Polymer composition

Abstract

Provided is a polymer composition having excellent impact absorption and adhesiveness against a wide range of materials. Provided is a polymer composition containing: a silane-modified hydrogenated block copolymer (I) that has a silane-containing functional group and that is obtained by modifying, by using an unsaturated silane modifying agent, a hydrogenated block copolymer (i) having an aromatic vinyl polymer block (Ar1), a hydrogenated polymer block (HD) of a conjugated diene polymer, and an aromatic vinyl polymer block (Ar2) in the stated order; and a modified polyolefin (II) having a polar group.

Description

polymer composition

[0001] The present invention relates to a polymer composition, and more particularly to a polymer composition that has excellent adhesion to a wide range of materials and excellent impact absorption properties.

[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 resin composition containing a hydrogenated block copolymer composition having a predetermined hydrogenated block copolymer A and a predetermined hydrogenated block copolymer B, and a polyolefin-based thermoplastic resin C, wherein the weight ratio (A / B) of the hydrogenated block copolymer A to the hydrogenated block copolymer B in the hydrogenated block copolymer composition is 10 / 90 to 80 / 20, and the hydrogenation rate of the olefin in the polymer components constituting the hydrogenated block copolymer composition is 10 to 100%. The technology of Patent Document 1 provides a resin composition that achieves high levels of both tensile stress and restoring force and is capable of giving a molded article that is excellent in impact resistance and thermal stability.

[0004] International Publication No. 2022 / 085492

[0005] An object of the present invention is to provide a polymer composition that has excellent adhesion to a wide range of materials and excellent impact absorption 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 using a combination of a silane-modified hydrogenated block copolymer (I) having a silane-containing functional group, which is obtained by modifying a predetermined hydrogenated block copolymer (i) with an unsaturated silane modifier, and a modified polyolefin (II) having a polar group, and have thus completed the present invention.

[0007] That is, according to the present invention, the following polymer composition is provided.

[0008] [1] A polymer composition comprising: a silane-modified hydrogenated block copolymer (I) having a silane-containing functional group, the silane-modified hydrogenated block copolymer (I) being obtained by modifying a hydrogenated block copolymer (i) having, in this order, an aromatic vinyl polymer block (Ar1), a hydrogenated polymer block (HD) of a conjugated diene polymer, and an aromatic vinyl polymer block (Ar2) with an unsaturated silane modifier; and a modified polyolefin (II) having a polar group. [2] The polymer composition according to [1], wherein the hydrogenated block copolymer (i) comprises at least one of a hydrogenated block copolymer (A) represented by general formula (A) and a hydrogenated block copolymer (B) represented by general formula (B). 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 )) is 3.0 to 20. ) 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.) [3] The polymer composition according to [1] or [2], wherein the content of aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (i) is 20 to 60% by weight. [4] The polymer composition according to any one of [1] to [3], wherein the hydrogenated block copolymer (i) is a hydrogenated block copolymer composition containing the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). [5] The polymer composition according to any one of [4], wherein the weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) in the hydrogenated block copolymer composition is 10 / 90 to 80 / 20. [6] The polymer composition according to any one of [1] to [5], wherein the weight ratio (I / II) of the silane-modified hydrogenated block copolymer (I) to the modified polyolefin (II) in the polymer composition is 10 / 90 to 95 / 5. [7] The polymer composition according to any one of [1] to [6], wherein the weight-average molecular weight of the hydrogenated block copolymer (i) is 20,000 to 500,000. [8] The polymer composition according to any one of [1] to [7], wherein the hydrogenation rate of the olefin in the hydrogenated block copolymer (i) is 10 to 100%. [9] The polymer composition according to any one of [1] to [8], wherein the polar group is an acidic group.

[10] The polymer composition according to any one of [1] to [9], wherein the silane-modified hydrogenated block copolymer (I) has the silane-containing functional group as a side chain in the hydrogenated polymer block (HD) of the conjugated diene polymer.

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

[10] , 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 ４is a hydrocarbon group having a carbon-carbon unsaturated bond.)

[12] The polymer composition according to any one of [1] to

[11] , wherein the hydrogenated polymer block (HD) of the conjugated diene polymer has a vinyl bond content before hydrogenation of 1 to 80 mol %.

[13] The polymer composition according to any one of [1] to

[12] , which is used as an impact absorbing material, a covering material for a wind turbine, an adhesive for electronic substrates, a structural adhesive for automobiles, or an interlayer film for a bulletproof vest.

[0009] According to the present invention, it is possible to provide a polymer composition that has excellent adhesive properties to a wide range of materials and excellent impact absorption properties.

[0010] The polymer composition of the present invention contains a silane-modified hydrogenated block copolymer (I) having a silane-containing functional group and a modified polyolefin (II) having a polar group.

[0011] <Silane-Modified Hydrogenated Block Copolymer (I)> The silane-modified hydrogenated block copolymer (I) used in the present invention is a block copolymer obtained by modifying the hydrogenated block copolymer (i) with an unsaturated silane modifier, and has a skeleton and silane-containing functional groups derived from the hydrogenated block copolymer (i).

[0012] (Hydrogenated Block Copolymer (i)) The hydrogenated block copolymer (i) used in the present invention is a hydrogenated product of an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer constituted by aromatic vinyl polymer blocks Ar1 and Ar2 bonded to both ends of a conjugated diene polymer block HD.

[0013] The aromatic vinyl polymer blocks Ar1 and Ar2 are polymer blocks 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] Each aromatic vinyl polymer block may 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] The hydrogenated polymer block HD of the conjugated diene polymer 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 have been 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] The content of the conjugated diene monomer units (including hydrogenated conjugated diene monomer units) in the hydrogenated polymer block HD of the conjugated diene polymer 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 hydrogenated polymer block HD of the conjugated diene polymer.

