Masterbatch composition and aromatic vinyl-conjugated diene copolymer composition obtained by adding the masterbatch composition

Abstract

The present invention provides a masterbatch composition, which contains 30 to 98% by weight of an aromatic vinyl polymer containing at least one aromatic vinyl polymer block, and 2 to 70% by weight of a hydrocarbon compound group containing a plurality of hydrocarbon compounds having different carbon numbers within a range of 12 to 60, wherein, in the hydrocarbon compound group, when the total peak area of ​​the components within a range of 12 to 60 is taken as 100%, the total peak area of ​​the components having carbon numbers of 24 to 27 is 5% or more, the total peak area of ​​the components having carbon numbers of 27 to 30 is 5% or more, the total peak area of ​​the components having carbon numbers of 30 to 33 is 5% or more, the total peak area of ​​the components having carbon numbers of 33 to 36 is 5% or more, and the total peak area of ​​the components having carbon numbers of 27 or less is 45% or less.

Description

Technical Field

[0001] The present invention relates to a masterbatch composition and an aromatic vinyl-conjugated diene copolymer composition obtained by adding the masterbatch composition. Background Art

[0002] Aromatic vinyl-conjugated diene copolymers such as aromatic vinyl-conjugated diene-aromatic vinyl block copolymers are particularly elastic and soft among thermoplastic elastomers, and therefore one of their representative uses is as a material for stretchable films used in sanitary products such as disposable diapers and sanitary products.

[0003] Sanitary products such as disposable diapers and sanitary products require good tracking and fit to the wearer's movements, so stretchable films are used in various parts. For example, Patent Document 1 discloses a composition for forming an elastomer for sanitary products such as disposable diapers, which is a composition obtained by adding wax to a specific aromatic vinyl-conjugated diene copolymer, wherein the wax contains a linear hydrocarbon (normal hydrocarbon) and a branched hydrocarbon (isomeric hydrocarbon) at a weight ratio (normal hydrocarbon / isomeric hydrocarbon) of 30 / 70 to 99 / 1 and has a melting point of less than 80°C.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent document 1: International Publication No. 2020 / 045496. Summary of the invention

[0007] Problem that the invention aims to solve

[0008] On the other hand, aromatic vinyl-conjugated diene copolymers used in stretchable components of sanitary products such as pant-type diapers, which are a type of disposable diapers, are required to have ozone crack resistance in a wide temperature range of use. However, in the technology of the above-mentioned Patent Document 1, although ozone crack resistance at around room temperature (30° C.) is studied, ozone crack resistance in a wide temperature range is not focused on, and no specific method for improving ozone crack resistance in a wide temperature range is disclosed.

[0009] In addition, as in the technology of patent document 1, in order to improve the ozone crack resistance, in the case of adding additives such as wax to aromatic vinyl-conjugated diene copolymers, when formed into a film-shaped molded body, over time, additives such as wax will adhere to and accumulate on cooling bodies such as cooling rollers, and there are problems such as poor appearance caused by being transferred to the molded body, and the heat removal efficiency of cooling bodies such as cooling rollers is reduced, resulting in a problem of reduced manufacturing stability. In addition, although a method of adding additives such as wax in the form of a masterbatch composition can be considered, in the case of insufficient compatibility, there is also a problem such as causing the rupture of the film, etc.

[0010] The present invention has been completed in view of such actual conditions, and its purpose is to provide a masterbatch composition which has excellent compatibility with an aromatic vinyl-conjugated diene copolymer, thereby enabling excellent film formability (for example, when formed into a film, the occurrence of film breakage and poor appearance can be effectively prevented) when added to the aromatic vinyl-conjugated diene copolymer, and can also enable excellent ozone cracking resistance in a wide temperature range.

[0011] Solutions for solving problems

[0012] The present inventors conducted research to achieve the above-mentioned objectives and found that a masterbatch composition containing 30 to 98 weight % of an aromatic vinyl polymer and 2 to 70 weight % of a hydrocarbon compound group containing a specific amount of multiple hydrocarbon compounds with different carbon atom numbers can achieve the above-mentioned objectives, thereby completing the present invention.

[0013] That is, according to the present invention, there is provided a masterbatch composition comprising 30 to 98 wt % of an aromatic vinyl polymer and 2 to 70 wt % of a hydrocarbon compound group, wherein the aromatic vinyl polymer comprises at least one aromatic vinyl polymer block, the hydrocarbon compound group comprises a plurality of hydrocarbon compounds having different carbon atoms within a range of 12 to 60, and in the hydrocarbon compound group, the detection area ratio of hydrocarbon compound components having different carbon atoms as measured by gas chromatography-mass spectrometry (GC-MS) is between 0.1% and 0.2%. When the total peak area of ​​components within the range of 12 to 60 carbon atoms is taken as 100%, the total peak area of ​​components with a carbon number of 24 to 27 is 5% or more, the total peak area of ​​components with a carbon number of 27 to 30 is 5% or more, the total peak area of ​​components with a carbon number of 30 to 33 is 5% or more, the total peak area of ​​components with a carbon number of 33 to 36 is 5% or more, and the total peak area of ​​components with a carbon number of 12 to 27 is 45% or less.

[0014] In the masterbatch composition of the present invention, it is preferred that, in the above-mentioned hydrocarbon compound group, when the total peak area of ​​the components in the range of carbon numbers of 12 to 60 is taken as 100%, the total peak area of ​​the components with carbon numbers of 24 to 27 is 8 to 40%, the total peak area of ​​the components with carbon numbers of 27 to 30 is 8 to 50%, the total peak area of ​​the components with carbon numbers of 30 to 33 is 10 to 45%, the total peak area of ​​the components with carbon numbers of 33 to 36 is 7 to 30%, and the total peak area of ​​the components with carbon numbers of 12 to 27 is 10 to 40%.

[0015] In the masterbatch composition of the present invention, the aromatic vinyl polymer is preferably an aromatic vinyl-conjugated diene copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block.

[0016] In the masterbatch composition of the present invention, the aromatic vinyl-conjugated diene copolymer preferably comprises the general formula (A): Ar1 a -D a -Ar2 a The block copolymer A represented by a represents an aromatic vinyl polymer block having a weight average molecular weight of 5000 to 20000, D a Represents a conjugated diene polymer block, Ar2 a represents an aromatic vinyl polymer block having a weight average molecular weight greater than 20,000 to 400,000) and the general formula (B): Ar1 b -D b -Ar2 b The block copolymer B represented by b and Ar2 b Each represents an aromatic vinyl polymer block having a weight average molecular weight of 5,000 to 20,000, D b An aromatic vinyl-conjugated diene copolymer composition having a conjugated diene polymer block).

[0017] In the masterbatch composition of the present invention, the aromatic vinyl-conjugated diene copolymer preferably comprises the general formula (C): c -D c ) n -X represented by the block copolymer C (wherein, Ar c Denotes an aromatic vinyl polymer block, D c represents a conjugated diene polymer block, n represents an integer greater than 2, and X represents a residue of a coupling agent) and the general formula (D): Ard -D d The block copolymer D represented by d Denotes an aromatic vinyl polymer block, D d An aromatic vinyl-conjugated diene copolymer composition having a conjugated diene polymer block).

[0018] In addition, according to the present invention, an aromatic vinyl-conjugated diene copolymer composition can be provided, which comprises an aromatic vinyl-conjugated diene copolymer and the above-mentioned masterbatch composition, wherein the above-mentioned aromatic vinyl-conjugated diene copolymer has at least one aromatic vinyl polymer block and at least one conjugated diene polymer block.

[0019] According to the present invention, there is provided an elastomer formed from the above-mentioned aromatic vinyl-conjugated diene copolymer composition.

[0020] According to the present invention, there is provided a film formed from the above-mentioned aromatic vinyl-conjugated diene copolymer composition.

[0021] According to the present invention, there is provided a stretchable member obtained by using the above-mentioned elastic body or the above-mentioned film.

[0022] Effects of the Invention

[0023] According to the present invention, a masterbatch composition can be provided, which has excellent compatibility with an aromatic vinyl-conjugated diene copolymer, and thus when added to an aromatic vinyl-conjugated diene copolymer, excellent film formability can be achieved (for example, when formed into a film, the occurrence of film breakage and poor appearance can be effectively prevented), and excellent ozone crack resistance in a wide temperature range can be achieved. DETAILED DESCRIPTION

[0024] The masterbatch composition of the present invention contains 30 to 98 weight % of an aromatic vinyl polymer and 2 to 70 weight % of a hydrocarbon compound group, wherein the aromatic vinyl polymer includes at least one aromatic vinyl polymer block, and the hydrocarbon compound group contains a plurality of hydrocarbon compounds with different carbon atom numbers within a range of greater than 12 and less than 60.

[0025] Moreover, in the present invention, as a hydrocarbon compound group, the following hydrocarbon compound group is used: when the total peak area of ​​components with carbon numbers of 12 to 60 is taken as 100%, the detection area ratio of hydrocarbon compound components with carbon numbers of 24 to 27 is 5% or more, the total peak area of ​​components with carbon numbers of 27 to 30 is 5% or more, the total peak area of ​​components with carbon numbers of 30 to 33 is 5% or more, the total peak area of ​​components with carbon numbers of 33 to 36 is 5% or more, and the total peak area of ​​components with carbon numbers of 12 to 27 is 45% or less.

[0026] The masterbatch composition of the present invention is a masterbatch composition for adding to an aromatic vinyl-conjugated diene copolymer, and more specifically, is a masterbatch composition for adding the above-mentioned hydrocarbon compound group preferably to an aromatic vinyl-conjugated diene copolymer. Moreover, the masterbatch composition of the present invention has excellent compatibility with the aromatic vinyl-conjugated diene copolymer, and thus when added to the aromatic vinyl-conjugated diene copolymer, excellent film formability can be achieved (for example, when formed into a film, the occurrence of film breakage and poor appearance can be effectively prevented), and excellent ozone crack resistance in a wide temperature range can be achieved.

[0027] <Aromatic vinyl polymer>

[0028] The aromatic vinyl polymer constituting the masterbatch composition of the present invention comprises at least one aromatic vinyl polymer block. The aromatic vinyl polymer is not particularly limited as long as it contains at least one aromatic vinyl polymer block, and can include a homopolymer of an aromatic vinyl monomer (a polymer obtained by polymerizing only one or more aromatic vinyl monomers), an aromatic vinyl-conjugated diene copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block, and the like.

[0029] As the homopolymer of the aromatic vinyl monomer, as long as it is a polymer obtained by polymerizing only one or more aromatic vinyl monomers, it is not particularly limited. As the aromatic vinyl monomer, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl-4,6-dichlorostyrene, 2,4-dibromostyrene, vinylnaphthalene, etc. can be cited. Among these, styrene is preferably used. These aromatic vinyl monomers can be used alone or in combination of two or more.

[0030] The aromatic vinyl-conjugated diene copolymer is not particularly limited as long as it is a block copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block, but preferably includes the following aromatic vinyl-conjugated diene copolymer composition.

[0031] Suitable examples include those containing the general formula (A): Ar1 a -D a -Ar2 a The block copolymer A represented by the general formula (B): Ar1 b -D b -Ar2 b The block copolymer B represented is an aromatic vinyl-conjugated diene copolymer composition.

[0032] General formula (A): Ar1 a -D a -Ar2 a The block copolymer A represented is preferably the following block copolymer.

[0033] That is, in the formula, Ar1 a represents an aromatic vinyl polymer block having a weight average molecular weight of 5000 to 20000, D a Represents a conjugated diene polymer block, Ar2 a It refers to an aromatic vinyl polymer block having a weight average molecular weight greater than 20,000 to 400,000.

