂ , Ar2 ｂ Either one of (i.e., Ar1 ｂ or Ar2 ｂ Therefore, the polymerization conditions in step (1), including the amount of the aromatic vinyl monomer, may be determined depending on the target weight-average molecular weight of these polymer blocks.

[0117] The conjugated diene polymer chain formed in step (2) (the conjugated diene block constituting the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2)) is a hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (A). ａ and hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (B). ｂ Therefore, the polymerization conditions in step (2), including the amount of the conjugated diene polymer, may be determined depending on the target weight average molecular weight of these polymer blocks, etc.

[0118] When a Lewis base compound is used, the timing of adding the Lewis base compound is not particularly limited and may be appropriately determined depending on the structure of each target block copolymer. For example, the Lewis base compound may be added in advance before the start of polymerization, or may be added after some polymer blocks have been polymerized. Furthermore, the Lewis base compound may be added in advance before the start of polymerization, and then additionally added after some polymer blocks have been polymerized.

[0119] <Step (3)> Step (3) is the same as the above-mentioned step (3A) except that the active terminal is not inactivated, and the same conditions can be employed.

[0120] The aromatic vinyl polymer chain formed in step (3) (the aromatic vinyl block constituting the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end obtained in step (3)) is the aromatic vinyl polymer block Ar1 of the hydrogenated block copolymer (B). ｂ , Ar2 ｂ One of (i.e., Ar1 ｂ or Ar2 ｂ is a block different from the block formed in step (1), for example, Ar1 ｂ When the compound is formed, Ar2 ｂ Therefore, the polymerization conditions in step (3), including the amount of the aromatic vinyl monomer, may be determined depending on the target weight-average molecular weight of the polymer block, etc.

[0121] <Step (4)> Next, in step (4), a polymerization terminator is added to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends obtained in step (3) in an amount of less than 1 molar equivalent relative to the active ends, thereby deactivating a portion of the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends, thereby obtaining a solution containing block copolymer (B').

[0122] The block copolymer (B') obtained in the step (4) is the block copolymer before hydrogenation to obtain the hydrogenated block copolymer (B).

[0123] The amount of the polymerization terminator used may be determined depending on the ratio of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) constituting the hydrogenated block copolymer composition, and is not particularly limited as long as it is an amount less than 1 molar equivalent relative to the active terminal of the polymer. However, the amount of the polymerization terminator used is preferably in the range of 0.18 to 0.91 molar equivalents, more preferably in the range of 0.35 to 0.80 molar equivalents, relative to the active terminal of the polymer.

[0124] As described above, according to step (4), by adding a polymerization terminator to a solution containing an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends in an amount less than 1 molar equivalent relative to the active ends, the active ends of some of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymers having active ends are deactivated, and the copolymers with deactivated active ends become the block copolymer (B') before hydrogenation for constituting the hydrogenated block copolymer (B). The remaining portion of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends that did not react with the polymerization terminator remains unreacted in the solution, maintaining its active ends.

[0125] <Step (5)> Next, in step (5), an aromatic vinyl monomer is added to the solution containing the block copolymer (B') obtained in step (4) above, and the aromatic vinyl monomer is polymerized to obtain a solution containing the block copolymer (B') and the block copolymer (A').

[0126] According to step (5), when an aromatic vinyl monomer is added to the solution obtained in step (4), the aromatic vinyl monomer is further polymerized from the aromatic vinyl polymer chain on the side having the active end of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end that has remained unreacted with the polymerization terminator, thereby extending the aromatic vinyl polymer chain and producing block copolymer (A'). Note that block copolymer (A') is an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer obtained by extending the aromatic vinyl polymer chain, and serves as the block copolymer before hydrogenation for producing hydrogenated block copolymer (A).

[0127] The aromatic vinyl polymer chain extended in step (5) is an aromatic vinyl polymer block Ar2 having a relatively large weight average molecular weight of the hydrogenated block copolymer (A). ａ Therefore, the polymerization conditions in step (5), including the amount of the aromatic vinyl monomer, are set so as to achieve the above-mentioned aromatic vinyl polymer block Ar2. ａThe polymerization conditions may be determined depending on the target weight average molecular weight, etc. (for example, the polymerization conditions may be determined within the ranges explained in the above step (1A)).

[0128] <Steps (6) and (7)> ​​A hydrogenated block copolymer composition can be obtained by the above-described steps (6) and (7) using the solution containing block copolymer (B') and block copolymer (A') obtained in step (5). Note that the above-described steps (6) and (7) are similar to the above-described steps (4A) and (5A), and similar conditions can be used for these steps.