[0020] The hydrogenated polymer block HD of the conjugated diene polymer 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 content of the monomer unit other than the conjugated diene monomer unit (including hydrogenated conjugated diene monomer unit) in the hydrogenated polymer block HD of the conjugated diene polymer is determined by the following formula: 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 hydrogenation rate of the olefin in the hydrogenated block copolymer (i) 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 adhesiveness and impact absorption of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved. 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 (i) 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.

[0022] The content of the aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (i) is not particularly limited, but is preferably 10 to 90% by weight, more preferably 15 to 75% by weight, and even more preferably 20 to 60% by weight. By setting the content of the aromatic vinyl monomer units within the above range, the adhesiveness and impact absorption of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0023] 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.

[0024] The weight average molecular weight of the hydrogenated block copolymer (i) is not particularly limited, but is preferably 20,000 to 500,000, more preferably 30,000 to 400,000, even more preferably 35,000 to 150,000, and particularly preferably 40,000 to 100,000.

[0025] The weight average molecular weight (Mw(Ar1), Mw(Ar2)) of each aromatic vinyl polymer block is preferably 1,000 to 250,000, more preferably 2,000 to 120,000, and even more preferably 3,000 to 80,000.

[0026] The weight average molecular weight (Mw(HD)) of the hydrogenated polymer block HD of the conjugated diene polymer is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, still more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000.

[0027] By setting the weight-average molecular weight of the hydrogenated block copolymer (i) and each polymer block within the above range, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0028] The vinyl bond content (proportion of 1,2-vinyl bonds and 3,4-vinyl bonds in all conjugated diene monomer units) of the hydrogenated polymer block HD of the conjugated diene polymer before hydrogenation 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, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved. The vinyl bond content of the hydrogenated polymer block HD of the conjugated diene polymer before hydrogenation can be adjusted by using deuterated chloroform as a solvent. １ It can be determined by H-NMR.

[0029] The molecular weight distribution of the hydrogenated block copolymer (i), which is expressed as the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 2, more preferably 1.001 to 1.5, and even more preferably 1.01 to 1.15.

[0030] The molecular weight distribution of each polymer block constituting the hydrogenated block copolymer (i), 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, more preferably 1.05 or less. 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.

[0031] Specific examples of the hydrogenated block copolymer (i) include the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) described below. The hydrogenated block copolymer (i) preferably contains at least one of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B).

[0032] The hydrogenated block copolymer (A) is an asymmetric triblock copolymer represented by the general formula (A): 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 )) is 3.0 to 20.

[0033] The hydrogenated block copolymer (A) is a conjugated diene polymer block HD. ａAt both ends of each of the two aromatic vinyl polymer blocks Ar1 ａ , Ar2 ａ The hydrogenated block copolymer (I) is a hydrogenated product of an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer formed by the bonding of the following units. By modifying the hydrogenated block copolymer (A) with an unsaturated silane modifier, a silane-modified hydrogenated block copolymer (A-Si) having a silane-containing functional group is obtained. From the viewpoint of providing a polymer composition with even more excellent impact absorption properties, it is preferable to use the silane-modified hydrogenated block copolymer (A-Si) as the silane-modified hydrogenated block copolymer (I).

[0034] Aromatic vinyl polymer block Ar1 ａ and Ar2 ａ is a polymer block composed of aromatic vinyl monomer units. ａ and Ar2 ａ Examples of the monomers used to form the aromatic vinyl polymer block of the hydrogenated block copolymer (i) include the monomers described above as the monomers used to form the aromatic vinyl polymer block of the hydrogenated block copolymer (i). The preferred types and preferred contents of each monomer are the same as the preferred types and preferred contents of the aromatic vinyl polymer block of the hydrogenated block copolymer (i).

[0035] Hydrogenated polymer block HD of conjugated diene polymer ａ 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. ａ Examples of the monomers used to form the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i) include the monomers described above as the monomers used to form the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i). The preferred types and preferred contents of each monomer are the same as the preferred types and preferred contents of the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i).

[0036] The hydrogenated block copolymer (A) is Ar1 ａ Weight average molecular weight (Mw(Ar1ａ )) 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.

[0037] 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 content of the polymer composition within the above range, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0038] The hydrogenation rate of the olefin in the hydrogenated block copolymer (A) is preferably within the suitable range of the hydrogenation rate of the olefin in the hydrogenated block copolymer (i).

[0039] The content of aromatic vinyl monomer units relative to all monomer units in 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, the adhesiveness and impact absorption of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0040] 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.

[0041] Aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight 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.

[0042] Aromatic vinyl polymer block Ar2 having a relatively high weight average molecular weight 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.

[0043] Hydrogenated polymer block HD of conjugated diene polymer 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.

[0044] By setting the weight average molecular weights of the hydrogenated block copolymer (A) and each polymer block within the above ranges, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0045] Hydrogenated polymer block HD of conjugated diene polymer ａ The vinyl bond content before hydrogenation of the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i) is preferably within the suitable range of the vinyl bond content before hydrogenation of the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i).

[0046] 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.

[0047] The hydrogenated block copolymer (B) is a symmetric triblock copolymer represented by the 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.

[0048] 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 The block copolymer (B) is a hydrogenated aromatic vinyl-conjugated diene-aromatic vinyl block copolymer formed by the bonding of the following: By modifying the hydrogenated block copolymer (B) with an unsaturated silane modifier, a silane-modified hydrogenated block copolymer (B-Si) having a silane-containing functional group is obtained.

