Thermoplastic elastomer composition and multilayer molded article

Abstract

The objective is to obtain a thermoplastic elastomer composition that exhibits good heat-sealing properties with various base resins and has excellent fluidity and transparency, which are indicators that affect the molded appearance. [Solution] A thermoplastic elastomer composition containing a polymer hydrogenated block copolymer (I) that satisfies predetermined conditions, a non-aromatic softener (II), and an olefin resin (III), wherein the composition contains 20 to 400 parts by mass of the non-aromatic softener (II) and 10 to 200 parts by mass of the olefin resin (III) per 100 parts by mass of the polymer hydrogenated block copolymer (I).

Description

[Technical Field]

[0001] The present invention relates to thermoplastic elastomer compositions and multilayer molded articles. [Background technology]

[0002] Styrene-based thermoplastic elastomers are block copolymers in which polystyrene blocks are hard blocks and polymer blocks of conjugated diene compounds such as polybutadiene and polyisoprene are soft blocks. Conventionally, they have been widely used as materials with thermoplastic and rubber elasticity in asphalt modifiers, adhesives, medical tubes, infusion bag films, automobile bumpers, automobile interior surface materials, footwear, cable coatings, protective films, and electronic materials such as semiconductor substrates.

[0003] Furthermore, thermoplastic elastomer compositions (elastomer compounds: mixtures of thermoplastic elastomer, softener, resin, and other additives) have long been used in a wide variety of fields due to their broad design flexibility and superior moldability, aesthetic appeal, hygiene, and recyclability compared to vulcanized rubber. One particular application is in multilayer molded articles.

[0004] In the aforementioned multilayer molded articles, polar group-containing thermoplastic resins, known as engineering plastics, are widely used as the base resin for the multilayer laminate due to their excellent heat resistance and mechanical properties. Known multilayer molded articles include those in which a soft material such as a thermoplastic elastomer is bonded to the surface or part of a base material made of a polar group-containing thermoplastic resin. Examples of such multilayer molded articles include automotive interior surfaces, grips, cushioning materials, and sealing members such as gaskets.

[0005] Methods for bonding a soft material to a thermoplastic resin substrate containing polar groups include, for example, bonding with an adhesive or bonding by heat fusion during molding. In the method using an adhesive, the soft material and the base material can be firmly adhered through the adhesive. However, in addition to the step of applying the adhesive, a curing step is required, which has the problem of slow production speed. In recent years, especially from the perspective of low VOC (volatile organic compounds), the need for adhesive loss has been increasing. On the other hand, as an adhesion method by heat fusion during molding, adhesion methods in injection molding such as insert molding and two-color molding can be mentioned. In these adhesion methods by injection molding, since heat fusion can be achieved simultaneously with molding, a significant improvement in production speed is possible. In recent years, the adhesion method by heat fusion in injection molding has been increasing.

[0006] However, in the adhesion method by heat fusion, the affinity of the soft material to be adhered to the base material of the thermoplastic resin is an important factor. When a non-polar resin composition is used as the soft material, there is a problem that the adhesion strength becomes weak. Therefore, for the purpose of promoting the interaction with various materials and improving the adhesion strength and the like, as the soft material, a thermoplastic elastomer having a functional group, a composition for thermal adhesion containing a modifying component, and technologies related to adhesives using the composition have been widely proposed.

[0007] For example, Patent Document 1 discloses an asphalt composition using a hydrogenated styrene-based thermoplastic elastomer with a specific structure for the purpose of improving the adhesion between asphalt and aggregates (sand and stones). Further, Patent Document 2 discloses a thermoplastic elastomer composition containing a hydrogenated styrene-based thermoplastic elastomer, a softening agent for hydrocarbon rubber, polypropylene, a thermoplastic polyurethane elastomer, and an acid-modified hydrogenated styrene-based elastomer. Furthermore, Patent Document 3 discloses a technology related to a thermoplastic polymer composition containing a thermoplastic elastomer, a polyvinyl acetal resin and / or a polar group-containing polypropylene-based resin, and an adhesive body composed of the thermoplastic polymer composition and an insert member.

Prior Art Documents

Patent Documents

[0008] [Patent Document 1] International Publication No. 2015 / 108150 [Patent Document 2] Japanese Patent Publication No. 2009-209273 [Patent Document 3] Japanese Patent Publication No. 2014-168940 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, the hydrogenated styrene-based thermoplastic elastomer having a specific structure disclosed in Patent Document 1, while possessing a distinctive structure, has only been studied as an asphalt composition and has not been sufficiently studied as a thermoplastic elastomer composition (elastomer compound). As a result, it has the problem that there is room for improvement regarding its heat-sealing properties to various base resins.