[0034] The content of the aromatic vinyl monomer unit in the block copolymer A is 25 to 80% by weight based on the total monomer units constituting the block copolymer A.

[0035] General formula (B): Ar1 b -D b -Ar2 bThe block copolymer B represented is preferably the following block copolymer.

[0036] That is, in the formula, Ar1 b and Ar2 b Each represents an aromatic vinyl polymer block having a weight average molecular weight of 5,000 to 20,000, D b represents a conjugated diene polymer block.

[0037] The content of the aromatic vinyl monomer unit in the block copolymer B is 10 to 90% by weight based on the total monomer units constituting the block copolymer B.

[0038] (Block copolymer A)

[0039] The block copolymer A is a copolymer represented by the following general formula (A).

[0040] General formula (A): Ar·1 a -D a -Ar·2 a

[0041] (Wherein, Ar1 a represents an aromatic vinyl polymer block having a weight average molecular weight of 5000 to 20000, D a Represents a conjugated diene polymer block, Ar2 a It refers to an aromatic vinyl polymer block with a weight average molecular weight greater than 20,000 to 400,000.

[0042] Aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) is a polymer block composed of an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer as a main repeating unit.

[0043] Used to form aromatic vinyl polymer blocks (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a) is not particularly limited as long as it is an aromatic vinyl compound, and examples thereof include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl-4,6-dichlorostyrene, 2,4-dibromostyrene, vinylnaphthalene, etc. Among these, styrene is preferably used. These aromatic vinyl monomers can be used alone or in combination of two or more. In addition, the two aromatic vinyl polymer blocks can be composed of the same aromatic vinyl monomer units or different aromatic vinyl monomer units.

[0044] In addition, the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a As long as the aromatic vinyl monomer unit is the main repeating unit, other monomer units may be included. a ) and aromatic vinyl polymer blocks (Ar2 a ) may contain monomer units other than aromatic vinyl monomer units, for example: conjugated diene monomers such as 1,3-butadiene and isoprene (2-methyl-1,3-butadiene); α,β-unsaturated nitrile monomers, unsaturated carboxylic acid or anhydride monomers, unsaturated carboxylic acid ester monomers, non-conjugated diene monomers, etc. Aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) is preferably 20 wt% or less, more preferably 10 wt% or less, and particularly preferably substantially 0 wt%. That is, the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) is preferably substantially composed of only one or more aromatic vinyl monomer units, and is particularly preferably composed of only styrene units.

[0045] In the block copolymer A, the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer block (Ar2 a ) have different weight average molecular weights.

[0046] Aromatic vinyl polymer block (Ar1 a) has a weight average molecular weight of 5,000 to 20,000, more preferably 6,000 to 18,000, and further preferably 7,000 to 16,000.

[0047] Aromatic vinyl polymer block (Ar2 a ) has a weight average molecular weight of greater than 20,000 and not more than 400,000, more preferably 25,000 to 300,000, further preferably 30,000 to 200,000, and further preferably 40,000 to 100,000.

[0048] Conjugated diene polymer block (D a ) is a polymer block composed of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer as a main repeating unit.

[0049] Used to form the conjugated diene polymer block (D a ) is not particularly limited as long as it is a conjugated diene compound, and examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, myrcene, farnesene, etc. Among these, 1,3-butadiene and / or isoprene are preferably used, and isoprene is particularly preferably used. These conjugated diene monomers can be used alone or in combination of two or more. Furthermore, the conjugated diene polymer block (D a ) undergoes a hydrogenation reaction on a portion of the unsaturated bonds.

[0050] In addition, the conjugated diene polymer block (D a As long as the conjugated diene monomer unit is the main repeating unit, other monomer units may be included. a ) may contain monomer units other than conjugated diene monomer units, for example: aromatic vinyl monomers such as styrene and α-methylstyrene; α, β-unsaturated nitrile monomers, unsaturated carboxylic acid or anhydride monomers, unsaturated carboxylic acid ester monomers, and non-conjugated diene monomers. Conjugated diene polymer block (D a The content of monomer units other than the conjugated diene monomer units in the conjugated diene polymer block (D) is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably substantially 0% by weight. a ) is preferably substantially composed of only one or more conjugated diene monomer units, and is particularly preferably composed of only isoprene units.

[0051] Conjugated diene polymer block (D a ) vinyl bond content (in the conjugated diene polymer block (D a) in all the conjugated diene monomer units, the ratio of 1,2-vinyl bond units and 3,4-vinyl bond units is not particularly limited, but is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and particularly preferably 3 to 10 mol%. When the vinyl bond content is too high, the flexibility of the obtained elastomer tends to be impaired.

[0052] Conjugated diene polymer block (D a ) has a weight average molecular weight of preferably 40,000 to 400,000, more preferably 45,000 to 350,000, further preferably 50,000 to 300,000, and further preferably 70,000 to 130,000.

[0053] The weight average molecular weight of the block copolymer A (that is, the weight average molecular weight of the entire block copolymer A) is preferably 65,000 to 800,000, more preferably 70,000 to 700,000, further preferably 75,000 to 650,000, and further preferably 120,000 to 240,000.

[0054] In the present invention, the weight average molecular weight of each polymer block and the weight average molecular weight of the entire block polymer are determined as polystyrene-equivalent values ​​by measurement using a high performance liquid chromatograph.

[0055] The weight average molecular weight of each polymer block and the weight average molecular weight of the entire block polymer can be adjusted by adjusting the amount of each monomer used to form each polymer block, the amount of the polymerization initiator, and the amount of the polymerization terminator when obtaining the block copolymer by polymerization reaction.

[0056] The content of the aromatic vinyl monomer unit in the block copolymer A is 25 to 80% by weight based on the total monomer units constituting the block copolymer A.

[0057] The block copolymer A is preferably obtained by a manufacturing method in which an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer are polymerized in this order to form a polymer block. Therefore, the block copolymer A preferably does not contain a coupling agent residue. The details of such a manufacturing method are described later. However, as long as a polymer having Ar1 a -D a -Ar2 a The method for producing a block copolymer having the structure shown above is not particularly limited, and the block copolymer may be produced using a coupling agent and may contain a residue of the coupling agent.

[0058] (Block copolymer B)

[0059] The block copolymer B is a copolymer represented by the following general formula (B).

[0060] General formula (B): Ar1 b -D b -Ar2 b

[0061] (Wherein, Ar1 b and Ar2 b respectively represent aromatic vinyl polymer blocks with a weight average molecular weight of 5000 to 20000, D b represents a conjugated diene polymer block. )

[0062] Aromatic vinyl polymer block (Ar1 b ) and aromatic vinyl polymer blocks (Ar2 b ) is a polymer block composed of an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer as a main repeating unit.

[0063] Used to form aromatic vinyl polymer blocks (Ar1 b ) and aromatic vinyl polymer blocks (Ar2 b The aromatic vinyl monomer of the aromatic vinyl monomer unit of Ar1 is not particularly limited as long as it is an aromatic vinyl compound, and examples thereof include aromatic vinyl monomers that are compatible with the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a )The same aromatic vinyl monomer.

[0064] Aromatic vinyl polymer block (Ar1 b ) and aromatic vinyl polymer blocks (Ar2 b As long as the aromatic vinyl monomer unit is the main repeating unit, other monomer units may be included. As monomers constituting monomer units other than the aromatic vinyl monomer unit, for example, the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) are the same monomers, and their contents are also the same. b ) and aromatic vinyl polymer blocks (Ar2 b ) is preferably substantially composed of only one or more aromatic vinyl monomer units, and is particularly preferably composed of only styrene units.

[0065] In the block copolymer B, the aromatic vinyl polymer block (Ar1 b ) and aromatic vinyl polymer blocks (Ar2 b ) have a weight average molecular weight in the range of 5,000 to 20,000.

[0066] Aromatic vinyl polymer block (Ar1 b ) and aromatic vinyl polymer blocks (Ar2 b ) has a weight average molecular weight of 5,000 to 20,000, more preferably 6,000 to 18,000, and further preferably 7,000 to 16,000.

[0067] Aromatic vinyl polymer block (Ar1 b ) and aromatic vinyl polymer blocks (Ar2 b ) are within the above range, the weight average molecular weights may be equal or different from each other, but are preferably substantially equal. b ) and aromatic vinyl polymer blocks (Ar2 b The weight average molecular weight of the aromatic vinyl polymer block (Ar1) of the block copolymer A is preferably equal to that of the aromatic vinyl polymer block (Ar2) of the block copolymer A having a relatively small weight average molecular weight. a ) have substantially the same weight average molecular weight.

[0068] Conjugated diene polymer block (D b ) is a polymer block composed of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer as a main repeating unit.

[0069] Used to form the conjugated diene polymer block (D b The conjugated diene monomer of the conjugated diene monomer unit of (D ) is not particularly limited as long as it is a conjugated diene compound, and examples thereof include a ) the same conjugated diene monomer.

[0070] In addition, the conjugated diene polymer block (D b As long as the conjugated diene monomer unit is the main repeating unit, other monomer units may be included. As monomers constituting monomer units other than the conjugated diene monomer unit, for example, the conjugated diene polymer block (D a ) are the same monomers, and their content and vinyl bond content are also the same. b ) is also preferably substantially composed of only one or more conjugated diene monomer units, and is particularly preferably composed of only isoprene units.

[0071] Conjugated diene polymer block (D b The vinyl bond content of the conjugated diene polymer block (D a ) have substantially the same vinyl bond content.

[0072] Conjugated diene polymer block (D b) has a weight average molecular weight of preferably 40,000 to 400,000, more preferably 45,000 to 350,000, further preferably 50,000 to 300,000, and further preferably 70,000 to 130,000.

[0073] Conjugated diene polymer block (D b The weight average molecular weight of the conjugated diene polymer block (D a ) have substantially the same weight average molecular weight.

[0074] The weight average molecular weight of the block copolymer B (that is, the weight average molecular weight of the entire block copolymer B) is preferably 65,000 to 800,000, more preferably 70,000 to 700,000, further preferably 75,000 to 600,000, and further preferably 80,000 to 160,000.

[0075] The content of the aromatic vinyl monomer unit in the block copolymer B is 10 to 90% by weight, preferably 14 to 50% by weight, more preferably 16 to 40% by weight, and most preferably 20 to 30% by weight, based on all monomer units constituting the block copolymer B.

[0076] The block copolymer B is preferably obtained by a manufacturing method in which an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer are polymerized in this order to form a polymer block. Therefore, the block copolymer B preferably does not contain a coupling agent residue. The details of such a manufacturing method are described later. However, as long as a polymer having Ar1 b -D b -Ar2 b The method for producing a block copolymer having the structure shown above is not particularly limited, and the block copolymer may be produced using a coupling agent and may contain a residue of the coupling agent.

[0077] The content ratio of block copolymer A and block copolymer B in the aromatic vinyl-conjugated diene copolymer composition used in the present invention is preferably 10 to 70% by weight of block copolymer A and 30 to 90% by weight of block copolymer B, more preferably 30 to 55% by weight of block copolymer A and 45 to 70% by weight of block copolymer B, further preferably 35 to 50% by weight of block copolymer A and 50 to 65% by weight of block copolymer B, and even more preferably 36 to 44% by weight of block copolymer A and 56 to 64% by weight of block copolymer B.

[0078] Block copolymer A and block copolymer B can be manufactured according to a conventional method. As the most common manufacturing method, the following method can be cited: by anionic living polymerization, aromatic vinyl monomers and conjugated diene monomers are polymerized in sequence to form polymer blocks, and coupling agents are reacted as required to couple. In addition, a method for forming polymer blocks by sequentially polymerizing according to the order of aromatic vinyl monomers, conjugated diene monomers, and then aromatic vinyl monomers can also be used. In addition, each polymer can be manufactured according to a conventional polymerization method, other polymer components are added as required, and then they are mixed according to conventional methods such as mixing and solution mixing, thus manufactured. In addition, as described later, block copolymers A and B can also be manufactured simultaneously.