[0049] Aromatic vinyl polymer block Ar1 ｂ and Ar2 ｂ is a polymer block composed of aromatic vinyl monomer units. ｂ and Ar2 ｂExamples of the monomers used to form the aromatic vinyl polymer block of the hydrogenated block copolymer (i) include the monomers described above as the monomers used to form the aromatic vinyl polymer block of the hydrogenated block copolymer (i). The preferred types and preferred contents of each monomer are the same as the preferred types and preferred contents of the aromatic vinyl polymer block of the hydrogenated block copolymer (i).

[0050] Hydrogenated polymer block HD of conjugated diene polymer 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 Examples of the monomers used to form the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i) include the monomers described above as the monomers used to form the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i). The preferred types and preferred contents of each monomer are the same as the preferred types and preferred contents of the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i).

[0051] In addition, when the hydrogenated block copolymer (B) is produced by a production method using, for example, a coupling agent, the hydrogenated polymer block HD of the conjugated diene polymer 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

[0052] 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’’ The residue X of the coupling agent may be a residue of a bifunctional coupling agent, which will be described later.

[0053] The hydrogenated block copolymer (B) isｂ 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 0.97 to 1.03. ｂ ) / Mw(Ar1 ｂ By setting the content of the polymer composition within the above range, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0054] The hydrogenation rate of the olefin in the hydrogenated block copolymer (B) is preferably within the suitable range of the hydrogenation rate of the olefin in the hydrogenated block copolymer (i).

[0055] The content of the 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. By setting the content of the aromatic vinyl monomer units within the above range, the adhesiveness and impact absorption of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0056] 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.

[0057] Aromatic vinyl polymer block Ar1 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 , 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.

[0058] Hydrogenated polymer block HD of conjugated diene polymer 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.

[0059] By setting the weight average molecular weights of the hydrogenated block copolymer (B) and each polymer block within the above ranges, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0060] Hydrogenated polymer block HD of conjugated diene polymer ｂ The vinyl bond content before hydrogenation of the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i) is preferably within the suitable range of the vinyl bond content before hydrogenation of the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i).

[0061] 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.

[0062] (Hydrogenated Block Copolymer Composition) The hydrogenated block copolymer (i) is preferably a hydrogenated block copolymer composition containing the above-mentioned hydrogenated block copolymer (A) and the above-mentioned hydrogenated block copolymer (B). That is, the silane-modified hydrogenated block copolymer (I) of the present invention is preferably a silane-modified hydrogenated block copolymer composition obtained by modifying a hydrogenated block copolymer composition containing the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) with an unsaturated silane modifier.

[0063] In the hydrogenated block copolymer composition, the two aromatic vinyl polymer blocks Ar1 of the hydrogenated block copolymer (B) 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.

[0064] In the hydrogenated block copolymer composition, the hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (B) 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.

[0065] The weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) 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, the adhesiveness and impact absorption properties of the polymer composition can be further improved, and the moldability and mechanical properties of the polymer composition 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.

[0066] (Silane-Containing Functional Group) The silane-modified hydrogenated block copolymer (I) used in the present invention is a block copolymer obtained by modifying the hydrogenated block copolymer (i) with an unsaturated silane modifier. The silane-modified hydrogenated block copolymer (I) 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 (I) 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.

[0067] Here, when the hydrogenated block copolymer (i) is modified with an unsaturated silane modifier, the unsaturated silane modifier usually acts on the carbon atoms in the hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (i) to introduce a silane-containing functional group as a side chain into the hydrogenated polymer block HD of the conjugated diene polymer. In this case, the silane-modified hydrogenated block copolymer (I) has the silane-containing functional group as a side chain in the hydrogenated polymer block HD of the conjugated diene polymer.

[0068] 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.

[0069] 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 ４ may be the same or different.

[0070] R１ ~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 effects of the present invention can be enhanced.

[0071] 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.

[0072] 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 effects of the present invention can be enhanced.

[0073] For example, R ４ is a vinyl group-containing hydrocarbon group, the compound (1) is a compound (2) represented by the following general formula (2):

[0074] In the above general formula (2), R１ ~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.

[0075] 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):

[0076] The unsaturated silane modifier is preferably a compound (4) represented by the following general formula (4).

[0077] 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.

[0078] 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 ８may 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).

[0079] 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).

[0080] The amount of silane-containing functional groups in the silane-modified hydrogenated block copolymer (I) is not particularly limited. The amount of silane-containing functional groups per 100 g of the silane-modified hydrogenated block copolymer (I) 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, the effects of the present invention can be enhanced.

[0081] (Method for Producing Silane-Modified Hydrogenated Block Copolymer (I)) The silane-modified hydrogenated block copolymer (I) used in the present invention can be produced by a production method including a modification step of reacting the hydrogenated block copolymer (i) with an unsaturated silane modifier.

[0082] The hydrogenated block copolymer (i) 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 (i) used in the present invention is preferably a production method comprising the following steps (1i) to (5i): (1i): 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. (2i): A step of adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having an active end obtained in the step (1i) above and polymerizing the conjugated diene monomer to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having an active end. (3i): 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 (2i) above and polymerizing the aromatic vinyl monomer to obtain a solution containing block copolymer (i'). (4i): A step of hydrogenating the solution containing block copolymer (i') obtained in the step (3i) above to obtain a solution containing hydrogenated block copolymer (i). (5i): A step of recovering hydrogenated block copolymer (i) from the solution containing hydrogenated block copolymer (i) obtained in the step (4i).

[0083] <Step (1i)> In the above production method, first, in step (1i), 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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 3 to 60% by weight, more preferably 5 to 45% by weight, and even more preferably 7 to 30% by weight.

[0091] Furthermore, when producing the hydrogenated block copolymer (i), 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.

[0092] In producing the hydrogenated block copolymer (i), 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.

[0093] 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.