[0129] According to the above-described method for producing a hydrogenated block copolymer composition, the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) can be continuously produced in the same reaction vessel, and therefore the target hydrogenated block copolymer composition can be produced with superior productivity compared to the case where each hydrogenated block copolymer is produced separately and then mixed.

[0130] In addition to the above-described preferred production method (a production method comprising steps (1) to (7)), a production method for a hydrogenated block copolymer composition comprising the following steps (1a) to (6a) is also preferably used when producing the hydrogenated block copolymer composition. (1a): A step of polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active terminal. (2a): A step of adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having an active terminal obtained in the step (1a) above and polymerizing the conjugated diene monomer to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having an active terminal. (3a): A step of adding a bifunctional coupling agent to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal obtained in the step (2a) above in an amount such that the total number of functional groups relative to the active terminals is less than 1 molar equivalent, thereby coupling a part of the aromatic vinyl-conjugated diene block copolymer having an active terminal to obtain a solution containing block copolymer (B'). (4a): A step of adding an aromatic vinyl monomer to the solution containing block copolymer (B') obtained in the step (3a) above and polymerizing the aromatic vinyl monomer to obtain a solution containing block copolymer (B') and block copolymer (A'). (5a): A step of subjecting the solution containing the block copolymer (B') and the block copolymer (A') obtained in the step (4a) above to a hydrogenation reaction to obtain a solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A). (6a): A step of recovering a hydrogenated block copolymer composition from the solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A) obtained in the step (5a) above.

[0131] <Step (1a) and Step (2a)> Step (1a) and step (2a) are similar to the above-described step (1) and step (2), and similar conditions can be employed.

[0132] <Step (3a)> In step (3a), a bifunctional coupling agent is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having active ends obtained in step (2a) in an amount such that the total amount of functional groups relative to the active ends is less than 1 molar equivalent, thereby coupling a portion of the aromatic vinyl-conjugated diene block copolymer having active ends to obtain a solution containing block copolymer (B'). Block copolymer (B') obtained in step (3a) serves as the block copolymer before hydrogenation to obtain hydrogenated block copolymer (B).

[0133] The bifunctional coupling agent is not particularly limited as long as it has two functional groups that react with the active terminal, and examples thereof include bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, and dibromomethane; and bifunctional tin halides such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, and dibutyldichlorotin. The amount of the bifunctional coupling agent used may be determined depending on the ratio of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) that constitute the hydrogenated block copolymer composition.

[0134] As described above, according to step (3a), by adding a bifunctional coupling agent to a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends in an amount such that the total amount of functional groups relative to the active ends is less than 1 molar equivalent, a portion of the aromatic vinyl-conjugated diene block copolymer having active ends is coupled to form block copolymer (B') before hydrogenation for constituting hydrogenated block copolymer (B). The remaining portion of the aromatic vinyl-conjugated diene block copolymer having active ends that did not react with the bifunctional coupling agent remains unreacted in the solution, maintaining its active ends.

[0135] <Step (4a)> Next, in step (4a), an aromatic vinyl monomer is added to the solution containing the block copolymer (B′) obtained in step (3a) above, and the aromatic vinyl monomer is polymerized to obtain a solution containing the block copolymer (B′) and the block copolymer (A′).

[0136] According to step (4a), when an aromatic vinyl monomer is added to the solution obtained in step (3a), the aromatic vinyl monomer is polymerized from the active end of the aromatic vinyl-conjugated diene block copolymer having an active end that remains unreacted with the bifunctional coupling agent, thereby forming an aromatic vinyl polymer chain, thereby obtaining block copolymer (A'). Note that block copolymer (A') is the block copolymer before hydrogenation for obtaining hydrogenated block copolymer (A).

[0137] At this time, in the step (4a), the aromatic vinyl polymer chain formed is an aromatic vinyl polymer block Ar2 having a relatively large weight average molecular weight of the hydrogenated block copolymer (A). ａ Therefore, the polymerization conditions in step (4a), including the amount of the aromatic vinyl monomer, are set so as to achieve the above-mentioned aromatic vinyl polymer block Ar2. ａ The polymerization conditions may be determined depending on the target weight average molecular weight, etc. (for example, the polymerization conditions may be determined within the ranges explained in the above step (1)).

[0138] <Steps (5a) and (6a)> Then, the solution containing block copolymer (B') and block copolymer (A') obtained in step (4a) is used to obtain a hydrogenated block copolymer composition through the operations in steps (5a) and (6a) described above. Note that steps (5a) and (6a) described above are similar to steps (6) and (7) described above, and similar conditions can be used for these steps.

[0139] <Modification Step> The polymer composition of the present invention can be produced by a production method including a modification step of reacting a hydrogenated block copolymer composition with an unsaturated silane modifier. Preferably, the polymer composition of the present invention can be produced by mixing the hydrogenated block copolymer composition with the unsaturated silane modifier in the presence of a peroxide.