[0079] In addition, in the present invention, commercially available block copolymers can also be used, for example, "Quintac (registered trademark)" (manufactured by Nippon Zeon Co., Ltd.), "JSR-SIS (registered trademark)" (manufactured by JSR Corporation), "Vector (registered trademark)" (manufactured by DEXCO Polymers Co., Ltd.), "Asaprene (registered trademark)", "Tufprene (registered trademark)", "Tuftec (registered trademark)" (manufactured by Asahi Kasei Chemicals Corporation), "SEPTON (registered trademark)" (manufactured by Kuraray Co., Ltd.), "Kraton (registered trademark)" (manufactured by Kraton Corporation), etc. can be used.

[0080] The block copolymer A and the block copolymer B are preferably produced by a method of forming a polymer block by sequentially polymerizing an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer in this order.

[0081] In more detail, block copolymer A and block copolymer B are preferably manufactured by the following manufacturing method. That is, the manufacturing method preferably includes the following steps: a first polymerization step, in a solvent, in the presence of a polymerization initiator, a monomer containing an aromatic vinyl monomer is polymerized to obtain a solution containing an aromatic vinyl polymer block chain; a second polymerization step, a monomer containing a conjugated diene monomer is added to the solution containing the aromatic vinyl polymer block chain, and polymerization is performed to obtain a solution containing a diblock chain; a third polymerization step, a monomer containing an aromatic vinyl monomer is added to the solution containing the diblock chain, and polymerization is performed to obtain a solution containing a triblock chain; a termination step, a polymerization terminator is added to the solution containing the triblock chain in an amount less than 1 molar equivalent relative to the active end of the triblock chain, so that a part of the active end is inactivated to obtain a solution containing block copolymer B and a triblock chain; and a fourth polymerization step, a monomer containing an aromatic vinyl monomer is added to the solution containing the triblock chain and block copolymer B, and polymerization is performed to obtain a solution containing block copolymer A and block copolymer B.

[0082] In the above-mentioned manufacturing method, first, a polymerization initiator is used in a solvent to polymerize a monomer containing an aromatic vinyl monomer as a main component (the first polymerization step). As the polymerization initiator used, organic alkali metal compounds, organic alkaline earth metal compounds, organic lanthanide rare earth metal compounds, etc., which are generally known to have anionic polymerization activity for aromatic vinyl monomers and conjugated diene monomers, can be used. As an organic alkali metal compound, it is particularly preferred to use an organic lithium compound having one or more lithium atoms in the molecule, as a specific example thereof, there can be cited: organic monolithium compounds such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium, dialkyl lithium amide, diphenyl lithium amide, and bistrimethylsilyl lithium amide; organic dilithium compounds such as methylene dilithium, tetramethylene dilithium, hexamethylene dilithium, isoprenyl dilithium, 1,4-dilithium-ethylcyclohexane; and organic trilithium compounds such as 1,3,5-trilithium benzene. Among these, organic monolithium compounds are particularly preferably used.

[0083] As organic alkaline earth metal compounds used as polymerization initiators, for example, n-butyl magnesium bromide, n-hexyl magnesium bromide, ethoxy calcium, calcium stearate, tert-butoxy strontium, ethoxy barium, isopropoxy barium, ethyl mercapto barium, tert-butoxy barium, phenoxy barium, diethylamino barium, barium stearate, ethyl barium, etc. can be cited. In addition, as specific examples of other polymerization initiators, there can be cited: composite catalysts composed of lanthanum rare earth metal compounds containing neodymium, samarium, gadolinium, etc. / alkyl aluminum / alkyl aluminum halide / alkyl aluminum hydride; metallocene catalysts containing titanium, vanadium, samarium, gadolinium, etc., which form a uniform system in an organic solvent and have active polymerization properties, etc. In addition, these polymerization initiators can be used alone or in combination of two or more.

[0084] The amount of the polymerization initiator used is not particularly limited and may be determined according to 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, based on 100 g of all monomers used.

[0085] The solvent used in the polymerization is not particularly limited as long as it is inactive to the polymerization initiator, and for example, a chain hydrocarbon solvent, a cyclic hydrocarbon solvent or a mixed solvent thereof can be used. 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, neopentane, and n-hexane. In addition, specific examples of cyclic hydrocarbon solvents include aromatic compounds such as benzene, toluene, and xylene; and alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane. These solvents can be used alone or in combination of two or more.

[0086] The amount of the solvent used in the polymerization is not particularly limited, but is preferably set so that the concentration of the block copolymer in the finally obtained block copolymer solution is preferably in the range of 5 to 60 wt %, more preferably in the range of 10 to 55 wt %, and particularly preferably in the range of 20 to 50 wt %.

[0087] In order to control the structure of each polymer block, a Lewis base compound may be added to the reactor used for polymerization. Examples of the Lewis base compound include tetrahydrofuran, diethyl ether, dihydrogen sulfoxide, and dihydrogen sulfoxide. Ethers such as alkanes, 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 tert-amyl alcoholate and potassium tert-butoxide; phosphines such as triphenylphosphine, etc. These Lewis base compounds can be used alone or in combination of two or more, and can be appropriately selected within the scope that does not impair the purpose of the present invention.

[0088] The timing of adding the Lewis base compound during the polymerization reaction is not particularly limited, as long as it is appropriately determined according to the structure of each block copolymer as the target. For example, it can be added in advance before initiating polymerization, it can also be added after a portion of the polymer blocks are polymerized, and it can also be further added after a portion of the polymer blocks are polymerized on the basis of adding in advance before initiating polymerization.

[0089] The polymerization reaction temperature is preferably 10 to 150° C., more preferably 30 to 130° C., and further preferably 40 to 90° C. The time required for the polymerization varies depending on the conditions, but is generally within 48 hours, preferably 0.5 to 10 hours. The polymerization pressure is not particularly limited as long as it is within the above-mentioned polymerization temperature range and is sufficient to maintain the monomer and the solvent in a liquid phase.

[0090] Under the above conditions, a polymerization initiator is used in a solvent to polymerize a monomer containing an aromatic vinyl monomer as a main component, thereby obtaining a solution containing an aromatic vinyl polymer block chain. In addition, the aromatic vinyl polymer block chain obtained by polymerization usually has an active end. In addition, the obtained aromatic vinyl polymer block chain forms an aromatic vinyl polymer block (Ar1 a ) or aromatic vinyl polymer block (Ar1 b ), therefore, the amount of the monomer used in the first polymerization step is determined according to the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer block (Ar1 b ) can be determined by the weight average molecular weight.

[0091] Next, a monomer containing a conjugated diene monomer as a main component is added to the solution containing the aromatic vinyl polymer block chain obtained in the first polymerization step to perform polymerization (second polymerization step). Thus, a solution containing a diblock chain can be obtained. In addition, the diblock chain obtained by polymerization usually has an active end. In addition, the diblock chain obtained in the second polymerization step is the aromatic vinyl polymer block (Ar1 a ) or aromatic vinyl polymer block (Ar1 b ) is further bonded to the polymer chain to form a conjugated diene polymer block (D a ) or conjugated diene polymer block (D b ) is formed by polymer chains, so the amount of the monomer used in the second polymerization step is determined according to the conjugated diene polymer block (D a ) and conjugated diene polymer block (D b ) can be determined by the weight average molecular weight. In addition, the polymerization reaction temperature, polymerization time, and polymerization pressure can be controlled within the same range as the first polymerization step.

[0092] Next, a monomer containing an aromatic vinyl monomer as a main component is added to the solution containing the diblock chain obtained in the second polymerization step to perform polymerization (third polymerization step). Thus, a solution containing a triblock chain can be obtained. In addition, the triblock chain obtained by polymerization usually has an active end. In addition, the triblock chain obtained in the third polymerization step is the aromatic vinyl polymer block (Ar1 a ) or aromatic vinyl polymer block (Ar1 b ) and conjugated diene polymer block (D a ) or conjugated diene polymer block (D b ) is further bonded to the polymer chain to form an aromatic vinyl polymer block (Ar2 a) or a portion of the aromatic vinyl polymer block (Ar2 b ) polymer chain, so the amount of the monomer used in the third polymerization step is based on the aromatic vinyl polymer block (Ar2 b ) can be determined by the weight average molecular weight. In addition, the polymerization reaction temperature, polymerization time, and polymerization pressure can be controlled within the same range as the first polymerization step.

[0093] Next, a polymerization terminator is added to the solution containing the triblock chain obtained in the third polymerization step in an amount less than 1 molar equivalent relative to the active ends of the triblock chain (termination step). As a result, a portion of the active ends of the triblock chain are inactivated, and a block copolymer with inactivated active ends is obtained. The block copolymer has the general formula (B): Ar1 b -D b -Ar2 b The block copolymer B represented.

[0094] The polymerization terminator is not particularly limited as long as it can react with the active terminal to inactivate the active terminal and does not react with the other active terminal after reacting with one active terminal. From the viewpoint of suppressing the moisture absorption of the obtained composition, the polymerization terminator is preferably a compound that does not contain a halogen atom, and particularly preferably a polymerization terminator that generates a metal alkoxide, a metal aryl oxide or a metal hydroxide when reacting with the active terminal. Examples of particularly preferred compounds for use as the polymerization terminator include: water; monohydric alcohols such as methanol and ethanol; and monohydric phenols such as phenol and cresol.

[0095] The amount of the polymerization terminator used is determined according to the weight ratio of block copolymer A to block copolymer B, and is not particularly limited as long as it is less than 1 molar equivalent relative to the active ends of the triblock chain. Generally, the amount of the polymerization terminator is in the range of 0.18 to 0.91 molar equivalents relative to the active ends, and preferably in the range of 0.35 to 0.80 molar equivalents.

[0096] As described above, when a polymerization terminator is added to a solution containing triblock chains having active terminals in an amount less than 1 molar equivalent relative to the active terminals, a portion of the active terminals of the triblock chains having active terminals are inactivated, and the polymer having the inactivated active terminals becomes block copolymer B. Furthermore, the remaining portion of the triblock chains having active terminals that have not reacted with the polymerization terminator remains in the solution in an unreacted state.

[0097] Next, a monomer containing an aromatic vinyl monomer as a main component is added to the solution containing the triblock chain and the block copolymer B obtained in the termination step to carry out polymerization (the fourth polymerization step). Thus, a copolymer containing the general formula (A): Ar1 a -D a-Ar2 a The block copolymer A obtained in the fourth polymerization step is a solution of the block copolymer A and the block copolymer B. The block copolymer A obtained in the fourth polymerization step is a block copolymer of the triblock chain obtained in the third polymerization step. a ) is formed by a polymer chain of a part of the aromatic vinyl polymer block (Ar2 a ) can be determined by the weight average molecular weight. In addition, the polymerization reaction temperature, polymerization time, and polymerization pressure can be controlled in the same range as the first polymerization step.

[0098] After the fourth polymerization step, the polymer component can be recovered from the solution containing block copolymer A and block copolymer B (recovery process). The method of recovery can be in accordance with conventional methods, and is not particularly limited. For example, it is possible to add polymerization terminators such as water, methanol, ethanol, propanol, hydrochloric acid, citric acid as needed after the reaction is completed, and further add additives such as antioxidants as needed, and then apply known methods such as direct drying method and stripping method to the solution, thereby recovering. In the case where the polymer component is recovered as slurry using stripping method, any dehydrator such as extruder type squeezer is used for dehydration, and pellets with a moisture content below a specified value are made, and any drying machine such as belt dryer or expansion extrusion dryer is further used to dry the pellets. The block copolymer obtained as described above can be used after being processed into a particle shape according to a conventional method.