[0010] Furthermore, the thermoplastic elastomer composition disclosed in Patent Document 2, as mentioned above, contains a hydrogenated thermoplastic styrene elastomer and a thermoplastic polyurethane elastomer. However, these are incompatible and have different refractive indices, resulting in an opaque thermoplastic elastomer composition that is unsuitable for applications requiring transparency. In addition, the target base resin for heat fusion is limited to specific types, and insufficient research has been conducted.

[0011] Furthermore, the thermoplastic polymer composition disclosed in Patent Document 3, as described above, contains a thermoplastic elastomer and a polyvinyl acetal resin and / or a polar group-containing polypropylene resin. However, the thermoplastic elastomer and the polyvinyl acetal resin are similarly incompatible and have different refractive indices. Therefore, the resulting thermoplastic polymer composition is opaque and unsuitable for applications requiring transparency. In addition, the thermoplastic elastomer has low fluidity, which can lead to poor molded appearance.

[0012] As described above, conventionally proposed thermoplastic elastomer compositions and thermoplastic polymer compositions for heat fusion have problems in that there is room for improvement in terms of heat fusion properties to various base resins, transparency, and fluidity.

[0013] Therefore, the present invention aims to provide a thermoplastic elastomer composition that exhibits good heat-sealing properties with various base resins, as well as excellent fluidity and transparency. [Means for solving the problem]

[0014] As a result of diligent research to solve the problems of the prior art described above, the present inventors have found that a thermoplastic elastomer composition containing a polymer hydrogenated block copolymer having a predetermined structure, a non-aromatic softener, and an olefin resin in predetermined ratios can solve the problems of the prior art described above, and have completed the present invention. In other words, the present invention is as follows:

[0015] [1] High polymer hydrogenated block copolymer (I), Non-aromatic softener (II), Olefin resin (III) and A thermoplastic elastomer composition containing, The polymer hydrogenated block copolymer (I) satisfies the following conditions (a) to (g): The product contains 20 to 400 parts by mass of the non-aromatic softener (II) and 10 to 200 parts by mass of the olefin resin (III) per 100 parts by mass of the polymer hydrogenated block copolymer (I). Thermoplastic elastomer composition. <Condition (a)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A1 mainly composed of vinyl aromatic monomer units, and polymer block B1 and / or polymer block C1 mainly composed of conjugated diene monomers, comprising vinyl aromatic monomer units and conjugated diene monomer units. <Condition (b)> The total vinyl aromatic monomer content is 20-60% by mass. <Condition (c)> The content of the polymer block A1 is 15 to 40% by mass. <Condition (d)> The amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 25 moles or more. <Condition (e)> The hydrogenation rate of the double bond in the conjugated diene monomer unit is between 50 ml and 90 ml. <Condition (f)> The weight-average molecular weight (Mw) is between 150,000 and 300,000. <Condition (g)> The molecule contains at least one functional group selected from the group consisting of amino groups, amide groups, hydroxyl groups, acid anhydride groups, epoxy groups, silanol groups, and alkoxysilyl groups. [2] The thermoplastic elastomer composition further contains a hydrogenated block copolymer (IV) that satisfies the following conditions (h) to (m): The thermoplastic elastomer composition described in [1] above. <Condition (h)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A2 mainly composed of vinyl aromatic monomer units and a polymer block C2 mainly composed of conjugated diene monomer units. <Condition (i)> The total vinyl aromatic monomer content is 15% by mass or more and 70% by mass or less. <Condition (j)> The amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 30 moles or more. <Condition (k)> The hydrogenation rate of the double bond in the conjugated diene monomer unit is 50 ml or more. <Condition(l)> The weight-average molecular weight (Mw) is between 30,000 and 150,000. <Condition(m)> The MFR value measured at 230℃ and 2.16kg is 2.0g / 10min or higher. [3] The hydrogenated block copolymer (IV) has at least one functional group selected from the group consisting of an amino group, a hydroxyl group, an acid anhydride group, a silanol group, and an alkoxysilyl group in its molecule. The thermoplastic elastomer composition described in [2] above. [4] The hydrogenated block copolymer (IV) is contained in an amount of 50 to 200 parts by mass relative to 100 parts by mass of the polymer hydrogenated block copolymer (I). The thermoplastic elastomer composition described in [2] or [3] above. [5] The MFR value measured at 230℃ and 2.16kg is 70g / 10min or higher. A thermoplastic elastomer composition according to any one of the above [1] to [4]. [6] A layer L1 of the thermoplastic elastomer composition according to any one of [1] to [5] above, Thermoplastic resin substrate layer L2, A multilayer molded body having the following characteristics. [7] The thermoplastic resin constituting the thermoplastic resin substrate layer L2 is It is at least one selected from the group consisting of olefin resins, styrene resins, polycarbonates, polyesters, acrylic resins, polyamides, and mixtures thereof. The multilayer molded body described in [6] above. [Effects of the Invention]