[0094] 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 (1i) will constitute the aromatic vinyl polymer block Ar1 or Ar2 of the hydrogenated block copolymer (i). Therefore, the polymerization conditions in step (1i), including the amount of aromatic vinyl monomer, can be determined depending on the target weight-average molecular weight of these polymer blocks, etc.

[0095] <Step (2i)> Next, in step (2i), a conjugated diene monomer is added to the solution containing the aromatic vinyl polymer having active ends obtained in step (1i) above, and the conjugated diene monomer is polymerized to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends.

[0096] According to the step (2i), by adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having active ends obtained in the step (1i), 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.

[0097] The conjugated diene polymer chain formed in step (2i) (the conjugated diene block constituting the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2i)) will constitute the hydrogenated polymer block HD of the conjugated diene polymer in the hydrogenated block copolymer (i). Therefore, the polymerization conditions in step (2i), including the amount of 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 (1i) above).

[0098] <Step (3i)> Next, in step (3i), an aromatic vinyl monomer is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2i), and the aromatic vinyl monomer is polymerized to obtain a solution containing block copolymer (i′).

[0099] According to the step (3i), by adding an aromatic vinyl monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active end obtained in the above step (2i), 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.

[0100] The aromatic vinyl polymer chain formed in step (3i) (the aromatic vinyl polymer block constituting the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end obtained in step (3i)) will constitute one of the aromatic vinyl polymer blocks Ar1 and Ar2 of the hydrogenated block copolymer (i) (i.e., Ar1 or Ar2 is a block different from the block formed in step (1i); for example, when Ar1 is formed in step (1i), Ar2 will be the corresponding block). Therefore, the polymerization conditions in step (3i), including the amount of aromatic vinyl monomer, may be determined depending on the target weight-average molecular weight of the polymer block (for example, the polymerization conditions may be determined within the ranges explained in step (1i) above).

[0101] 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 (i'). Note that block copolymer (i') obtained in step (3i) is the block copolymer before hydrogenation for obtaining hydrogenated block copolymer (i).

[0102] 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.

[0103] <Step (4i)> Next, in step (4i), the solution containing the block copolymer (i′) obtained in step (3i) is subjected to a hydrogenation reaction to obtain a solution containing the hydrogenated block copolymer (i).

[0104] The method for hydrogenating the solution containing the block copolymer (i') is not particularly limited, and examples thereof include a method of contacting the solution containing the block copolymer (i') with hydrogen in the presence of a hydrogenation catalyst.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] <Step (5i)> Next, in the step (5i), the target hydrogenated block copolymer (i) is recovered from the solution containing the hydrogenated block copolymer (i) obtained in the step (4i).

[0109] 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.

[0110] When the hydrogenated block copolymer (i) 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 (i) 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 (i) thus obtained may be processed into pellets or the like according to a conventional method before use.

[0111] The solid (pellet-like, crumb-like, etc.) hydrogenated block copolymer (i) thus obtained is preferably used after reducing the water content in the solid hydrogenated block copolymer (i) 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.

[0112] <Modification Step> The silane-modified hydrogenated block copolymer (I) used in the present invention can be produced by a production method including a modification step of reacting the hydrogenated block copolymer (i) with an unsaturated silane modifier. Preferably, the silane-modified hydrogenated block copolymer (I) can be produced by melt-kneading the hydrogenated block copolymer (i), the unsaturated silane modifier, and a peroxide.

[0113] 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.

[0114] 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, 1,3-bis(t-butylperoxyisopropyl)benzene, p-chlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t-butylbenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane. These can be used alone or in combination of two or more.

[0115] 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.

[0116] The method for melt-kneading the hydrogenated block copolymer (i), the unsaturated silane modifier, and the peroxide is not particularly limited, and examples thereof include a method in which each component is 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 suppress 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.

[0117] (Method for Producing Silane-Modified Hydrogenated Block Copolymer Composition) Next, an example of a method for producing the silane-modified hydrogenated block copolymer (I) of the present invention is described below, in which the silane-modified hydrogenated block copolymer composition is obtained by modifying a hydrogenated block copolymer composition containing the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) with an unsaturated silane modifier.

[0118] 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.

[0119] 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).

[0120] <Steps (1) and (2)> Steps (1) and (2) are similar to the above-described steps (1i) and (2i), and similar conditions can be employed for these steps.

[0121] 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 aromatic vinyl polymer block Ar1 of 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.

[0122] 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 the 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.

[0123] 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.

[0124] <Step (3)> Step (3) is the same as the above-mentioned step (3i) except that the active terminal is not inactivated, and the same conditions can be employed.

[0125] The aromatic vinyl polymer chain formed in step (3) (the aromatic vinyl polymer 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.

[0126] <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').

[0127] The block copolymer (B') obtained in the step (4) is the block copolymer before hydrogenation to obtain the hydrogenated block copolymer (B).

[0128] 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.

[0129] 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.

[0130] <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').

[0131] 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).

[0132] 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 (1i)).

[0133] <Steps (6) and (7)> ​​A hydrogenated block copolymer composition can be obtained by using the solution containing block copolymer (B') and block copolymer (A') obtained in step (5) and performing the operations in steps (6) and (7). Note that steps (6) and (7) are similar to steps (4i) and (5i) described above, and similar conditions can be used for these steps.

[0134] 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.

[0135] In addition to the production method including the above-described steps (1) to (7), a production method for a hydrogenated block copolymer composition including 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.

[0136] <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.

[0137] <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).

[0138] 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.

[0139] 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.

[0140] <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′).

[0141] 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).

[0142] 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)).

[0143] <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.