[0140] The conditions for the modification step can be the same as those for the modification step in which the hydrogenated block copolymer (A) is reacted with the unsaturated silane modifier.

[0141] <Crosslinked Product> The crosslinked product of the present invention can be obtained by crosslinking the silane-modified hydrogenated block copolymer (A-Si) of the present invention or the polymer composition of the present invention. The crosslinked product of the present invention not only has excellent compression recovery, but also excellent moldability, transparency, and compression set resistance (particularly, compression set resistance under high temperature environments).

[0142] The crosslinked product of the present invention preferably has a crosslinked structure derived from the silane-containing functional group in the silane-modified hydrogenated block copolymer (A-Si) (and the silane-modified hydrogenated block copolymer (B-Si)). Furthermore, the crosslinked structure derived from the silane-containing functional group preferably contains a —Si—O—Si— bond. This structure can further enhance compression recovery and moldability.

[0143] The melt flow rate of the crosslinked product of the present invention is not particularly limited, but is preferably 0.05 to 100 g / 10 min, more preferably 0.05 to 50 g / 10 min, even more preferably 0.1 to 30 g / 10 min, and particularly preferably 0.3 to 30 g / 10 min. By setting the melt flow rate within the above range, compression recovery, moldability, and compression set resistance can be further improved. Furthermore, when extremely excellent compression set resistance is required, the melt flow rate of the crosslinked product of the present invention is preferably 0.3 to 15 g / 10 min, and even more preferably 0.3 to 10 g / 10 min. In the present invention, the melt flow rate of the crosslinked product is measured in accordance with ISO 1133 (G conditions, 200°C, 5 kg). The melt flow rate of the crosslinked product of the present invention can be adjusted, for example, by adjusting the type of hydrogenated block copolymer (A) or hydrogenated block copolymer composition used in the production, the type and modification conditions of the unsaturated silane modifier, the crosslinking conditions, etc.

[0144] (Method for Producing Crosslinked Product) The crosslinked product of the present invention can be preferably produced by a method in which a silane-modified hydrogenated block copolymer (A-Si) or a polymer composition is brought into contact with a condensation reaction catalyst for condensing silane-containing functional groups. By such a production method, a crosslinked structure derived from the silane-containing functional groups can be introduced between polymer chains. Furthermore, when the silane-modified hydrogenated block copolymer (A-Si) or polymer composition is obtained using an unsaturated silane modifier having an alkoxy group as the unsaturated silane modifier, a crosslinked structure containing an —Si—O—Si— bond can be introduced between polymer chains by contacting the silane-modified hydrogenated block copolymer (A-Si) or polymer composition with a condensation reaction catalyst.

[0145] Examples of condensation reaction catalysts include polycarboxylic acids such as maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid, and acid anhydrides thereof; sulfonic acids such as paratoluenesulfonic acid; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, and didecyl phosphate. phosphoric acids or phosphoric acid esters such as propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, allyl glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, Cardura E, Epicoat 828, and Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd., and the like; Adducts with phosphate esters; titanium compounds such as titanium acetylacetonate, isopropyl tristearoyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, and bis(dioctyl pyrophosphate) oxyacetate titanate; tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin thioglycolate, dibutyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin maleate, and tin octylate; aluminum isoprene Examples of suitable alkoxy compounds include aluminum compounds such as aluminum propylate, aluminum tris(ethylacetonate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate; zirconium compounds such as tetra-n-butoxyzirconium, zirconium octylate, and reaction products of alkoxyzirconium with acetylacetone or acetoacetic ester; amines such as hexylamine, di-2-ethylhexylamine, and N,N-dimethyldodecylamine; and alkaline compounds such as sodium hydroxide and potassium hydroxide.As the condensation reaction catalyst, a mixture or reaction product of an acidic organic compound and a basic compound can also be used.

[0146] Among these, polycarboxylic acids, titanium compounds, and tin compounds are preferred, succinic acid, titanium acetylacetonate, and dibutyltin dilaurate are more preferred, and succinic acid and titanium acetylacetonate are even more preferred.

[0147] The amount of the condensation reaction catalyst used is not particularly limited, but is preferably 0.1 to 10 g, more preferably 0.2 to 5 g, per 100 g of the polymer component to be subjected to crosslinking.

[0148] The method for contacting the silane-modified hydrogenated block copolymer (A-Si) or the polymer composition with the condensation reaction catalyst is not particularly limited, but a method in which the silane-modified hydrogenated block copolymer (A-Si) or the polymer composition is mixed with the condensation reaction catalyst is preferred.