[0099] The block copolymer A and the block copolymer B can be produced in the above-described manner.

[0100] When only the block copolymer B is obtained, there may be mentioned a method in which all active terminals are inactivated in the above-mentioned termination step without performing polymerization in the fourth polymerization step.

[0101] Furthermore, as the aromatic vinyl-conjugated diene copolymer, the following aromatic vinyl-conjugated diene copolymer composition can also be preferably used.

[0102] That is, preferably, a compound containing the general formula (C): (Ar c -D c ) n -X represented by the block copolymer C and the general formula (D): Ar d -D d The block copolymer D represented is an aromatic vinyl-conjugated diene copolymer composition.

[0103] General formula (C): (Ar c -D c ) nThe block copolymer C represented by -X is preferably the following block copolymer.

[0104] That is, in the formula, Ar c Denotes an aromatic vinyl polymer block, D c represents a conjugated diene polymer block, n represents an integer of 2 or more, and X represents a residue of a coupling agent.

[0105] The content of the aromatic vinyl monomer unit in the block copolymer C is not particularly limited, but is preferably less than 50% by weight based on the total monomer units constituting the block copolymer C.

[0106] General formula (D): Ar d -D d The block copolymer D represented is preferably the following block copolymer.

[0107] That is, in the formula, Ar d Denotes an aromatic vinyl polymer block, D d represents a conjugated diene polymer block.

[0108] (Block copolymer C)

[0109] The block copolymer C is a copolymer represented by the following general formula (C).

[0110] General formula (C): (Ar c -D c ) n -X

[0111] (Where Ar c Denotes an aromatic vinyl polymer block, D c represents a conjugated diene polymer block, n represents an integer greater than 2, and X represents a residue of a coupling agent.

[0112] The block copolymer C has n diblocks (Ar c -D c ) are bonded to each other via the residue (X) of a coupling agent. n in the general formula (C) represents the number of branches in the block copolymer C. The block copolymer C may be a mixture of two or more block copolymers in which diblock bodies are bonded in different numbers. n is an integer greater than 2, preferably an integer of 2 to 8, and more preferably an integer of 2 to 4. The residue (X) of the coupling agent is not particularly limited as long as it is the residue of an n-valent coupling agent, and is preferably a residue of a silicon atom-containing coupling agent, and more preferably a residue of a halogenated silane or an alkoxysilane. Examples of coupling agents constituting the residue of the coupling agent include the coupling agents described below.

[0113] As the block copolymer C, a mixture of a block copolymer C1 in which n is 2, a block copolymer C2 in which n is 3, and a block copolymer C3 in which n is 4 is particularly preferred. In this case, the weight ratio of the block copolymers C1 to C3 (C1 / C2 / C3) is preferably 40 to 80 / 30 to 10 / 30 to 10.

[0114] Aromatic vinyl polymer block (Ar c ) is a polymer block composed of an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer as a main repeating unit.

[0115] Used to form aromatic vinyl polymer blocks (Ar c The aromatic vinyl monomer of the aromatic vinyl monomer unit of Ar1 is not particularly limited as long as it is an aromatic vinyl compound, and examples thereof include aromatic vinyl monomers that are compatible with the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a )The same aromatic vinyl monomer.

[0116] Aromatic vinyl polymer block (Ar c As long as the aromatic vinyl monomer unit is the main repeating unit, other monomer units may be included. As monomers constituting monomer units other than the aromatic vinyl monomer unit, for example, the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) are the same monomers, and their contents are also the same. In addition, each aromatic vinyl polymer block in the block copolymer C may be composed of the same aromatic vinyl monomer units, or may be composed of different aromatic vinyl monomer units. c ) is also preferably composed essentially of only one or two or more aromatic vinyl monomer units, and is particularly preferably composed of only styrene units.

[0117] Aromatic vinyl polymer block (Ar c ) has a weight average molecular weight of preferably 4,000 to 18,000, more preferably 5,000 to 16,000, and further preferably 6,000 to 14,000.

[0118] The block copolymer C has a plurality of aromatic vinyl polymer blocks (Ar c ) may be equal to or different from each other as long as the weight average molecular weight is within the above range, but they are preferably substantially equal.

[0119] Conjugated diene polymer block (D c) is a polymer block composed of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer as a main repeating unit.

[0120] Used to form the conjugated diene polymer block (D c The conjugated diene monomer of the conjugated diene monomer unit of (D ) is not particularly limited as long as it is a conjugated diene compound, and examples thereof include a ) the same conjugated diene monomer. In addition, each conjugated diene polymer block in the block copolymer C may be composed of the same conjugated diene monomer unit, or may be composed of different conjugated diene monomer units.

[0121] In addition, the conjugated diene polymer block (D c As long as the conjugated diene monomer unit is the main repeating unit, other monomer units may be included. As monomers constituting monomer units other than the conjugated diene monomer unit, for example, the conjugated diene polymer block (D a ) are the same monomers, and their content and vinyl bond content are also the same. c ) is also preferably substantially composed of only one or more conjugated diene monomer units, and is particularly preferably composed of only isoprene units.

[0122] Conjugated diene polymer block (D c ) has a weight average molecular weight of preferably 20,000 to 200,000, more preferably 25,000 to 180,000, further preferably 30,000 to 150,000, and further preferably 70,000 to 130,000.

[0123] The block copolymer C has a plurality of conjugated diene polymer blocks (D c ) may be equal to or different from each other as long as the weight average molecular weight is within the above range, but they are preferably substantially equal.

[0124] The weight average molecular weight of the block copolymer C (that is, the weight average molecular weight of the entire block copolymer C) is preferably 60,000 to 800,000, more preferably 80,000 to 600,000, and further preferably 180,000 to 320,000.

[0125] The content of the aromatic vinyl monomer unit of the block copolymer C is not particularly limited relative to the total monomer units constituting the block copolymer C, but is preferably less than 50% by weight, preferably less than 40% by weight, further preferably less than 30% by weight, more preferably less than 20% by weight, and most preferably less than 16% by weight. The lower limit is not particularly limited and may be 5% by weight or more.

[0126] Block copolymer C is preferably obtained by polymerizing an aromatic vinyl monomer and a conjugated diene monomer to form a diblock chain, and reacting the diblock chain with a coupling agent to couple the diblock chain. Therefore, block copolymer C contains a residue of a coupling agent. The details of such a production method are described later.

[0127] (Block copolymer D)

[0128] The block copolymer D is a copolymer represented by the following general formula (D).

[0129] General formula (D): Ar d -D d

[0130] (Where Ar d Denotes an aromatic vinyl polymer block, D d represents a conjugated diene polymer block. )

[0131] Aromatic vinyl polymer block (Ar d ) is a polymer block composed of an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer as a main repeating unit.

[0132] Used to form aromatic vinyl polymer blocks (Ar d The aromatic vinyl monomer of the aromatic vinyl monomer unit of Ar1 is not particularly limited as long as it is an aromatic vinyl compound, and examples thereof include aromatic vinyl monomers that are compatible with the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) the same aromatic vinyl monomer.

[0133] Aromatic vinyl polymer block (Ar d As long as the aromatic vinyl monomer unit is the main repeating unit, other monomer units may be included. As monomers constituting monomer units other than the aromatic vinyl monomer unit, for example, the aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer blocks (Ar2 a ) are the same monomers, and their contents are also the same. d ) is also preferably composed essentially of only one or two or more aromatic vinyl monomer units, and is particularly preferably composed of only styrene units.

[0134] Aromatic vinyl polymer block (Ar d ) has a weight average molecular weight of preferably 4,000 to 18,000, more preferably 5,000 to 16,000, and further preferably 6,000 to 14,000.

[0135] Aromatic vinyl polymer block (Ar d The weight average molecular weight of the aromatic vinyl polymer block (Ar c ) have substantially the same weight average molecular weight.

[0136] Conjugated diene polymer block (D d ) is a polymer block composed of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer as a main repeating unit.

[0137] Used to form the conjugated diene polymer block (D d The conjugated diene monomer of the conjugated diene monomer unit of (D ) is not particularly limited as long as it is a conjugated diene compound, and examples thereof include a ) the same conjugated diene monomer.

[0138] In addition, the conjugated diene polymer block (D d As long as the conjugated diene monomer unit is the main repeating unit, other monomer units may be included. As monomers constituting monomer units other than the conjugated diene monomer unit, for example, the conjugated diene polymer block (D a ) are the same monomers, and their content and vinyl bond content are also the same. d ) is also preferably substantially composed of only one or two or more conjugated diene monomer units, and is particularly preferably composed of isoprene units.

[0139] Conjugated diene polymer block (D d The vinyl bond content of the conjugated diene polymer block (D c ) have substantially the same vinyl bond content.

[0140] Conjugated diene polymer block (D d ) has a weight average molecular weight of preferably 20,000 to 200,000, more preferably 25,000 to 180,000, further preferably 30,000 to 150,000, and further preferably 70,000 to 130,000.

[0141] Conjugated diene polymer block (D d The weight average molecular weight of the conjugated diene polymer block (D c ) have substantially the same weight average molecular weight.

[0142] The weight average molecular weight of the block copolymer D (that is, the weight average molecular weight of the entire block copolymer D) is preferably 30,000 to 200,000, more preferably 40,000 to 180,000, and further preferably 70,000 to 150,000.

[0143] The content of the aromatic vinyl monomer units in the block copolymer D is not particularly limited relative to the total monomer units constituting the block copolymer D, but is preferably less than 50% by weight, preferably less than 40% by weight, further preferably less than 30% by weight, more preferably less than 20% by weight, and most preferably less than 16% by weight. The lower limit is not particularly limited and may be 5% by weight or more.

[0144] The content ratio of block copolymer C and block copolymer D in the aromatic vinyl-conjugated diene copolymer composition used in the present invention is preferably 25 to 98% by weight of block copolymer C and 2 to 75% by weight of block copolymer D, more preferably 75 to 95% by weight of block copolymer C and 5 to 25% by weight of block copolymer D, further preferably 80 to 92% by weight of block copolymer C and 8 to 20% by weight of block copolymer D, and even more preferably 84 to 92% by weight of block copolymer C and 8 to 16% by weight of block copolymer D.

[0145] Block copolymer C and block copolymer D can be manufactured according to a conventional method. As the most common manufacturing method, the following method can be cited: by anionic living polymerization, aromatic vinyl monomers and conjugated diene monomers are polymerized in sequence to form polymer blocks, and coupling agents are reacted as required. In addition, a method for forming polymer blocks by sequentially polymerizing according to the order of aromatic vinyl monomers, conjugated diene monomers, and then aromatic vinyl monomers can also be used. In addition, each polymer can be manufactured according to a conventional polymerization method, other polymer components are added as required, and then they are mixed according to conventional methods such as mixing, solution mixing, and thus manufactured. In addition, as described later, block copolymers C and D can also be manufactured simultaneously.

[0146] In addition, in the present invention, commercially available block copolymers can also be used, for example, "Quintac (registered trademark)" (manufactured by Nippon Zeon Co., Ltd.), "JSR-SIS (registered trademark)" (manufactured by JSR Corporation), "Vector (registered trademark)" (manufactured by DEXCO Polymers Co., Ltd.), "Asaprene (registered trademark)", "Tufprene (registered trademark)", "Tuftec (registered trademark)" (manufactured by Asahi Kasei Chemicals Corporation), "SEPTON (registered trademark)" (manufactured by Kuraray Co., Ltd.), "Kraton (registered trademark)" (manufactured by Kraton Corporation), etc. can be used.

[0147] The block copolymer C is preferably produced by polymerizing an aromatic vinyl monomer and a conjugated diene monomer to form a diblock chain, and reacting the diblock chain with a coupling agent to perform coupling.