[0144] The silane-modified hydrogenated block copolymer composition can be produced by a production method including a modification step of reacting the hydrogenated block copolymer composition with an unsaturated silane modifier. Preferably, the silane-modified hydrogenated block copolymer composition can be produced by mixing the hydrogenated block copolymer composition with the unsaturated silane modifier in the presence of a peroxide.

[0145] The conditions for the modification step can be the same as those for the modification step in which the hydrogenated block copolymer (i) is reacted with the unsaturated silane modifier.

[0146] The silane-modified hydrogenated block copolymer (I) used in the present invention may be a crosslinked product. The crosslinked product preferably has a crosslinked structure derived from the silane-containing functional group in the silane-modified hydrogenated block copolymer (I). Furthermore, the crosslinked structure derived from the silane-containing functional group preferably contains a —Si—O—Si— bond.

[0147] The crosslinked product can be preferably produced by a method of contacting the silane-modified hydrogenated block copolymer (I) with a condensation reaction catalyst for condensing the silane-containing functional groups. This production method allows for the introduction of a crosslinked structure derived from the silane-containing functional groups between polymer chains. Furthermore, when the silane-modified hydrogenated block copolymer (I) is obtained using an unsaturated silane modifier having an alkoxy group as the unsaturated silane modifier, contacting the silane-modified hydrogenated block copolymer (I) with a condensation reaction catalyst allows for the introduction of a crosslinked structure containing an —Si—O—Si— bond between polymer chains.

[0148] 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.

[0149] Among these, polycarboxylic acids, titanium compounds, and tin compounds are preferred, and succinic acid, titanium acetylacetonate, and dibutyltin dilaurate are more preferred.

[0150] 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.

[0151] The method for contacting the silane-modified hydrogenated block copolymer (I) with the condensation reaction catalyst is not particularly limited, but a method in which the silane-modified hydrogenated block copolymer (I) is mixed with the condensation reaction catalyst is preferred.

[0152] The method for mixing the silane-modified hydrogenated block copolymer (I) and 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, more preferably 200 to 240°C. The mixing time is preferably 0.5 to 20 minutes, more preferably 1 to 10 minutes.

[0153] It is also preferable to carry out the modification step for obtaining the silane-modified hydrogenated block copolymer (I) 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.

[0154] Specifically, a preferred method is to mix the hydrogenated block copolymer (i), which is the raw material for the silane-modified hydrogenated block copolymer (I), with an unsaturated silane modifier in the presence of a peroxide (modification step), and then add a condensation reaction catalyst to the resulting mixture and further mix them (crosslinking step). In this production method, after the addition of the condensation reaction catalyst, the modification reaction and the crosslinking reaction may proceed simultaneously.

[0155] <Modified Polyolefin (II)> The polymer composition of the present invention further contains a modified polyolefin (II) having a polar group. The modified polyolefin (II) used in the present invention is a polymer having a polar group and containing an olefin as the main repeating unit. The modified polyolefin (II) may be used alone or in combination of two or more.

[0156] As the olefin, α-olefins such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene are preferred, and ethylene and propylene are more preferred.

[0157] Examples of polar groups include polar groups having an oxygen atom such as a carboxy group (hydroxycarbonyl group), a sulfonic acid group, a phosphate group, or a hydroxyl group; polar groups having a nitrogen atom such as a primary amino group, a secondary amino group, a primary amide group, or a secondary amide group (imide group); and polar groups having a sulfur atom such as a thiol group. Examples of polar groups also include salts formed from acidic groups such as a carboxy group, a sulfonic acid group, or a phosphate group and a metal atom such as lithium, sodium, potassium, calcium, magnesium, or aluminum, or ammonium. Specific examples of polar groups include carboxylate groups, sulfonate groups, and phosphate groups. The modified polyolefin (II) used in the present invention may have only one type of polar group, or may have two or more types of polar groups.

[0158] The polar group is preferably an acidic group, more preferably a carboxyl group. When the modified polyolefin (II) used in the present invention has an acidic group as the polar group, the silane-modified hydrogenated block copolymer (I) used in the present invention and the modified polyolefin (II) each have different functional groups, i.e., an acidic group and a silane-containing functional group, respectively, which unexpectedly further improves the adhesiveness of the polymer composition of the present invention.

[0159] The modified polyolefin (II) may be, for example, a polyolefin having no polar groups, such as an olefin homopolymer, a copolymer of two or more olefins, or a copolymer of an olefin and a monomer other than an olefin, in which a polar group has been introduced by reacting the polyolefin with a modifier containing a polar group. Specifically, the modified polyolefin (II) may be a graft copolymer obtained by graft-modifying a polyolefin having no polar groups with a polar group-containing monomer. The modified polyolefin (II) may also be an olefin-polar group-containing monomer copolymer containing units derived from the polar group-containing monomer in the main chain. Furthermore, the modified polyolefin (II) may be an ionomer resin obtained by reacting a modified polyolefin having an acidic group as the polar group with Na ions, Zn ions, or the like. Among these, the modified polyolefin (II) is preferably a graft copolymer obtained by graft-modifying a polyolefin having no polar groups with a polar group-containing monomer.

[0160] Examples of polyolefins having no polar group include homopolymers or copolymers of α-olefins such as ethylene and propylene, for example, α-olefin homopolymers such as polyethylenes such as linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and metallocene polyethylene, polypropylene, metallocene polypropylene, polymethylpentene, and polybutene; and copolymers of ethylene and other α-olefins such as ethylene-propylene random copolymers, ethylene-propylene block copolymers, ethylene-butene-1 copolymers, ethylene-propylene-butene-1 copolymers, and ethylene-cyclic olefin copolymers.

[0161] The polar group-containing monomer preferably has a carbon-carbon unsaturated bond in the molecule. The polar group-containing monomer may have a polar group in the molecule, or may have a group that forms a polar group after reaction with the polyolefin (such as an acid anhydride group).