[0149] The method for mixing the silane-modified hydrogenated block copolymer (A-Si) or polymer composition with the condensation reaction catalyst is not particularly limited, and examples thereof include a method in which the components are heated and melt-mixed using a kneading device such as a roll, a Banbury mixer, a kneader, a Labo Plastomill, a single-screw extruder, or a twin-screw extruder, and a method in which the components are dissolved in a solvent and mixed uniformly, and then the solvent is removed by heating or the like. Among these, the heated and melt-mixed method is preferred from the viewpoint of more efficient mixing. The conditions for the heated and melt-mixed mixture are preferably those that can suppress excessive decomposition of the components and the progression of unexpected reactions. For example, the mixing temperature is preferably 180 to 260°C, and more preferably 200 to 240°C. The mixing time is preferably 0.5 to 20 minutes, and more preferably 1 to 10 minutes.

[0150] It is also preferable to carry out the modification step to obtain the silane-modified hydrogenated block copolymer (A-Si) or polymer composition and the crosslinking step consecutively. By such a method, a crosslinked product can be obtained with high productivity while suppressing excessive decomposition of each component and the progression of unexpected reactions.

[0151] Specifically, a preferred method involves mixing the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition, which is the raw material for the silane-modified hydrogenated block copolymer (A-Si) or the polymer composition, with an unsaturated silane modifier in the presence of a peroxide (modification step), and then adding a condensation reaction catalyst to the resulting mixture and further mixing (crosslinking step). In this production method, the modification reaction and the crosslinking reaction may proceed simultaneously after the addition of the condensation reaction catalyst.

[0152] The silane-modified hydrogenated block copolymer (A-Si), polymer composition, and crosslinked product of the present invention may be molded into a desired shape (e.g., pellets, sheets, strands, chips) depending on the application. Furthermore, the silane-modified hydrogenated block copolymer (A-Si), polymer composition, and crosslinked product of the present invention may be foamed to form a foam depending on the application.

[0153] <Applications> The silane-modified hydrogenated block copolymer (A-Si), polymer composition, and crosslinked product of the present invention can be suitably used in a variety of applications, such as clothing, daily necessities, medical devices, electronic devices, electrical appliances, packaging materials, transportation equipment, building materials, and parts thereof. For example, they can be suitably used in buffer materials such as buffer materials for batteries, weather strips, impact absorbing materials such as reinforced plastics (CFRP, etc.), glass interlayers, shoe soles, and sealants (particularly heat dissipation sealants) for electronic devices, etc.

[0154] The silane-modified hydrogenated block copolymer (A-Si), polymer composition, and crosslinked product of the present invention can also be suitably used in adhesive applications, particularly as adhesives for bonding dissimilar materials, such as glass, silicon wafers, ceramics, metals, plastics, reinforcing fibers, wood, leather, stone, concrete, rock, paper, corrugated cardboard, fabrics, glass, bricks, plaster, cement, tiles, mortar, and asphalt.

[0155] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "parts" and "%" are by weight unless otherwise specified. The test methods used in these examples and comparative examples are as follows.

[0156] [Weight-average molecular weight and molecular weight distribution of polymer composition] A chart based on the molecular weight in terms of polystyrene was obtained by high-performance liquid chromatography using tetrahydrofuran as a carrier at a flow rate of 0.35 ml / min, and the weight-average molecular weight and molecular weight distribution of the polymer composition were determined based on the obtained chart. The instrument used was a Tosoh HLC8320, and the column consisted of three connected Shodex (registered trademark) KF-404HQ columns manufactured by Showa Denko K.K. (column temperature: 40°C). The detectors used were a differential refractometer and an ultraviolet detector. Molecular weight calibration was performed using 12 standard polystyrenes (5 to 3 million) manufactured by Polymer Laboratory.

[0157] [Weight Ratio of Each Polymer] The weight ratio of each polymer was determined from the area ratio of the peak corresponding to each polymer in the chart obtained by the above high performance liquid chromatography.

[0158] [Weight-Average Molecular Weight of Styrene Polymer Block of Each Block Copolymer] According to the method described in Rubber Chem. Technol., 45, 1295 (1972), the (hydrogenated) block copolymer was reacted with ozone and reduced with lithium aluminum hydride to decompose the isoprene polymer block of the (hydrogenated) block copolymer. Specifically, the following procedure was performed. 300 mg of sample was dissolved in a reaction vessel containing 100 ml of dichloromethane treated with molecular sieves. The reaction vessel was placed in a cooling bath and cooled to -25°C. Ozone generated by an ozone generator was then introduced into the reaction vessel while oxygen was flowing into the reaction vessel at a flow rate of 170 ml / min. Thirty minutes after the start of the reaction, the completion of the reaction was confirmed by introducing the gas flowing out of the reaction vessel into an aqueous potassium iodide solution. Next, 50 ml of diethyl ether and 470 mg of lithium aluminum hydride were placed in a separate reaction vessel purged with nitrogen. While cooling the reaction vessel with ice water, the solution reacted with ozone was slowly added dropwise to the reaction vessel. The reaction vessel was then placed in a water bath, gradually heated, and refluxed at 40°C for 30 minutes. Dilute hydrochloric acid was then added dropwise to the reaction vessel in small amounts while stirring the solution, and the addition was continued until hydrogen generation was almost completely eliminated. After the reaction, the solid product formed in the solution was filtered, and the solid product was extracted with 100 ml of diethyl ether for 10 minutes. This extract and the filtrate were combined, and the solvent was distilled off to obtain a solid sample. The weight-average molecular weight of the sample thus obtained was measured according to the above-described method for measuring weight-average molecular weight, and the resulting value was taken as the weight-average molecular weight of the styrene polymer block.