[0148] In more detail, block copolymer C and block copolymer D are preferably manufactured by the following manufacturing method. That is, the manufacturing method preferably includes the following steps: a first polymerization step, in a solvent, in the presence of a polymerization initiator, a monomer containing an aromatic vinyl monomer is polymerized to obtain a solution containing an aromatic vinyl polymer block chain; a second polymerization step, to the solution containing an aromatic vinyl polymer block chain, a monomer containing a conjugated diene monomer is added to the solution containing the aromatic vinyl polymer block chain, and polymerization is performed to obtain a solution containing a diblock chain; and a reaction step, to the solution containing the diblock chain, a coupling agent is preferably added in an amount of 0.05 to 1.0 molar equivalent relative to the active end of the diblock chain, thereby obtaining block copolymers C and block copolymers D.

[0149] In the above-mentioned manufacture method, first, use polymerization initiator in solvent, will comprise aromatic vinyl monomer as main component monomer polymerization (first polymerization process).The solvent and its consumption, polymerization initiator and its consumption used in the first polymerization process can be identical with the first polymerization process in the preferred manufacture method of above-mentioned block copolymer A and block copolymer B.In addition, also can add Lewis base compound similarly with the first polymerization process in the preferred manufacture method of above-mentioned block copolymer A and block copolymer B.In addition, also can adopt the polymerization reaction temperature, polymerization time and polymerization pressure identical with the first polymerization process in the preferred manufacture method of above-mentioned block copolymer A and block copolymer B.

[0150] Under the above conditions, a polymerization initiator is used in a solvent to polymerize the monomer containing the aromatic vinyl monomer as the main component, thereby obtaining a solution containing an aromatic vinyl polymer block chain. In addition, the aromatic vinyl polymer block chain obtained by polymerization usually has an active end. In addition, the obtained aromatic vinyl polymer block chain forms an aromatic vinyl polymer block (Ar c ), so the amount of the monomer used in the first polymerization step is based on the aromatic vinyl polymer block (Ar c ) can be determined by the weight average molecular weight.

[0151] Next, a monomer containing a conjugated diene monomer as a main component is added to the solution containing the aromatic vinyl polymer block chain obtained in the first polymerization step to perform polymerization (second polymerization step). Thus, a solution containing a diblock chain can be obtained. In addition, the diblock chain obtained by polymerization usually has an active end. In addition, the diblock chain obtained in the second polymerization step is the aromatic vinyl polymer block (Ar obtained in the first polymerization step). c ) is further bonded to the polymer chain to form a conjugated diene polymer block (D c ) is formed by polymer chains, so the amount of the monomer used in the second polymerization step is determined according to the conjugated diene polymer block (D c ) can be determined by the weight average molecular weight of . In addition, the polymerization reaction temperature, polymerization time, and polymerization pressure can be controlled within the same range as the first polymerization step.

[0152] Next, a coupling agent is added to the solution containing the diblock chains (reaction step). Thus, the active ends of the diblock chains react with the coupling agent, and two or more diblock chains are bonded via the residues of the coupling agent to form a block copolymer C.

[0153] The coupling agent is not particularly limited as long as it has two or more functional groups capable of reacting with the active end of the diblock chain in one molecule. Preferably, it is a coupling agent having 2 to 8 functional groups capable of reacting with the active end of the diblock chain in one molecule, and more preferably, it is a coupling agent having 2 to 4 functional groups capable of reacting with the active end of the diblock chain in one molecule. In addition, the coupling agent preferably contains a silicon atom, and more preferably a halogenated silane and an alkoxysilane.

[0154] As a coupling agent having two functional groups capable of reacting with the active ends of the diblock chain in one molecule (bifunctional coupling agent), for example, bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional alkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; bifunctional halogenated alkanes such as dichloroethane, dibromoethane, dichloromethane, and dibromomethane; bifunctional halogenated tin halides such as tin dichloride, monomethyltin dichloride, dimethyltin dichloride, monoethyltin dichloride, diethyltin dichloride, monobutyltin dichloride, and dibutyltin dichloride; dibromobenzene, benzoic acid, CO, 2-chloropropylene, etc. Among these, it is particularly preferred to use bifunctional halogenated silanes or bifunctional alkoxysilanes. These bifunctional coupling agents can be used alone or in combination of two or more.

[0155] As coupling agents having three functional groups capable of reacting with the active ends of the diblock chain in one molecule (trifunctional coupling agents), for example, trifunctional halogenated alkanes such as trichloroethane and trichloropropane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; trifunctional alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, etc. These trifunctional coupling agents can be used alone or in combination of two or more.

[0156] As coupling agents having four functional groups capable of reacting with the active ends of the diblock chain in one molecule (tetrafunctional coupling agents), for example, tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; tetrafunctional halogenated silanes such as tetrachlorosilane and tetrabromosilane; tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; tetrafunctional tin halides such as tin tetrachloride and tin tetrabromide, etc. These tetrafunctional coupling agents can be used alone or in combination of two or more.

[0157] The value of n of block copolymer C, i.e. the number of branches of block copolymer C can be adjusted by adjusting the type, amount, timing of addition, amount of Lewis base compound, etc. of coupling agent. In addition, reaction terminators such as methanol can also be used to adjust the coupling rate and the number of branches of block copolymer C. In addition, the number of branches of block copolymer C can be adjusted by combining two or more coupling agents having different numbers of functional groups that can react with the active ends of diblock chains. Furthermore, the diblock chains obtained in the second polymerization step can be left in an unreacted state by these methods, and finally recovered as block copolymer D.

[0158] The amount of the coupling agent used can be adjusted to an appropriate amount depending on the number of branches of the target block copolymer C. The amount of the coupling agent used is preferably 0.25 to 1.00 molar equivalent, more preferably 0.40 to 1.0 molar equivalent, relative to the active terminal of the diblock chain.

[0159] The reaction temperature is preferably 10 to 150° C., more preferably 30 to 130° C., and even more preferably 40 to 90° C. The time required for the reaction varies depending on the conditions, but is usually within 48 hours, preferably 0.5 to 10 hours.

[0160] After the reaction process, the polymer component can be recovered from the solution containing block copolymer C and block copolymer D (recovery process). The method of recovery can be in accordance with conventional methods, and is not particularly limited. For example, it is possible to add polymerization terminators such as water, methanol, ethanol, propanol, hydrochloric acid, citric acid as needed after the reaction is completed, and further add additives such as antioxidants as needed, and then apply known methods such as direct drying method and stripping method to the solution, thereby recovering. In the case where the polymer component is recovered as slurry using stripping method, any dehydrator such as extruder type squeezer is used for dehydration, and pellets with a moisture content below a specified value are made, and any drying machine such as belt dryer or expansion extrusion dryer is further used to dry the pellets. The block copolymer obtained as described above can be used after being processed into granules according to conventional methods.

[0161] In the above-described manner, the block copolymer C and the block copolymer D can be produced.

[0162] <Hydrocarbon compound group>

[0163] The masterbatch composition of the present invention is obtained by adding a hydrocarbon compound group containing a specific amount of a plurality of hydrocarbon compounds having different carbon atoms within a range of 12 to 60 to the above-mentioned aromatic vinyl polymer.

[0164] The hydrocarbon compound group used in the present invention contains a plurality of hydrocarbon compounds with different carbon numbers within the range of 12 to 60, that is, it is a mixture of a plurality of hydrocarbon compounds with different carbon numbers, and the detection area ratio of the hydrocarbon compound components with different carbon numbers measured by gas chromatography-mass spectrometry (GC-MS) analysis is within the following range when the total peak area of ​​the components with carbon numbers within the range of 12 to 60 is taken as 100%. In addition, the total peak area represents the content ratio of each component on a mass basis.

[0165] That is, the total peak area of ​​components having a carbon number of 24 or more and 27 or less is 5% or more, the total peak area of ​​components having a carbon number of 27 or more and 30 or less is 5% or more, the total peak area of ​​components having a carbon number of 30 or more and 33 or less is 5% or more, the total peak area of ​​components having a carbon number of 33 or more and 36 or less is 5% or more, and the total peak area of ​​components having a carbon number of 12 or more and 27 or less is 45% or less.

[0166] According to the present invention, by using such a hydrocarbon compound group, the masterbatch composition of the present invention has excellent compatibility with the aromatic vinyl block copolymer, so that when added to the aromatic vinyl block copolymer, excellent film formability can be achieved (for example, when formed into a film, the occurrence of film breakage and poor appearance can be effectively prevented), and excellent ozone crack resistance in a wide temperature range can also be achieved.

[0167] The total peak area of ​​the components having each carbon number is preferably in the following range.

[0168] That is, the total peak area of ​​components having 24 or more and 27 or less carbon atoms is preferably 8 to 40%, more preferably 10 to 36%, further preferably 12 to 32%, and further preferably 12 to 31%.

[0169] The total peak area of ​​components having 27 or more and 30 or less carbon atoms is preferably 8 to 50%, more preferably 10 to 45%, further preferably 12 to 40%, and further preferably 15 to 39%.

[0170] The total peak area of ​​components having 30 or more and 33 or less carbon atoms is preferably 10 to 45%, more preferably 12 to 40%, further preferably 15 to 35%, and further preferably 17 to 31%.

[0171] The total peak area of ​​components having 33 or more and 36 or less carbon atoms is preferably 7 to 30%, more preferably 9 to 28%, further preferably 10 to 25%, and further preferably 11 to 24%.

[0172] Furthermore, the total peak area of ​​components having 12 or more and 27 or less carbon atoms is preferably 10 to 40%, more preferably 11 to 38%, further preferably 12 to 32%, and further preferably 14 to 24%.

[0173] When the total peak area of ​​the composition of more than 24 and less than 27 carbon atoms, the total peak area of ​​the composition of more than 27 and less than 30 carbon atoms are respectively too small, when being added to aromatic vinyl block copolymers, ozone crack resistance, particularly the ozone crack resistance in low temperature region deteriorates. In addition, when the total peak area of ​​the composition of more than 30 and less than 33 carbon atoms, the total peak area of ​​the composition of more than 33 and less than 36 carbon atoms are respectively too small, when being added to aromatic vinyl block copolymers, ozone crack resistance, particularly the ozone crack resistance in high temperature region deteriorates. In addition, when the total peak area of ​​the composition of more than 12 and less than 27 carbon atoms is too large, when being added to aromatic vinyl block copolymers, being formed into film-like molded bodies, etc., as time passes, hydrocarbon compounds from hydrocarbon compound groups adhere to, accumulate in cooling bodies such as cooling rollers, and they are transferred to molded bodies, causing the heat removal efficiency of cooling bodies such as poor appearance and rollers to reduce, thus manufacturing stability reduction.

[0174] In addition, the hydrocarbon compound group used in the present invention refers to a collection of compounds that are essentially composed only of carbon and hydrogen. Therefore, it does not include compounds that also contain polar groups and metal elements in the hydrocarbon skeleton (such as fatty acid amides and fatty acid metal salts used as lubricants). In addition, as the hydrocarbon compound group used in the present invention, when the total peak area of ​​the components with carbon atoms of 12 or more and 60 or less that are essentially composed only of carbon and hydrogen is taken as 100%, as long as the total peak area of ​​the components with each carbon atom number is within the above range. It can contain hydrocarbon compounds with carbon atoms of 11 or less and hydrocarbon compounds with carbon atoms of 61 or more, and it is preferably essentially composed of hydrocarbon compounds with carbon atoms in the range of 12 or more and 60 or less (for example, it is preferably contained in a ratio of 99% by weight or more of hydrocarbon compounds with carbon atoms in the range of 12 or more and 60 or less).

[0175] The hydrocarbon compound group used in the present invention may be a commercially available wax having a total peak area of ​​components having different carbon numbers within the above range, or may be a mixture of a plurality of commercially available waxes having a total peak area of ​​components having different carbon numbers within the above range.