[0162] Examples of the polar group-containing monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassidic acid, atropic acid, and cinnamic acid; unsaturated polycarboxylic acids and anhydrides thereof such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and unsaturated alcohols such as allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, and 2-hexen-1-ol. Further, examples of the polar group-containing monomer include salts of the above-mentioned unsaturated carboxylic acids with ammonium or a metal atom such as lithium, sodium, potassium, calcium, magnesium, or aluminum. Among these, the polar group-containing monomer is preferably an unsaturated carboxylic acid or an unsaturated polycarboxylic acid anhydride, more preferably an unsaturated polycarboxylic acid or an unsaturated polycarboxylic acid anhydride, and even more preferably maleic acid or maleic anhydride.

[0163] From the viewpoint of heat resistance, the modified polyolefin (II) preferably has an α-olefin unit content of 50% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight or more. The modified polyolefin (II) preferably has an aromatic vinyl polymer unit content of 10% by weight or less, more preferably 1% by weight or less (substantially no aromatic vinyl polymer unit).

[0164] The weight ratio (I / II) of the silane-modified hydrogenated block copolymer (I) to the modified polyolefin (II) in the polymer composition of the present invention is not particularly limited, but is preferably 10 / 90 to 95 / 5, more preferably 20 / 80 to 92 / 8, even more preferably 30 / 70 to 90 / 10, particularly preferably 40 / 60 to 88 / 12, particularly preferably 50 / 50 to 85 / 15, and most preferably 55 / 45 to 85 / 15. By setting the weight ratio (I / II) within the above range, the adhesiveness and impact absorption of the polymer composition can be further improved, and further, the moldability and mechanical properties of the polymer composition can be improved.

[0165] (Other Components) The polymer composition of the present invention may contain other polymer components in addition to the silane-modified hydrogenated block copolymer (I) and the modified polyolefin (II), as long as the effects of the present invention are not impaired, or may contain only the silane-modified hydrogenated block copolymer (I) and the modified polyolefin (II) as polymer components.

[0166] Examples of other polymer components include aromatic vinyl-conjugated diene-aromatic vinyl block copolymers other than the silane-modified hydrogenated block copolymer (I), 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 other than the modified polyolefin (II); 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 components is not particularly limited, and may be before or after the modification step with the unsaturated silane modifier.

[0167] In the polymer composition of the present invention, the content of polymer components other than the silane-modified hydrogenated block copolymer (I) and the modified polyolefin (II) 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 (I) and the modified polyolefin (II) in the polymer composition of the present invention.

[0168] The polymer composition of the present invention may further contain, as necessary, an antioxidant, zinc oxide, filler, softener, antibacterial agent, light stabilizer, ultraviolet absorber, dye, lubricant, 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.

[0169] The polymer composition of the present invention can be produced, for example, by mixing the silane-modified hydrogenated block copolymer (I), the modified polyolefin (II), and various additives used as needed.

[0170] The method for mixing these components is not particularly limited, and examples thereof include a method in which each component is heated and melted and 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 each component is dissolved in a solvent and mixed uniformly, and then the solvent is removed by heating or the like. Among these, the heated and melted mixing method is preferred from the viewpoint of more efficient mixing. The temperature during the heated and melted mixing is preferably within a temperature range that can suppress excessive decomposition of each component and the progression of unexpected crosslinking reactions, for example, 90 to 150°C is preferred, and 100 to 130°C is more preferred.

[0171] The polymer composition of the present invention may be molded into a desired shape (for example, pellets, sheets, strands, or chips) depending on the application.

[0172] <Applications> The polymer composition of the present invention has excellent adhesive properties and impact absorption properties for a wide range of materials, and can therefore be suitably used in a variety of applications, such as impact absorbing materials such as reinforced plastics (CFRP, etc.) used in aircraft, etc., covering materials for wind turbines, adhesives for electronic substrates (power module systems), structural adhesives for automobiles, and interlayer films for bulletproof vests.

[0173] In particular, the polymer composition of the present invention can be suitably used as an adhesive for bonding dissimilar materials. For example, it can be suitably used as an adhesive for bonding materials such as glass, silicon wafers, ceramics, metals, plastics, reinforcing fibers, wood, leather, stone, concrete, rock, paper, corrugated cardboard, fabric, glass, brick, plaster, cement, tiles, mortar, and asphalt. Furthermore, since the polymer composition of the present invention has excellent impact absorption properties, when dissimilar materials are bonded together using the polymer composition of the present invention, the resulting bonded body has excellent impact resistance.

[0174] 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.

[0175] [Weight-average molecular weight and molecular weight distribution of (hydrogenated) block copolymers] A chart based on the polystyrene-equivalent molecular weight was obtained by high-performance liquid chromatography using tetrahydrofuran as a carrier at a flow rate of 0.35 ml / min. The weight-average molecular weight and molecular weight distribution of the (hydrogenated) block copolymer were determined based on the obtained chart. The analyzer 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.

[0176] [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.

[0177] [Weight-Average Molecular Weight of Styrene Polymer Block in 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.

[0178] Specifically, the procedure was as follows: 300 mg of sample was dissolved in a reaction vessel containing 100 ml of molecular sieve-treated dichloromethane. The reaction vessel was then 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, 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 the reaction vessel was cooled 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. Subsequently, while stirring the solution, dilute hydrochloric acid was added dropwise in small amounts to the reaction vessel until hydrogen generation was almost completely eliminated. After the reaction, the solid product formed in the solution was filtered and 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-mentioned method for measuring weight-average molecular weight, and the value was taken as the weight-average molecular weight of the styrene polymer block.

[0179] [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.