[0159] [Weight-Average Molecular Weight of (Hydrogenated) Isoprene Polymer Block of Each Block Copolymer] The weight-average molecular weight of the corresponding styrene polymer block was subtracted from the weight-average molecular weight of each polymer determined as described above, and the weight-average molecular weight of the (hydrogenated) isoprene polymer block was determined based on the calculated value.

[0160] [Vinyl bond content of (hydrogenated) isoprene polymer block] Deuterated chloroform was used as the solvent. １ It was determined based on H-NMR measurement.

[0161]

[0046] The styrene unit content of each block copolymer was determined based on the ratio of the detection intensities of the differential refractometer and the ultraviolet detector in the high performance liquid chromatography measurement. Copolymers having different styrene unit contents were prepared in advance, and a calibration curve was created using these copolymers.

[0162] [Styrene unit content of polymer composition] Deuterated chloroform was used as the solvent. １ The styrene unit content of the polymer composition was determined based on the H-NMR measurement.

[0163] [Olefin Hydrogenation Ratio (Mole %) of Polymer Composition] Deuterated chloroform was used as the solvent. １ The olefin amount was determined for each of the block copolymer composition before hydrogenation and the hydrogenated block copolymer composition after hydrogenation by H-NMR spectrum measurement, and the olefin hydrogenation rate (mol %) was calculated based on the difference between the olefin amounts before and after hydrogenation. １ In the H-NMR spectrum measurement, deuterated chloroform was used as the solvent, and a JMN-AL series AL400 (manufactured by JEOL) was used as the NMR measurement apparatus. In the present examples and comparative examples, both the block copolymer composition before hydrogenation and the hydrogenated block copolymer composition after hydrogenation contained only isoprene units as olefin-derived monomer units, and therefore the hydrogenation rate of isoprene was determined in the measurement, and this was taken as the olefin hydrogenation rate.

[0164] [Shore A Hardness of Hydrogenated Block Copolymer Composition] The Shore A hardness of the hydrogenated block copolymer composition was determined in accordance with ISO 7619.

[0165] [Transparency] The sheet was visually observed, and if the sheet was transparent with no cloudy areas, it was judged to have good transparency. On the other hand, if the sheet had cloudy areas, it was judged to have poor clarity.

[0166] [Melt Flow Rate] The melt flow rate was measured in accordance with ISO 1133 (G condition, 200°C, 5 kg).

[0167] [Compression recovery] The sheet was punched into a circle with a diameter of 13 mm to obtain a circular sample. Using a universal testing machine (Instron dual column tabletop universal testing system 5969, load cell type, 50 kN), the sample was compressed to a thickness of 40% (compression ratio 60%) at a temperature of 23°C and a compression rate of 1.0 mm / min. The sample was then restored at a restoration rate of 1.0 mm / min. Based on the obtained stress-strain hysteresis loop, the 50% compressive stress at compression and the 50% compressive stress at restoration were calculated. The compression recovery index was then calculated according to the following formula. The closer the compression recovery index is to 1, the better the compression recovery is judged to be. Compression recovery index = 50% compressive stress at compression / 50% compressive stress at restoration

[0168] [Compression set resistance] The sheet was punched into a circle with a diameter of 13 mm, and three of the resulting circular sheets were stacked to prepare a sample. In accordance with JIS-K6262, the compression set of the sample was measured under compression conditions of a compression ratio of 25%, a temperature of 23°C, and a compression time of 24 hours. Furthermore, the compression set of the sample in a high-temperature environment was measured in the same manner, except that the temperature was changed to 50°C. A gear-type aging tester (AG-1110, manufactured by Ueshima Seisakusho Co., Ltd.) was used for heating.

[0169] [Peel Strength] With the sheet placed on a glass substrate, the glass and the sheet were compression molded at 160°C and 0.2 MPa for 5 minutes to bond the glass substrate and the sheet together. Next, a test was conducted to peel the sheet from the glass substrate in accordance with ASTM F88, and the peel strength to the glass (unit: N / 10 mm) was determined.