[0176] In the masterbatch composition of the present invention, the proportion of the aromatic vinyl polymer and the hydrocarbon compound group is 30 to 98 weight % and 2 to 70 weight % of the aromatic vinyl polymer and the hydrocarbon compound group, preferably 50 to 95 weight % and 5 to 50 weight % of the aromatic vinyl polymer and the hydrocarbon compound group, more preferably 60 to 90 weight % and 10 to 40 weight % of the aromatic vinyl polymer and the hydrocarbon compound group.

[0177] In addition, the masterbatch composition of the present invention is added to an aromatic vinyl-conjugated diene copolymer, etc., as described later, to make an aromatic vinyl block copolymer composition, and is finally used to make a film-like molded body, etc. The content of the hydrocarbon compound group in such a film-like molded body, etc. can be adjusted as needed by the content of the hydrocarbon compound group contained in the masterbatch composition and the addition amount of the masterbatch composition when manufacturing the film-like molded body. The addition amount of the masterbatch composition in the film-like molded body, etc. is preferably adjusted to make the content of the hydrocarbon compound group in the film-like molded body 0.1 to 10 weight %, preferably 0.2 to 5 weight %, more preferably 0.3 to 3 weight %, and more preferably 0.8 to 2.5 weight %.

[0178] When the ratio of the aromatic vinyl polymer in the masterbatch composition is too little, as described later, when being added to aromatic vinyl-conjugated diene copolymers etc., the compatibility of the masterbatch composition and the aromatic vinyl-conjugated diene copolymers is reduced, and the bad appearance and film fracture of the film are caused due to the bad mixing. In addition, due to the bad mixing and bad transportation in the masterbatch manufacturing, it is difficult to obtain the masterbatch product. In addition, the obtained product can not keep shapes such as particles, and the operation is difficult.

[0179] When the proportion of the aromatic vinyl polymer in the masterbatch composition is too much, when adding to the aromatic vinyl-conjugated diene copolymer and the like as described later to manufacture a film-shaped body, a large amount of the masterbatch composition needs to be added, and the film-shaped body cannot be obtained with good productivity. In addition, the aromatic vinyl polymer used in the masterbatch composition is processed twice in total, so when the addition amount of the masterbatch composition increases, the thermal history applied to the film-shaped body as a whole increases, which becomes the cause of quality reduction.

[0180] In addition, the masterbatch composition of the present invention may further contain fatty acid amide, antioxidant, tackifying resin, softener, antibacterial agent, light stabilizer, ultraviolet absorber, dye (pigment), lubricant, etc. in addition to the aromatic vinyl polymer and hydrocarbon compound group as needed.

[0181] The preparation method of the masterbatch composition of the present invention is not particularly limited. It can be prepared by mixing the above-mentioned aromatic vinyl polymer, the above-mentioned hydrocarbon compound group, and each component added as needed. For example, the following method can be cited: after each component is dissolved in a solvent and uniformly mixed, the solvent is removed by heating, etc.; each component is melt-mixed by a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc. Among these methods, from the viewpoint of more effectively mixing, melt mixing is preferred, and a twin-screw extruder and a Banbury mixer are particularly preferably used. In addition, the temperature when melt mixing is not particularly limited, usually in the range of 100 to 230°C.

[0182] As a method for recovering the masterbatch composition, pelletization is preferred, and a strand cutting pelletizer, a thermal cutting pelletizer, or an underwater cutting pelletizer can be used. A thermal cutting pelletizer or an underwater cutting pelletizer is particularly preferred.

[0183] The particles may or may not be subjected to external additives for preventing mutual adhesion. In the case of externally adding a release agent, silicon dioxide, talc, polyethylene wax, polypropylene wax, magnesium stearate, calcium stearate, fatty acid amide, etc. can be used. The external addition amount is usually in the range of 0.05 to 1.00 phr.

[0184] <Aromatic vinyl block copolymer composition>

[0185] The aromatic vinyl-conjugated diene copolymer composition of the present invention is a composition in which the masterbatch composition of the present invention is contained in an aromatic vinyl-conjugated diene copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block.

[0186] According to the present invention, by adding a hydrocarbon compound group having a total peak area of ​​components of each carbon number within the above range to an aromatic vinyl-conjugated diene copolymer as a base resin in the form of a masterbatch of an aromatic vinyl polymer, excellent compatibility can be achieved, thereby making it possible to make the obtained aromatic vinyl-conjugated diene copolymer composition have excellent film formability (for example, when formed into a film, the occurrence of film breakage and poor appearance can be effectively prevented) and excellent ozone crack resistance in a wide temperature range.

[0187] The aromatic vinyl-conjugated diene copolymer is not particularly limited as long as it has at least one aromatic vinyl polymer block and at least one conjugated diene polymer block. In the present invention, the following aromatic vinyl-conjugated diene copolymer composition can be preferably used.

[0188] That is, preferably, a compound containing the general formula (A): Ar1 a -D a -Ar2 a The block copolymer A represented by the general formula (B): Ar1 b -D b -Ar2 b The block copolymer B represented by the general formula (C): (Ar c -D c ) n -X represented by the block copolymer C, and the general formula (D): Ar d -D dThe aromatic vinyl-conjugated diene copolymer composition of the represented block copolymer D can be prepared in the same manner as the aromatic vinyl-conjugated diene copolymer composition preferably used in the above-mentioned masterbatch composition. In addition, the above-mentioned aromatic vinyl-conjugated diene copolymer composition can be prepared by mixing a mixture of block copolymer A and block copolymer B and a mixture of block copolymer C and block copolymer D in the same manner as the above-mentioned masterbatch composition.

[0189] The weight ratio (A / B / C / D) of the block copolymers A to D is preferably 10 to 30 / 20 to 40 / 12.5 to 49 / 1 to 37.5, more preferably 15 to 27.5 / 22.5 to 35 / 37.5 to 47.5 / 2.5 to 12.5, further preferably 17.5 to 25 / 25 to 32.5 / 40 to 46 / 4 to 10, and still more preferably 18 to 22 / 28 to 32 / 42 to 46 / 4 to 18.

[0190] The content ratio of the aromatic vinyl-conjugated diene copolymer and the masterbatch composition in the aromatic vinyl-conjugated diene copolymer composition of the present invention is not particularly limited, preferably the ratio of the aromatic vinyl-conjugated diene copolymer is 60-99 weight %, and the ratio of the masterbatch composition is 1-40 weight %, more preferably the ratio of the aromatic vinyl-conjugated diene copolymer is 80-98 weight %, and the ratio of the masterbatch composition is 2-20 weight %, further preferably the ratio of the aromatic vinyl-conjugated diene copolymer is 88-97 weight %, and the ratio of the masterbatch composition is 3-12 weight %, and further preferably the ratio of the aromatic vinyl-conjugated diene copolymer is 92-96 weight %, and the ratio of the masterbatch composition is 4-8 weight %. By making the content ratio the above range, the effect of the present invention can be more preferably improved.

[0191] The aromatic vinyl-conjugated diene copolymer composition of the present invention may further contain a lubricant, an antioxidant, a tackifier resin, a softener, an antibacterial agent, a light stabilizer, an ultraviolet absorber, a dye (pigment), etc. as required.

[0192] Examples of the lubricant include synthetic PE-WAX, oxidized PE-WAX, PP-based WAX, magnesium stearate, calcium stearate, and fatty acid amide.

[0193] The fatty acid amide may be an aliphatic monoamide or an aliphatic bisamide. The aliphatic monoamide is not particularly limited as long as it is a compound formed by a hydrocarbon group and an amide group (-NHCO) being bonded together, but preferably a monoamide of a higher saturated fatty acid having 12 or more carbon atoms (i.e., a compound formed by a chain alkyl group having 12 or more carbon atoms and an amide group (-NHCO) being bonded together) is used.

[0194] Specific examples of fatty acid monoamides include saturated fatty acid monoamides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide; and unsaturated fatty acid monoamides such as oleic acid amide and erucic acid amide.

[0195] The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-p-cresol, di-tert-butyl-4-methylphenol, 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and 4,6-bis(octylmethyl)-o-cresol; thiodicarboxylates such as dilaurylthiopropionate; and phosphites such as trinonylphenyl phosphite and butylenebis(3-methyl-6-tert-butylphenyl)-di-tridecylphosphite.

[0196] The ultraviolet absorber is not particularly limited, and triazine-based, benzoate-based, benzophenone-based, benzotriazole-based compounds and the like can be used, and they can also be used in combination. In particular, triazine-based and benzotriazole-based compounds are preferred, and specifically, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-[4,6-bis(1,1′-biphenyl-4-yl)-1,3,5-triazine-2-yl]-5-[(2-ethylhexyl)oxy]phenol and the like can be used.

[0197] The light stabilizer is not particularly limited, and for example, a hindered amine light stabilizer can be used, such as tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)=butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy- mixed esters of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)=sebacate, and the like.

[0198] A light stabilizer can be used together with a UV absorber.

[0199] The aromatic vinyl-conjugated diene copolymer composition of the present invention can be prepared by mixing an aromatic vinyl-conjugated diene copolymer, a masterbatch composition, and other components used as needed. For example, the method of removing the solvent by heating after dissolving each component in a solvent and uniformly mixing it; the method of melt-mixing each component by a kneader, etc. Among these methods, melt mixing is preferred from the viewpoint of more effective mixing. In particular, melt mixing using a twin-screw extruder, a single-screw extruder, a kneader, and a Banbury mixer is preferred. In addition, the temperature during melt mixing is not particularly limited, and is usually in the range of 100 to 230°C.

[0200] The aromatic vinyl-conjugated diene copolymer composition of the present invention can be used, for example, in the following applications: as molding materials for films, threads (elastic threads), gloves, elastic bands, condoms, various rolls for office automation equipment, office use, etc., packaging films and sheets, shock-proof sheets for electrical and electronic equipment, shock-proof rubber, impact-absorbing sheets, impact-buffering films and sheets, shock-absorbing sheets for housing, shock-absorbing materials, etc.; as adhesives for tapes, adhesive sheets, adhesive labels, dust removal rollers, etc.; as adhesives for sanitary products and binding; as elastic fibers for clothing, sporting goods, etc., etc.

[0201] The aromatic vinyl-conjugated diene copolymer composition of the present invention can be preferably used for films, and particularly, because of its excellent ozone crack resistance in a wide temperature range, such properties can be effectively utilized and preferably used for stretch films (film-like stretchable members for sanitary materials) for sanitary products such as paper diapers, sanitary pants, and masks. In addition, it can also be used for stretch yarns for sanitary products.

[0202] Example

[0203] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "parts" are based on weight unless otherwise specified.

[0204] The test methods performed in the present examples and comparative examples are as follows.

[0205] [Weight average molecular weight of each block copolymer]

[0206] The weight average molecular weight was determined as the polystyrene-equivalent molecular weight by high performance liquid chromatography using tetrahydrofuran as a carrier at a flow rate of 0.35 ml / min. The apparatus used was HLC8320 manufactured by Tosoh Corporation, the column used was a column formed by connecting three Shodex KF-404HQ manufactured by Showa Denko K.K. (column temperature 40° C.), the detector used was a differential refractometer and an ultraviolet detector, and the molecular weight was calibrated at 12 points using standard polystyrene (5 to 3 million) manufactured by Tosoh Corporation.

[0207] [Weight Ratio of Each Block Copolymer in the Block Copolymer Composition]

[0208] The ratio was determined from the area ratio of the peaks corresponding to the respective block copolymers in the chart obtained by the above-mentioned high performance liquid chromatography.