[0180] [Vinyl bond content of isoprene polymer block (before hydrogenation)] Deuterated chloroform was used as the solvent. １ It was determined based on H-NMR measurement.

[0181]

[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.

[0182] [Styrene unit content of (hydrogenated) block copolymer] Deuterated chloroform was used as the solvent. １ The styrene unit content of the (hydrogenated) block copolymer was determined based on the H-NMR measurement.

[0183] [Olefin hydrogenation rate (mol%) of hydrogenated block copolymer] Deuterated chloroform was used as the solvent. １ The olefin amount was determined for each of the block copolymer before hydrogenation and the hydrogenated block copolymer 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 device. In the present examples and comparative examples, both the block copolymer before hydrogenation and the hydrogenated block copolymer 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.

[0184] [Shore A Hardness of Hydrogenated Block Copolymer Composition] According to ISO 7619, the Shore A hardness of the hydrogenated block copolymer composition was determined.

[0185] [Adhesion] The polymer composition was fed into a heat press set at 180°C and molded into a 12.5 mm long x 25 mm wide x 0.1 mm thick adhesive sheet. The resulting adhesive sheet was used to bond a 100 mm long x 25 mm wide CFRP sheet (manufactured by Standard Test Piece Co., Ltd., a CFRP (matt) evaluation specimen for JIS K6850 adhesion testing) to the ends of a 100 mm long x 25 mm wide aluminum sheet (a 12.5 mm long x 25 mm wide region at the longitudinal end) to prepare an adhesive sample measuring approximately 187.5 mm long x 25 mm wide. Specifically, the sheet-like polymer composition obtained above was placed on the end of the CFRP sheet, and the end of the aluminum sheet was placed on top of it in a manner that prevented direct contact between the CFRP sheet and the aluminum sheet. This was placed in a pressure autoclave and held at 150°C, 0.8 MPa, and 30 minutes to prepare an adhesive sample. The tensile shear adhesive strength of the adhesive sample was measured in accordance with JIS K6850 using a precision universal testing machine (product name "Autograph AG-10kN X plus," manufactured by Shimadzu Corporation) at a testing temperature of 23°C and a testing speed of 1 mm / min. If the tensile shear adhesive strength is 5 MPa or more, it can be determined that the polymer composition has excellent adhesiveness to a wide range of materials. Furthermore, if the tensile shear adhesive strength is even greater, it can be determined that the adhesiveness of the polymer composition is even better.

[0186] [Impact Absorbency] A polymer composition was fed into a heat press set at 180°C and molded into a size of 25 mm length x 25 mm width x 1 mm thickness to obtain a sheet of the polymer composition. The obtained sheet was placed in the center of a CFRP sheet (manufactured by Standard Test Piece Co., Ltd., a CFRP (matt) evaluation specimen for JIS K6850 adhesion test), which was then placed in a pressurized autoclave and maintained at 150°C, 0.8 MPa, and 30 minutes to prepare a sample. A drop weight test was performed in which a 4 kg weight equipped with an acceleration sensor was dropped from a height of 100 mm onto the center of the sample. The maximum acceleration in the acceleration-time diagram recorded in each drop weight test was then determined, and the drop impact acceleration (X １In addition, a drop weight test was carried out in the same manner except that a single CFRP sheet was used instead of the sample, and the drop impact acceleration (X ０ ) was calculated. The drop impact acceleration (X ０ ) as the standard, the drop impact acceleration (X １ ) Decrease rate (1-X １ / X ０ The greater the reduction rate of the drop impact acceleration, the more excellent the impact absorption of the polymer composition.

[0187] Detailed conditions for the drop weight test are as follows: Test room temperature: 23±2°C Tip shape of the falling object: SUS, R10 hemispherical Weight of the falling object: Approximately 4 kg Drop height: Approximately 10 cm Acceleration measurement sensor: PCB Piezotronics, model: M350B04 Acceleration recorder: OROS, FFT analyzer, model: OR35-4 Small compression load cell: Kyowa Dengyo, model: LCX-A-10kN-ID

[0188] [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%.

[0189] 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%.

[0190] 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%.

[0191] 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).

[0192] 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%.

[0193] 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.

[0194] (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) ２The 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.

[0195] (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.

[0196] 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.

[0197] 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 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 before hydrogenation was used.

[0198]

[0199]

[0200] Example 1 100 parts of the hydrogenated block copolymer composition (Polymer 1) obtained in Production Example 1, 3 parts of vinyltrimethoxysilane, and 0.25 parts of 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 (Xplore MC40) and melt-kneaded at 220°C for 3 minutes. 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 (group (3)) derived from vinyltrimethoxysilane was introduced as a side chain into the silane-modified polymer 1. As a result, a silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) containing the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) was obtained.

[0201] 80 parts of the obtained silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) and 20 parts of maleic acid-modified polypropylene polymer 1 (trade name "Admer QE060", manufactured by Mitsui Chemicals, Inc., a graft copolymer obtained by graft-modifying an ethylene-propylene random copolymer having propylene as the main repeating unit with maleic anhydride, melting point 140 ° C., MFR (190 ° C.) 7.0 g / 10 min) as modified polyolefin (II) were fed to a small twin-screw kneader (trade name "Xplore MC40", manufactured by Xplore Instruments) and melt-kneaded at 200 ° C. for 3 minutes to obtain a polymer composition. The obtained polymer composition was evaluated for adhesion and impact absorption according to the above-mentioned methods. The results are shown in Table 3.