[0170] [Production Example 1] (1) Production of Block Copolymer Composition Before Hydrogenation 56.6 kg of cyclohexane, 387 mmol of dibutyl ether, and 1.23 kg of styrene were added to a pressure reactor. While stirring the entire contents at 50°C, 208 mmol of n-butyllithium (1.6 M solution) was added. After the addition was completed, the temperature was raised to 55°C and a polymerization reaction was carried out for 1 hour (first stage of polymerization). The polymerization conversion of styrene at this time was 100%.

[0171] Subsequently, 5.00 kg of isoprene was continuously added to the reactor over 1 hour while controlling the temperature to maintain a temperature of 50 to 60°C. After the addition of isoprene was completed, the polymerization reaction was continued for another 1 hour (second-stage polymerization). The polymerization conversion of isoprene at this time was 100%.

[0172] Next, 1.23 kg of styrene was continuously added over 1 hour while controlling the temperature to maintain it at 50 to 60°C. After the addition of styrene was completed, the polymerization reaction was continued for another 1 hour to obtain a solution containing a styrene-isoprene-styrene triblock copolymer having active terminals (third polymerization stage). The polymerization conversion of styrene at this time was 100%.

[0173] Next, 145 mmol of methanol was added as a polymerization terminator, and the mixture was mixed to deactivate some of the active ends of the styrene-isoprene-styrene triblock copolymer having active ends, thereby obtaining a solution containing a styrene-isoprene-styrene triblock copolymer that would become block copolymer (B') for obtaining hydrogenated block copolymer (B).

[0174] Thereafter, 2.53 kg of styrene was continuously added over 1 hour while continuing to control the temperature to maintain it at 50 to 60°C. After the addition of styrene was completed, the polymerization reaction was continued for another 1 hour to obtain a solution containing a styrene-isoprene-styrene triblock copolymer having active ends, which would become block copolymer (A') for obtaining hydrogenated block copolymer (A) (fourth polymerization stage). The polymerization conversion of styrene at this time was 100%.

[0175] Finally, 271 mmol of methanol was added as a polymerization terminator and mixed to deactivate all of the active ends of the styrene-isoprene-styrene triblock copolymer, thereby completing the polymerization reaction. The amounts of each reagent used in the reaction are summarized in Table 1.

[0176] (2) Hydrogenation Reaction of Block Copolymer Composition Before Hydrogenation A solution containing the block copolymer composition before hydrogenation obtained above was subjected to a hydrogenation reaction to obtain a solution containing a hydrogenated block copolymer composition. The hydrogenation reaction was carried out by adding Ni(AcAc) ２ The TIBAL catalyst was added in a proportion of 0.5% based on the block copolymer composition before hydrogenation, and the reaction was carried out under conditions of a hydrogen pressure of 3 MPa, a reaction temperature of 80°C, and a reaction time of 3 hours. A portion of the solution containing the hydrogenated block copolymer composition thus obtained was taken out and measured according to the method described above. The results are shown in Table 2.

[0177] (3) Recovery of Hydrogenated Block Copolymer Composition: 0.3 parts of 2,6-di-t-butyl-p-cresol as an antioxidant was added to 100 parts of the solution containing the hydrogenated block copolymer composition obtained as described above, and the mixture was mixed. The mixed solution was added dropwise in small amounts to warm water heated to 85 to 95°C to volatilize the solvent, yielding a precipitate. The resulting precipitate was pulverized and dried with hot air at 85°C to recover a crumb-like hydrogenated block copolymer composition. The crumb-like hydrogenated block copolymer composition was fed into a single-screw extruder equipped with an underwater hot cut device at the tip of the extruder and formed into cylindrical pellets with an average diameter of approximately 5 mm and an average length of approximately 5 mm. The pellets were placed in a hopper dryer heated to 60°C and dried for 10 hours while circulating dry air at 60°C to obtain a hydrogenated block copolymer composition (Polymer 1) containing hydrogenated block copolymer (A) and hydrogenated block copolymer (B). The Shore A hardness of the hydrogenated block copolymer composition was measured according to the method described above. The results are shown in Table 2.

[0178] A hydrogenated block copolymer composition (Polymer 2) containing hydrogenated block copolymer (A) and hydrogenated block copolymer (B) was obtained in the same manner as in Production Example 1, except that the amounts of each reagent used in the reaction were changed to those shown in Table 1, and measurements were carried out in the same manner. The results are shown in Table 2.