[0016] According to the present invention, a thermoplastic elastomer composition can be obtained that exhibits good heat-sealing properties with various base resins and has excellent fluidity and transparency, which are indicators that affect the molded appearance. [Modes for carrying out the invention]

[0017] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. The following embodiments are illustrative examples for explaining the present invention and are not intended to limit the present invention to the following content. The present invention can be implemented in various modified forms within the scope of its gist.

[0018] [Thermoplastic elastomer composition] The thermoplastic elastomer composition of this embodiment is High polymer hydrogenated block copolymer (I), Non-aromatic softener (II), Olefin resin (III) and A thermoplastic elastomer composition containing, The polymer hydrogenated block copolymer (I) satisfies the following conditions (a) to (g): The product contains 20 to 400 parts by mass of the non-aromatic softener (II) and 10 to 200 parts by mass of the olefin resin (III) per 100 parts by mass of the polymer hydrogenated block copolymer (I). <Condition (a)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A1 mainly composed of vinyl aromatic monomer units, and polymer block B1 and / or polymer block C1 mainly composed of conjugated diene monomers, comprising vinyl aromatic monomer units and conjugated diene monomer units. <Condition (b)> The total vinyl aromatic monomer content is 20-60% by mass. <Condition (c)> The content of the polymer block A1 is 15 to 40% by mass. <Condition (d)> The amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 25 moles or more. <Condition (e)> The hydrogenation rate of the double bond in the conjugated diene monomer unit is between 50 ml and 90 ml. <Condition (f)> The weight-average molecular weight (Mw) is between 150,000 and 300,000. <Condition (g)> The molecule contains at least one functional group selected from the group consisting of amino groups, amide groups, hydroxyl groups, acid anhydride groups, epoxy groups, silanol groups, and alkoxysilyl groups.

[0019] According to this embodiment, a thermoplastic elastomer composition is obtained that exhibits good heat-sealing properties with various base resins and has excellent fluidity and transparency.

[0020] The thermoplastic elastomer composition of this embodiment is suitable as a thermoplastic elastomer composition for multilayer molding, which is heat-fused with other components by injection molding. The following provides a detailed explanation of each component.

[0021] (Hydrogenated polymer block copolymer (I)) The thermoplastic elastomer composition of this embodiment contains a polymer hydrogenated block copolymer (I). The polymer hydrogenated block copolymer (I) satisfies the following conditions (a) to (g).

[0022] <Condition (a)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A1 mainly composed of vinyl aromatic monomer units, and polymer block B1 and / or polymer block C1 mainly composed of conjugated diene monomers, comprising vinyl aromatic monomer units and conjugated diene monomer units.

[0023] The polymer hydrogenated block copolymer (I) is obtained by hydrogenating (hereinafter also referred to as hydrogenation) a block copolymer composed of polymer block A1 mainly consisting of at least one vinyl aromatic monomer unit, polymer block B1 containing vinyl aromatic monomer units and conjugated diene monomer units, and / or polymer block C1 mainly consisting of conjugated diene monomer units.

[0024] The polymer block A1 mainly composed of vinyl aromatic monomer units is a polymer block in which the content of vinyl aromatic monomer units in polymer block A1 exceeds 80% by mass, and from the viewpoint of mechanical strength and heat deformation resistance of the thermoplastic elastomer composition of this embodiment, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0025] The polymer block B1 containing vinyl aromatic monomer units and conjugated diene monomer units is a polymer block in which the content of vinyl aromatic monomer units in polymer block B1 is 15% by mass or more and 80% by mass or less. From the viewpoint of the flexibility, softener retention and adhesion to the base resin of the thermoplastic elastomer of this embodiment, the content is preferably 15% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 70% by mass or less, even more preferably 15% by mass or more and 65% by mass or less, and even more preferably 15% by mass or more and 60% by mass or less.