[0209] [Weight average molecular weight of styrene polymer block of each block copolymer]

[0210] According to the method described in Rubber Chem. Technol., 45, 1295 (1972), the block copolymer is reacted with ozone and reduced with lithium aluminum hydride, thereby decomposing the isoprene polymer block of the block copolymer. Specifically, the following steps are performed. That is, in a reaction vessel to which 100 ml of dichloromethane treated with a useful molecular sieve is added, 300 mg of the sample is dissolved. The reaction vessel is placed in a cooling tank to -25 ° C, and then oxygen is introduced into the reaction vessel at a flow rate of 170 ml / min while the ozone generated by the ozone generator is introduced. After 30 minutes from the start of the reaction, the gas flowing out of the reaction vessel is introduced into an aqueous solution of potassium iodide to confirm that the reaction is complete. Then, 50 ml of diethyl ether and 470 mg of lithium aluminum hydride are added to another reaction vessel after nitrogen substitution, and the reaction vessel is cooled with ice water while the solution reacted with ozone is slowly added dropwise to the reaction vessel. Then, place the reaction container in a water bath, slowly raise the temperature, and reflux at 40°C for 30 minutes. After that, add dilute hydrochloric acid to the reaction container in small amounts while stirring the solution, and continue to add until the generation of hydrogen can hardly be confirmed. After the reaction, filter out the solid product produced in the solution, and extract the solid product with 100 ml of diethyl ether for 10 minutes. Combine the extract with the filtrate during filtration, and distill off the solvent to obtain a solid sample. For the sample obtained in this way, measure the weight average molecular weight according to the above-mentioned weight average molecular weight determination method, and use this value as the weight average molecular weight of the styrene polymer block.

[0211] [Weight Average Molecular Weight of Isoprene Polymer Block of Each Block Copolymer]

[0212] The weight average molecular weight of the isoprene polymer block was determined based on the calculated value by subtracting the weight average molecular weight of the corresponding styrene polymer block from the weight average molecular weight of each block copolymer determined as described above.

[0213] [Styrene unit content of each block copolymer]

[0214] It was determined based on the detection intensity ratio of the differential refractometer and the ultraviolet detector in the measurement using the above-mentioned high performance liquid chromatography. In addition, copolymers having different styrene unit contents were prepared in advance, and a calibration curve was prepared using these.

[0215] [Total peak area of ​​each component of hydrocarbon wax]

[0216] For hydrocarbon wax, gas chromatography-mass spectrometry (GC-MS) analysis is performed using a capillary gas chromatography-mass spectrometry analyzer and an aluminum-coated capillary column as the column, with helium as the carrier gas, a flow rate of 4 ml / min, a column temperature of 180 to 390°C, and a heating rate of 15°C / min. The total peak area of ​​the following components is determined when the total peak area of ​​the components within the range of 12 to 60 carbon atoms is taken as 100%.

[0217] Total peak area of ​​components with 22 or more and 23 or less carbon atoms

[0218] Total peak area of ​​components with 24 or more and 27 or less carbon atoms

[0219] Total peak area of ​​components with 27 or more and 30 or less carbon atoms

[0220] Total peak area of ​​components with 30 or more and 33 or less carbon atoms

[0221] Total peak area of ​​components with 33 or more and 36 or less carbon atoms

[0222] Total peak area of ​​components with 12 or more and 27 or less carbon atoms

[0223] Total peak area of ​​components with 37 or more and 60 or less carbon atoms

[0224] In addition, the hydrocarbon waxes 1 to 7 used in the present examples and comparative examples are all hydrocarbon compounds having a carbon number within a range of 12 to 60, and consisting essentially of only carbon atoms and hydrogen atoms.

[0225] [Film breakage during molding]

[0226] In the methods of Examples and Comparative Examples described below, when a film was produced continuously for 15 minutes using the aromatic vinyl block copolymer composition, the presence or absence of breakage of the film was confirmed and evaluated based on the following criteria.

[0227] ○: No breakage of the film molded body occurred at all.

[0228] ×: Breakage of the film molded body was confirmed.

[0229] [Amount of adhesion to cooling roller over time]

[0230] When a film molded body was produced continuously for 60 minutes using the aromatic vinyl block copolymer composition by the method of Examples and Comparative Examples described below, the amount of deposits deposited on the cooling roll over time was checked and evaluated according to the following criteria.

[0231] 0: Adhesion ≤ 0.5g / m 2

[0232] ×: Adhesion amount>0.5g / m 2

[0233] [Ozone crack resistance of film (10℃, 23℃, 40℃)]

[0234] The film of the aromatic vinyl block copolymer composition is fixed to a tension retainer with a distance of 4.0 cm between chucks. Then, the distance between chucks is extended to 5.0 cm, and the film is fixed in a 25% elongated state. In this state, it is allowed to stand for more than 24 hours in a specified temperature environment. Then, the fixed film is placed in a thermostatic bath at 50% RH and an ozone concentration of 5 pphm, and the time until cracks can be confirmed with the naked eye is measured, and the evaluation is performed according to the following criteria. In addition, the measurement is carried out at each temperature of 10°C, 23°C, and 40°C.

[0235] ○: No cracks occurred even after 2 hours.

[0236] ×: Cracks occurred within 2 hours.

[0237] [Production Example 1]

[0238] 23.3 kg of cyclohexane, 1.4 mmol of N,N,N′,N′-tetramethylethylenediamine (hereinafter referred to as "TMEDA"), and 1.04 kg of styrene were added to a pressure-resistant reactor, and 92.9 mmol of n-butyllithium was added while stirring at 40°C. The polymerization was carried out for 1 hour while the temperature was raised to 50°C. The polymerization conversion rate of styrene was 100%. While continuing to control the temperature at 50-60°C, 5.66 kg of isoprene was continuously added to the reactor over a period of 1 hour. After the addition of isoprene was completed, the polymerization was further carried out for 1 hour. The polymerization conversion rate of isoprene was 100%. Next, while continuing to control the temperature at 50-60°C, 1.04 kg of styrene was continuously added over a period of 1 hour. After the addition of styrene was completed, the polymerization was further carried out for 1 hour to form a triblock chain with an active end. The polymerization conversion rate of styrene was 100%. Next, 63.4 mmol of methanol as a polymerization terminator was added and mixed, thereby inactivating a portion of the active ends of the triblock chain with active ends to form a styrene-isoprene-styrene triblock copolymer B1. After this, 0.98 kg of styrene was continuously added over a period of 1 hour while further controlling the temperature at 50 to 60°C. After the addition of styrene was completed, further polymerization was performed for 1 hour to form a triblock chain with active ends. The polymerization conversion rate of styrene was 100%. Finally, 63.4 mmol of methanol as a polymerization terminator was added and mixed, thereby inactivating all the active ends of the triblock chain to form a styrene-isoprene-styrene triblock copolymer A1 (the formula is shown in Table 1). A portion of the obtained reaction solution was taken out, and the block copolymer was evaluated according to the above-mentioned measurement method. The results are shown in Table 2.

[0239] 0.3 parts of 2,6-di-tert-butyl-p-cresol as an antioxidant are added to 100 parts of the reaction solution obtained as above (containing 30 parts of polymer components) and mixed, and the mixed solution is added dropwise to hot water heated to 85-95°C in small amounts each time, and the solvent is volatilized to obtain a precipitate, which is crushed and dried with hot air at 85°C, thereby recovering a mixture containing block copolymer A1 and block copolymer B1. The mixture is further supplied to a uniaxial extruder and heated and melted at 170°C, and formed into granules using an underwater cutting granulator. In order to prevent the particles from sticking to each other, 0.2 parts of talc are added to the outside of 100 parts of the particles.

[0240] The weight ratio of the block copolymer A1 to the block copolymer B1 in the above mixture (block copolymer A1 / block copolymer B1) was 40 / 60.

[0241] [Table 1]

[0242] Table 1

[0243] Production Example 1 Cyclohexane(kg) 23.3 TMEDA (mmol) 1.4 n-Butyllithium (mmol) 92.9 Styrene (kg) [first stage of polymerization] 1.04 Isoprene (kg) [second stage of polymerization] 5.66 Styrene (kg) [polymerization third stage] 1.04 Methanol (mmol) [after the third stage of polymerization] 63.4 Styrene (kg) [Fourth stage of polymerization] 0.98 Methanol (mmol) [after the fourth stage of polymerization] 63

[0244] [Table 2]

[0245] Table 2

[0246] Production Example 1 Block copolymer A1 A1 <![CDATA[Weight-average molecular weight (×10 3 )]]> 173 <![CDATA[Ar1 a The weight average molecular weight (×10 3 )]]> 12 <![CDATA[Ar2 a The weight average molecular weight (×10 3 )]]> 67 <![CDATA[D a Vinyl bond content (mol%)]]> 7 <![CDATA[D a The weight average molecular weight (×10 3 )]]> 96 Styrene unit content (weight %) 48 Block copolymer B1 B1 <![CDATA[Weight-average molecular weight (×10 3 )]]> 120 <![CDATA[Ar1 b The weight average molecular weight (×10 3 )]]> 12 <![CDATA[Ar2 b The weight average molecular weight (×10 3 )]]> 12 <![CDATA[D b Vinyl bond content (mol%)]]> 7 <![CDATA[D b The weight average molecular weight (×10 3 )]]> 96 Styrene unit content (weight %) 27 Weight ratio A1 / B1 40 / 60 Total Styrene Content 35

[0247] [Production Example 2]

[0248] 23.2 kg of cyclohexane, 1.5 mmol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA), and 1.20 kg of styrene were added to a pressure-resistant reactor, and 101.7 mmol of n-butyllithium was added while stirring at 40°C, and polymerization was carried out for 1 hour while heating to 50°C. The polymerization conversion rate of styrene was 100%. While continuing to control the temperature at 50-60°C, 6.53 kg of isoprene was continuously added to the reactor over a period of 1 hour. After the addition of isoprene was completed, polymerization was further carried out for 1 hour to form a diblock chain with an active end. The polymerization conversion rate of isoprene was 100%. Next, 25.4 mmol of dimethyldichlorosilane and 9.7 mmol of tetramethoxysilane were added as coupling agents, and a coupling reaction was carried out for 2 hours to form a styrene-isoprene coupled block copolymer C1. After that, 203 mmol of methanol as a polymerization terminator was added and mixed, thereby completely deactivating the active ends of the diblock chains to form a styrene-isoprene diblock copolymer D1 (the formulation is shown in Table 3). A portion of the obtained reaction solution was taken out and the block copolymer was evaluated according to the above-mentioned measurement method. The results are shown in Table 4.

[0249] 0.3 parts of 2,6-di-tert-butyl-p-cresol as an antioxidant were added to 100 parts of the reaction solution obtained as above and mixed, and the mixed solution was added dropwise to hot water heated to 85-95°C in small amounts each time, and the solvent was volatilized to obtain a precipitate, which was crushed and dried with hot air at 85°C to recover a mixture containing block copolymer C1 and block copolymer D1. The mixture was further supplied to a uniaxial extruder and heated and melted at 170°C, and formed into granules using an underwater cutting granulator. In order to prevent the particles from sticking to each other, 0.2 parts of talc were added to the outside of 100 parts of the particles.

[0250] The weight ratio of the block copolymer C1 to the block copolymer D1 in the above mixture (block copolymer C1 / block copolymer D1) was 90 / 10.