[0179] Production Example 3 A hydrogenated block copolymer (B) (polymer 3) was obtained in the same manner as in Production Example 1, except that the amounts of each reagent used in the reaction were changed to those shown in Table 1, and measurements were performed in the same manner. The results are shown in Table 2. In Production Example 3, after the third polymerization stage, methanol was added as a polymerization terminator in the amount shown in Table 1, and mixed to deactivate all active ends of the styrene-isoprene-styrene triblock copolymer having active ends, thereby completing the polymerization reaction. This gave a solution containing the block copolymer composition before hydrogenation. A hydrogenated block copolymer (B) (polymer 3) was then obtained in the same manner as in Production Example 1, except that the obtained solution containing the block copolymer composition before hydrogenation was used.

[0180]

[0181]

[0182] Example 1 A hydrogenated block copolymer composition (Polymer 1), vinyltrimethoxysilane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, manufactured by NOF Corporation, organic peroxide) were supplied to a small twin-screw kneader (Xplore MC40) and melt-kneaded at 220°C for 3 minutes. Subsequently, succinic acid (a condensation reaction catalyst) was supplied to the small twin-screw kneader and melt-kneaded for another 3 minutes at 220°C. The feed ratio of each component was as shown in Table 3. As a result, the hydrogenated polymer block HD of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition (Polymer 1) was ａ and the hydrogenated polymer block HD of the hydrogenated block copolymer (B) ｂ A silane-containing functional group derived from vinyltrimethoxysilane and a crosslinked structure containing an -Si-O-Si- bond derived from the silane-containing functional group were introduced into the copolymer. As a result, a crosslinked product was obtained by crosslinking a polymer composition containing the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si). The resulting crosslinked product was press-molded in a press set at 200°C to obtain a sheet having a thickness of 2 mm. The resulting sheet was evaluated for transparency, melt flow rate, compression recovery, compression set resistance, and peel strength according to the methods described above. The results are shown in Table 3.

[0183] Examples 2 to 4 Crosslinked products and sheets were obtained and evaluated in the same manner as in Example 1, except that the type of block copolymer composition, the type of acid catalyst, and the amount of each component supplied were changed as shown in Table 1. The results are shown in Table 3. In Examples 2 to 4, the hydrogenated polymer block HD of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition (polymer 1 or 2) was ａ and the hydrogenated polymer block HD of the hydrogenated block copolymer (B) ｂ A silane-containing functional group derived from vinyltrimethoxysilane and a crosslinked structure containing an —Si—O—Si— bond derived from the silane-containing functional group were introduced into the polymer.

[0184] Examples 5 and 6 A hydrogenated block copolymer composition (Polymer 1), vinyltrimethoxysilane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, manufactured by NOF Corporation, organic peroxide) were fed to a small twin-screw kneader and melt-kneaded at 220°C for 3 minutes. The feed ratio of each component was as shown in Table 3. As a result, the hydrogenated polymer block HD of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition (Polymer 1 or 2) was ａ , and the hydrogenated polymer block HD of the hydrogenated block copolymer (B) ｂ A silane-containing functional group derived from vinyltrimethoxysilane was introduced into the copolymer. As a result, a polymer composition containing a silane-modified hydrogenated block copolymer (A-Si) and a silane-modified hydrogenated block copolymer (B-Si) was obtained. The obtained polymer composition was press-molded using a press set at 200°C to obtain a sheet having a thickness of 2 mm. The obtained sheet was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0185] Comparative Example 1 A crosslinked product was obtained by crosslinking the silane-modified hydrogenated block copolymer (B-Si) in the same manner as in Example 1, except that the hydrogenated block copolymer (B) (Polymer 3) was used instead of the hydrogenated block copolymer composition (Polymer 1). A sheet was obtained in the same manner as in Example 1, except that the obtained crosslinked product was used, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0186] Comparative Example 2 A hydrogenated block copolymer composition (Polymer 1), ethylene propylene rubber (trade name "Mitsui EPT 3092PM", manufactured by Mitsui Chemicals, Inc.), and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, manufactured by NOF Corporation, organic peroxide) were supplied to a small twin-screw kneader and kneaded at 220°C for 3 minutes to obtain a crosslinked composition. The supply ratio of each component was as shown in Table 3. The obtained crosslinked composition was press-molded using a press set to 200°C to obtain a sheet having a thickness of 2 mm. The obtained sheet was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0187] Comparative Example 3 An olefin-based thermoplastic elastomer (a thermoplastic elastomer mainly composed of crosslinked ethylene propylene terpolymer and polypropylene, trade name "Milastomer 8030NS", manufactured by Mitsui Chemicals, Inc.) was press-molded using a press set at 200°C to obtain a sheet having a thickness of 2 mm. The obtained sheet was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0188]

[0189] Table 3 confirms that the silane-modified hydrogenated block copolymers having silane-containing functional groups, which are obtained by modifying the hydrogenated block copolymer (A) represented by general formula (A) with an unsaturated silane modifier, have excellent compression recovery properties (Examples 1 to 6).