[0026] The polymer block C1 mainly composed of conjugated diene monomer units is a polymer block in which the content of conjugated diene monomer units in polymer block C1 exceeds 80% by mass, and from the viewpoint of the flexibility and softener retention of the thermoplastic elastomer composition of this embodiment, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0027] In this embodiment, the naming of each monomer unit constituting the block copolymer follows the naming of the monomer from which the monomer unit is derived. For example, "vinyl aromatic monomer unit" refers to a polymer unit produced as a result of polymerizing a vinyl aromatic compound which is a monomer, and its structure is a molecular structure in which the two carbon atoms of a substituted ethylene group derived from a substituted vinyl group are bonded sites. Furthermore, a "conjugated diene monomer unit" refers to a polymer constituent unit resulting from the polymerization of conjugated diene compounds, which are monomers. Its structure is a molecular structure in which the two carbon atoms of the olefin derived from the conjugated diene compound form the bonding sites.

[0028] In this embodiment, the vinyl aromatic compound that can be used to form vinyl aromatic monomer units in polymer block A1 and polymer block B1 refers to a compound having a vinyl group and an aromatic ring. Examples of vinyl aromatic compounds include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, styrene, α-methylstyrene, and divinylbenzene are preferred from the viewpoint of polymerizability. These vinyl aromatic compounds may be used individually or in combination of two or more.

[0029] The conjugated diene compounds that can be used to form conjugated diene monomer units in polymer blocks B1 and C1 are diolefins having a pair of conjugated double bonds (two double bonds bonded in a conjugated manner). Examples of the conjugated diene compound include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. Among these, from the viewpoint of polymerization property, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) are preferably used. These conjugated diene compounds may be used alone or in combination of two or more kinds.

[0030] The polymer hydrogenated block copolymer (I) has, for example, a structure represented by the following general formula, but is not limited thereto. Furthermore, the polymer hydrogenated block copolymer (I) may be a mixture containing a plurality of copolymers having a structure represented by the following general formula in an arbitrary ratio. (A1-B1) n 、A1-(B1-A1) n 、A1-(C1-B1-A1) n 、B1-(A1-B1) n 、(A1-C1) n 、C1-(A1-C1) n 、C1-(B1-A1) n、 [(B1-A1) n m -X、[(A1-B1) n m -X、[(A1-C1) n m -X、[(C1-A1) n m -X、[(B1-A1) n -B1] m -X、[(A1-B1) n -A1] m -X、[(A1-C1) n -A1] m -X、[(A1-B1-C1) n -A1] m -X

[0031] ​​​​In the above general formula, A1 is a polymer block mainly composed of vinyl aromatic monomer units, B1 is a polymer block containing vinyl aromatic monomer units and conjugated diene monomer units, and C1 is a polymer block mainly composed of conjugated diene monomer units. The boundaries between polymer block A1, polymer block B1, and polymer block C1 do not necessarily need to be clearly distinguishable. Furthermore, n is an integer greater than or equal to 1, preferably an integer between 1 and 5. m is an integer greater than or equal to 2, preferably between 2 and 11, more preferably between 2 and 8. X represents a coupling agent residue. Here, a coupling residue refers to the residue after a coupling agent has been applied to bond multiple copolymers of conjugated diene monomer units and vinyl aromatic monomer units between polymer blocks A1 and polymer blocks A1, polymer blocks B1 and polymer blocks B1, polymer blocks C1 and polymer blocks C1, polymer blocks A1 and polymer blocks B1, and polymer blocks A1 and polymer blocks C1. Examples of coupling agents include, but are not limited to, silicon halide compounds and acid esters, as described later. In the above general formula, the vinyl aromatic monomer units in polymer block A1, polymer block B1, and polymer block C1 may be uniformly distributed or tapered. Furthermore, if polymer block A1, polymer block B1, and polymer block C1 are copolymer blocks of vinyl aromatic monomer units and conjugated diene monomer units, there may be multiple portions in the copolymer block where the vinyl aromatic monomer units are uniformly distributed and multiple portions where they are distributed in a tapered manner. In addition, multiple portions with different vinyl aromatic monomer unit content may coexist within the copolymer block.