[0251] [Table 3]

[0252] Table 3

[0253] Production Example 2 Cyclohexane(Kg) 23.2 TMEDA (mmol) 1.5 n-Butyllithium (mmol) 101.7 Styrene (Kg) [First stage of polymerization] 1.20 Isoprene (Kg) [Second stage of polymerization] 6.53 Dimethyldichlorosilane (mmol) [after the second stage of polymerization] 25.4 Tetramethoxysilane (mmol) [after the second stage of polymerization] 9.7 Methanol (mmol) [after the second stage of polymerization] 203

[0254] [Table 4]

[0255] Table 4

[0256] Production Example 2 Block copolymer C1 C1 Proportion of branch number n=2 (weight %) 56 Proportion of branch number n=3 (weight %) 22 Proportion of branch number n=4 (weight %) 22 <![CDATA[Weight-average molecular weight (×10 3 )]]> 250 <![CDATA[Ar c The weight average molecular weight (×10 3 )]]> 9 <![CDATA[D c Vinyl bond content (mol%)]]> 7 <![CDATA[D c The weight average molecular weight (×10 3 )]]> 105 Styrene unit content (weight %) 14 Block copolymer D1 D1 <![CDATA[Weight-average molecular weight (×10 3 )]]> 112 <![CDATA[Ar d The weight average molecular weight (×10 3 )]]> 9 <![CDATA[D d Vinyl bond content (mol%)]]> 7 <![CDATA[D d The weight average molecular weight (×10 3 )]]> 105 Styrene unit content (weight %) 14 Weight ratio C1 / D1 90 / 10 Total Styrene Content 14

[0257] [Production Example 3]

[0258] 23.3 kg of cyclohexane, 3.6 mmol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA"), and 1.50 kg of styrene were added to a pressure-resistant reactor, and 120.5 mmol of n-butyllithium was added while stirring at 40°C, and polymerization was carried out for 1 hour while heating to 50°C. The polymerization conversion rate of styrene was 100%. While continuing to control the temperature at 50-60°C, 7.00 kg of isoprene was continuously added to the reactor over a period of 1 hour. After the addition of isoprene was completed, polymerization was further carried out for 1 hour. The polymerization conversion rate of isoprene was 100%. Next, while continuing to control the temperature at 50-60°C, 1.50 kg of styrene was continuously added over a period of 1 hour. After the addition of styrene was completed, polymerization was further carried out for 1 hour to form a triblock chain with an active end. The polymerization conversion rate of styrene was 100%. Next, 241 mmol of methanol as a polymerization terminator was added and mixed, thereby deactivating all the active ends of the triblock chains having active ends, and forming a styrene-isoprene-styrene triblock copolymer B2 (the formula is shown in Table 5). A portion of the obtained reaction solution was taken out, and the block copolymer was evaluated according to the above-mentioned measurement method. The results are shown in Table 6.

[0259] 0.3 parts of 2,6-di-tert-butyl-p-cresol as an antioxidant was added to 100 parts of the reaction solution obtained as above (containing 30 parts of polymer components) and mixed, and the mixed solution was added dropwise to hot water heated to 85-95°C in small amounts each time, and the solvent was volatilized to obtain a precipitate, which was crushed and hot-air dried at 85°C to recover a mixture containing block copolymer B2. The mixture was further supplied to a uniaxial extruder and heated and melted at 170°C, and formed into granules using an underwater cutting granulator. In order to prevent the particles from sticking to each other, 0.2 parts of talc were added to the outside of 100 parts of the particles.

[0260] [Table 5]

[0261] Table 5

[0262] Production Example 3 Cyclohexane(Kg) 23.3 TMEDA (mmol) 3.6 n-Butyllithium (mmol) 120.5 Styrene (Kg) [First stage of polymerization] 1.50 Isoprene (Kg) [Second stage of polymerization] 7.00 Styrene (Kg) [Polymerization third stage] 1.50 Methanol (mmol) [after the second stage of polymerization] 241

[0263] [Table 6]

[0264] Table 6

[0265] Production Example 3 Block copolymer B2 B2 <![CDATA[Weight-average molecular weight (×10 3 )]]> 120 <![CDATA[Ar1 e The weight average molecular weight (×10 3 )]]> 12 <![CDATA[Ar2 e The weight average molecular weight (×10 3 )]]> 12 <![CDATA[D e Vinyl bond content (mol%)]]> 7 <![CDATA[D e The weight average molecular weight (×10 3 )]]> 96 Styrene unit content (weight %) 30

[0266] [Example 1]

[0267] (Preparation of Masterbatch Composition)

[0268] A mixture of 55 parts by weight of the block copolymer A1 and block copolymer B1 obtained in Preparation Example 1, 40 parts by weight of hydrocarbon wax 1 (trade name "SUNNOC P", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), and 5 parts by weight of an ultraviolet absorber (2-[4,6-bis(1,1′-biphenyl-4-yl)-1,3,5-triazine-2-yl)-5-[(2-ethylhexyl)oxy]phenol) were mixed at 40 to 160° C. for 20 minutes using a Banbury mixer to prepare a masterbatch composition. The composition was directly supplied in a molten state to a single-screw extruder having a thermal cutting granulator and molded into pellets. In addition, hydrocarbon wax 1 was subjected to gas chromatography-mass spectrometry (GC-MS) analysis, and the total peak area of ​​each component is shown in Table 7.

[0269] (Preparation of aromatic vinyl-conjugated diene copolymer composition)

[0270] The mixture particles of the block copolymer A1 obtained in the manufacturing example 1 of 47.5 parts by weight and the block copolymer B1, the mixture particles of the block copolymer C1 obtained in the manufacturing example 2 of 47.5 parts by weight and the block copolymer D1, and the masterbatch composition particles obtained above of 5 parts by weight are put into a twin-shaft extruder equipped with a T-die in a state of pre-uniform dry mixing. Then, they are heated to melt and kneaded at 200 ° C in the twin-shaft extruder, and are cooled by extruding onto a cooling roll for 60 consecutive minutes, and then wound with a winding roll, thereby forming a film with an average thickness of 0.05 mm. At this time, the film fracture during molding and the determination of the amount of adhesion to the cooling roll over time are performed according to the above method. In addition, the film molding obtained is subjected to the determination of ozone crack resistance. The results are shown in Table 8. In addition, the details of the molding conditions of the film are as follows.

[0271] (Film Forming Conditions)

[0272] Additive processing speed: 5kg / hour

[0273] Film pulling speed: 4m / min

[0274] Extruder temperature: Adjust to 40℃ at the inlet and 200℃ at the T-die

[0275] Screw: Full flight (with kneading area)

[0276] Extruder L / D: 30

[0277] T-die: width 200mm, die lip 0.5mm

[0278] Distance between the top of the T-die and the cooling roller: 10mm

[0279] Temperature of cooling roller: 25℃

[0280] [Examples 2 to 5, Comparative Examples 1 to 5]

[0281] (Preparation of Masterbatch Composition)

[0282] A masterbatch composition was prepared in the same manner as in Example 1 except that the formulation composition was changed to that shown in Table 8.

[0283] In addition, each component is as follows. In addition, the following hydrocarbon waxes 2 to 6 were subjected to gas chromatography-mass spectrometry (GC-MS) analysis. The total peak area of ​​each component is shown in Table 7.

[0284] Hydrocarbon wax 2: Hydrocarbon wax (trade name "OZOACE 0355", manufactured by Nippon Seiro Co., Ltd.)

[0285] Hydrocarbon wax 3: a mixture of 50% by weight of a hydrocarbon wax (trade name "PW-135", manufactured by Nippon Seiro Co., Ltd.) and 50% by weight of a hydrocarbon wax (trade name "SUNNOC P", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

[0286] Hydrocarbon wax 4: Hydrocarbon wax (trade name "OZOACE 3201", manufactured by Nippon Seiro Co., Ltd.)

[0287] Hydrocarbon wax 5: Hydrocarbon wax (trade name "PW-135", manufactured by Nippon Seiro Co., Ltd.)

[0288] Hydrocarbon wax 6: Hydrocarbon wax (trade name "PW-115", manufactured by Nippon Seiro Co., Ltd.)

[0289] Hydrocarbon wax 7: Hydrocarbon wax (trade name "SANWAX 171P", manufactured by Sanyo Chemical Co., Ltd.)

[0290] Polystyrene: Polystyrene (trade name "GPPS679", manufactured by PS Japan Co., Ltd.)

[0291] Low-density polyethylene 1: low-density polyethylene (trade name "NOVATEC LL LJ802", manufactured by Japan Polyethylene Co., Ltd.)

[0292] Low-density polyethylene 2: low-density polyethylene (trade name "Dowlex 2047G", manufactured by Dow Chemical Company)

[0293] (Preparation of aromatic vinyl-conjugated diene copolymer composition)

[0294] Then, an aromatic vinyl-conjugated diene copolymer composition was prepared in the same manner as in Example 1 except that the masterbatch composition obtained above was used, and a film was produced and measured and evaluated in the same manner.

[0295] [Table 7]

[0296]

[0297] [Table 8]

[0298] Table 8

[0299]

[0300] As shown in Tables 7 and 8, when a masterbatch composition containing 30 to 98 wt % of an aromatic vinyl polymer and 2 to 70 wt % of a hydrocarbon wax (hydrocarbon compound group) having a total peak area of ​​each component within the range specified in the present invention is used, when it is added to an aromatic vinyl-conjugated diene copolymer and molded into a film, the film can be effectively prevented from breaking, and the amount of adhesion to the cooling roller over time can be suppressed, thereby suppressing the occurrence of poor appearance caused by such adhesion, achieving excellent film formability, and being able to form a film with excellent ozone cracking resistance in a wide temperature range (Examples 1 to 5).

[0301] On the other hand, when a hydrocarbon wax in which the total peak area of ​​each component is outside the range specified in the present invention is used as the hydrocarbon wax (hydrocarbon compound group), when formed into a film, the amount of adhesion to the cooling roller over time increases, resulting in poor appearance and poor ozone crack resistance at low temperatures (10°C) or high temperatures (40°C) (Comparative Examples 1 to 3).

[0302] Furthermore, when a polymer other than an aromatic vinyl polymer was used in preparing a masterbatch composition, when the composition was molded into a film, the film broke (Comparative Examples 4 and 5).

Claims

1. A masterbatch composition comprising 30 to 98% by weight of an aromatic vinyl polymer and The aromatic vinyl polymer comprises at least one aromatic vinyl polymer block. In the hydrocarbon compound group, the number of carbon atoms in each of the hydrocarbon compounds determined by gas chromatography-mass spectrometry (GC-MS) analysis is The total peak area of ​​components having 24 or more and 27 or less carbon atoms is 5% or more, The total peak area of ​​components having 27 or more and 30 or less carbon atoms is 5% or more, The total peak area of ​​components having 30 or more and 33 or less carbon atoms is 5% or more, The total peak area of ​​components having 33 or more and 36 or less carbon atoms is 5% or more, The total peak area of ​​components having 12 or more and 27 or less carbon atoms is 45% or less.

2. The masterbatch composition according to claim 1, wherein In the group of hydrocarbon compounds, The total peak area of ​​components having 24 or more and 27 or less carbon atoms is 8 to 40%, The total peak area of ​​components having 27 or more and 30 or less carbon atoms is 8 to 50%, The total peak area of ​​components having 30 or more and 33 or less carbon atoms is 10 to 45%, The total peak area of ​​components having 33 or more and 36 or less carbon atoms is 7 to 30%, The total peak area of ​​components having 12 or more and 27 or less carbon atoms is 10 to 40%.

3. The masterbatch composition according to claim 1 or 2, wherein: The aromatic vinyl polymer 4. The masterbatch composition according to claim 3, wherein The aromatic vinyl-conjugated 5. The masterbatch composition according to claim 3, wherein The aromatic vinyl-conjugated 6. An aromatic vinyl-conjugated diene copolymer composition comprising an aromatic vinyl-conjugated diene copolymer 7. An elastomer comprising the aromatic vinyl-conjugated diene copolymer according to claim 6 8. A film comprising the aromatic vinyl-conjugated diene copolymer composition according to claim 6 9. A telescopic member using the elastic body according to claim 7 or the film according to claim 8