[0190] On the other hand, when a hydrogenated block copolymer different from the hydrogenated block copolymer (A) was modified with an unsaturated silane modifier, it was confirmed that the compression recovery was poor (Comparative Example 1). Furthermore, when no modification with an unsaturated silane modifier was performed, it was confirmed that the compression recovery was also poor (Comparative Example 2). Furthermore, it was confirmed that an olefin-based thermoplastic elastomer also resulted in poor compression recovery (Comparative Example 3).

Claims

1. A silane-modified hydrogenated block copolymer having a silane-containing functional group, obtained by modifying a hydrogenated block copolymer (A) represented by the following general formula (A) with an unsaturated silane modifier: Ar1 ａ - HD ａ -Ar2 ａ (A) (In the above general formula (A), Ar1 ａ and Ar2 ａ is an aromatic vinyl polymer block, HD ａ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 ａ Weight average molecular weight (Mw(Ar1 ａ )) with respect to Ar2 ａ Weight average molecular weight (Mw(Ar2 ａ )) ratio (Mw(Ar2 ａ ) / Mw(Ar1 ａ )) is 3.0 to 20.

2. The silane-modified hydrogenated block copolymer according to claim 1, wherein the hydrogenation rate of the olefin in said hydrogenated block copolymer (A) is 10 to 100%.

3. The silane-containing functional group is added to the hydrogenated polymer block HD of the conjugated diene polymer. ａ 3. The silane-modified hydrogenated block copolymer according to claim 1, having a silane group as a side chain therein.

4. The silane-modified hydrogenated block copolymer according to any one of claims 1 to 3, wherein the content of aromatic vinyl monomer units in the total monomer units of the hydrogenated block copolymer (A) is 20 to 90% by weight.

5. The silane-modified hydrogenated block copolymer according to any one of claims 1 to 4, wherein the hydrogenated block copolymer (A) has a weight average molecular weight of 20,000 to 500,000.

6. In the above general formula (A), Ar1 ａ The weight average molecular weight of Ar2 is 1,000 to 40,000. ａ The weight average molecular weight of HD is 5,000 to 250,000. ａ 6. The silane-modified hydrogenated block copolymer according to claim 1, wherein the weight average molecular weight of said copolymer is from 10,000 to 300,000.

7. The silane-modified hydrogenated block copolymer according to any one of claims 1 to 6, wherein the unsaturated silane modifier is a compound (1) represented by the following general formula (1): (In the above general formula (1), R １ ~R ３ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R ４ is a hydrocarbon group having a carbon-carbon unsaturated bond.

8. In the above general formula (1), R １ ~R ３ 8. The silane-modified hydrogenated block copolymer according to claim 7, wherein at least one of the above is an alkoxy group having 1 to 6 carbon atoms.

9. A polymer composition comprising the silane-modified hydrogenated block copolymer (A-Si) according to any one of claims 1 to 8, and a silane-modified hydrogenated block copolymer (B-Si) having a silane-containing functional group, which is obtained by modifying a hydrogenated block copolymer (B) represented by the following general formula (B) with an unsaturated silane modifier. ｂ - HD ｂ -Ar2 ｂ (B) (In the above general formula (B), Ar1 ｂ and Ar2 ｂ is an aromatic vinyl polymer block, HD ｂ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 ｂ Weight average molecular weight (Mw(Ar1 ｂ )) with respect to Ar2 ｂ Weight average molecular weight (Mw(Ar2 ｂ )) ratio (Mw(Ar2 ｂ ) / Mw(Ar1 ｂ ) is 0.95 to 1.

05.

10. The polymer composition according to claim 9, which is obtained by modifying a hydrogenated block copolymer composition containing said hydrogenated block copolymer (A) and said hydrogenated block copolymer (B) with said unsaturated silane modifier.

11. A crosslinked product obtained by crosslinking the silane-modified hydrogenated block copolymer according to any one of claims 1 to 8 or the polymer composition according to any one of claims 9 to 10.

12. The crosslinked product according to claim 11, having a crosslinked structure derived from the silane-containing functional group.

13. The crosslinked product according to claim 11 or 12, wherein the crosslinked structure contains a --Si--O--Si-- bond.

14. The crosslinked product according to any one of claims 11 to 13, which has a melt flow rate of 0.05 to 100 g / 10 min, measured in accordance with ISO 1133 (G condition, 200°C, 5 kg).

15. The crosslinked product according to any one of claims 11 to 14, which is a cushioning material, a weather strip, a shock absorbing material, a glass interlayer film, a shoe sole, or a sealing material.