[0202] Examples 2 to 4 Polymer compositions were obtained in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 3, and evaluated in the same manner as in Example 1. The results are shown in Table 3. In Example 4, maleic acid-modified polypropylene polymer 2 (trade name "Admer QF500", manufactured by Mitsui Chemicals, Inc., a graft copolymer obtained by graft-modifying polypropylene with maleic anhydride, melting point 165°C, MFR (190°C) 3.0 g / 10 min) was used as the modified polyolefin (II).

[0203] Examples 5 to 8 A silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) containing the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer composition (polymer 2) obtained in Production Example 2 was used instead of the hydrogenated block copolymer composition (polymer 1) obtained in Production Example 1. Then, polymer compositions were obtained in the same manner as in Example 1, except that the silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) was used in the amount shown in Table 3 instead of the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1), and the type and amount of modified polyolefin (II) were changed as shown in Table 3. The results are shown in Table 3.

[0204] Example 9 A silane-modified hydrogenated block copolymer (B-Si) (silane-modified polymer 3) was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer (B) (polymer 3) obtained in Production Example 3 was used instead of the hydrogenated block copolymer composition (polymer 1) obtained in Production Example 1. A polymer composition was then obtained in the same manner as in Example 1, except that the silane-modified hydrogenated block copolymer (B-Si) (silane-modified polymer 3) was used instead of the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0205] A silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) was obtained in the same manner as in Example 1. Then, the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) alone, instead of the polymer composition, was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0206] A silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) was obtained in the same manner as in Example 2. Then, the silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) alone, instead of the polymer composition, was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0207] Comparative Example 3 A polymer composition was obtained in the same manner as in Example 1, except that 80 parts of a silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) was used instead of the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1), and 20 parts of LDPE (trade name "Novatec LD F161", manufactured by Japan Polyethylene Corporation, substantially free of polar groups) was used as the modified polyolefin (II). The results are shown in Table 3.

[0208] Comparative Example 4 A polymer composition was obtained in the same manner as in Comparative Example 3, except that the amounts of each component were changed as shown in Table 3, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0209] Comparative Example 5 Instead of the polymer composition, the maleic acid-modified polypropylene polymer 1 alone was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0210] Comparative Example 6 A polymer composition was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer composition (Polymer 2) obtained in Production Example 2 was used instead of the silane-modified hydrogenated block copolymer composition (Silane-modified Polymer 1), and was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0211] Comparative Example 7 A polymer composition was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer (B) (Polymer 3) obtained in Production Example 3 was used instead of the silane-modified hydrogenated block copolymer composition (Silane-modified Polymer 1), and was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0212]

[0213] As is clear from Table 3, the polymer compositions containing the silane-modified hydrogenated block copolymer (I) having a silane-containing functional group and the modified polyolefin (II) having a polar group were excellent in adhesion to a wide range of materials and impact absorption properties (Examples 1 to 9).

[0214] On the other hand, when no polyolefin was contained (Comparative Examples 1 and 2), when an unmodified polyolefin was used (Comparative Examples 3 and 4), when no hydrogenated block copolymer was contained (Comparative Example 5), and when a hydrogenated block copolymer (i) having no silane-containing functional group was used (Comparative Examples 6 and 7), the adhesiveness was poor. Furthermore, when no hydrogenated block copolymer was contained (Comparative Example 5), the impact absorption was also poor.

Claims

1. A polymer composition comprising: a silane-modified hydrogenated block copolymer (I) having a silane-containing functional group, the silane-modified hydrogenated block copolymer (I) being obtained by modifying a hydrogenated block copolymer (i) having, in this order, an aromatic vinyl polymer block (Ar1), a hydrogenated polymer block (HD) of a conjugated diene polymer, and an aromatic vinyl polymer block (Ar2) with an unsaturated silane modifier; and a modified polyolefin (II) having a polar group.

2. The polymer composition according to claim 1, wherein the hydrogenated block copolymer (i) comprises at least one of a hydrogenated block copolymer (A) represented by general formula (A) and a hydrogenated block copolymer (B) represented by general formula (B). 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 )) is 3.0 to 20. ) 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.

3. The polymer composition according to claim 1 or 2, wherein the content of aromatic vinyl monomer units in the hydrogenated block copolymer (i) is 20 to 60% by weight based on the total weight of all monomer units.

4. The polymer composition according to claim 2, wherein the hydrogenated block copolymer (i) is a hydrogenated block copolymer composition containing the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B).

5. The polymer composition according to claim 4, wherein the weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) in the hydrogenated block copolymer composition is 10 / 90 to 80 / 20.

6. The polymer composition according to any one of claims 1 to 5, wherein the weight ratio (I / II) of the silane-modified hydrogenated block copolymer (I) to the modified polyolefin (II) in the polymer composition is 10 / 90 to 95 / 5.

7. The polymer composition according to any one of claims 1 to 6, wherein the weight average molecular weight of the hydrogenated block copolymer (i) is 20,000 to 500,000.

8. The polymer composition according to any one of claims 1 to 7, wherein the hydrogenation rate of the olefin in the hydrogenated block copolymer (i) is 10 to 100%.

9. The polymer composition according to any one of claims 1 to 8, wherein the polar group is an acidic group.

10. The polymer composition according to any one of claims 1 to 9, wherein the silane-modified hydrogenated block copolymer (I) has the silane-containing functional group as a side chain in the hydrogenated polymer block (HD) of the conjugated diene polymer.

11. The polymer composition according to any one of claims 1 to 10, 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.

12. The polymer composition according to any one of claims 1 to 11, wherein the hydrogenated polymer block (HD) of the conjugated diene polymer has a vinyl bond content of 1 to 80 mol % before hydrogenation.

13. The polymer composition according to any one of claims 1 to 12, which is used as an impact absorbing material, a covering material for a wind turbine, an adhesive for electronic substrates, a structural adhesive for automobiles, or an interlayer film for a bulletproof vest.

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