[0032] <Condition (b)> The content of total vinyl aromatic monomer units in the polymer hydrogenated block copolymer (I) is 20% by mass or more and 60% by mass or less. The content is preferably 25% by mass or more and 55% by mass or less, more preferably 30% by mass or more and 50% by mass or less, and even more preferably 35% by mass or more and 45% by mass or less. Because the content of total vinyl aromatic monomer units in the polymer hydrogenated block copolymer (I) is within the aforementioned numerical range, when the thermoplastic elastomer composition of this embodiment is used to form a multilayer molded article with a predetermined substrate, the solubility parameter (hereinafter also referred to as the SP value) of the thermoplastic elastomer composition of this embodiment becomes closer to that of the substrate resin, and the heat-sealing properties of the thermoplastic elastomer composition of this embodiment tend to improve. Furthermore, because the refractive index becomes closer to that of the hydrogenated block copolymer (IV) described later, the transparency of the molded article of the thermoplastic elastomer composition of this embodiment tends to improve. Furthermore, since mechanical strength is a necessary property for material strength and flexibility is a property related to tactile feel, when the thermoplastic elastomer composition of this embodiment is used for grips, surface materials, and sealing materials, it is preferable to design the content of total vinyl aromatic monomer units in the polymer hydrogenated block copolymer (I) to be within the aforementioned numerical range suitable for these applications.

[0033] When the total vinyl aromatic monomer unit content in the polymer hydrogenated block copolymer (I) is 20% by mass or more, the mechanical strength, heat fusion properties to the base resin, and transparency of the thermoplastic elastomer composition of this embodiment tend to improve, and when the total vinyl aromatic monomer unit content is 60% by mass or less, the flexibility, resilience, and rebound elasticity of the thermoplastic elastomer composition of this embodiment tend to improve. Furthermore, the content of total vinyl aromatic monomer units in the polymer hydrogenated block copolymer (I) can be controlled to the above numerical range by adjusting the amount of monomer added during the polymerization process of the polymer hydrogenated block copolymer (I), and can be calculated using the absorption intensity at 262 nm with an ultraviolet spectrophotometer as described in the examples described later.

[0034] <Condition (c)> The content of polymer block A1, which mainly consists of vinyl aromatic monomer units constituting the polymer hydrogenated block copolymer (I), is 15% by mass or more and 40% by mass or less of the total polymer hydrogenated block copolymer (I), preferably 15% by mass or more and 35% by mass or less, and more preferably 15% by mass or more and 30% by mass or less. Because the content of polymer block A1 constituting the polymer hydrogenated block copolymer (I) is within the aforementioned numerical range, when the thermoplastic elastomer composition of this embodiment is formed into a multilayer molded article with a predetermined substrate, the adhesive strength and mechanical strength of the thermoplastic elastomer composition of this embodiment to the substrate resin tend to be good. The content of polymer block A1 can be controlled within the above numerical range by adjusting the amount of monomer added and the polymerization time during the polymerization process of the polymer hydrogenated block copolymer (I).

[0035] The microstructure (cis, trans, and vinyl bond amounts) of polymer blocks B1 and C1 in the polymer hydrogenated block copolymer (I) can be arbitrarily controlled by using modifiers such as polar compounds during the polymerization process of the polymer hydrogenated block copolymer (I). The adjusting agents will be discussed later.

[0036] <Condition (d)> The amount of vinyl bonds in the conjugated diene monomer units before hydrogenation in polymer block B1, which contains vinyl aromatic monomer units and conjugated diene monomer units constituting the polymer hydrogenated block copolymer (I), and polymer block C1, which mainly consists of conjugated diene monomer units, is 25 mol% or more, preferably 30 mol% or more, and more preferably 35 mol% or more. The amount of vinyl bonds in the conjugated diene monomer units in polymer block B1 and polymer block C1 constituting the polymer hydrogenated block copolymer (I) before hydrogenation is 25 mol% or more, which tends to improve the compatibility between the polymer hydrogenated block copolymer (I) and the olefin resin (III) described later, and tends to improve the transparency of the thermoplastic elastomer composition of this embodiment. In this specification, the term "amount of vinyl bonds before hydrogenation" is used because the bonds can no longer be called "vinyl bonds" after hydrogenation. This does not mean that the measurement must be performed on the copolymer before hydrogenation. The bonding mode of conjugated dienes can also be determined from the structure after hydrogenation, so it is possible to calculate the amount of vinyl bonds "before hydrogenation" by examining the structure after hydrogenation.

[0037] In this embodiment, the vinyl bond amount is, for example, in the case of butadiene, the ratio of the total molar amount of conjugated diene monomer units incorporated with 1,2-bonds and 3,4-bonds to the total molar amount of conjugated diene monomer units incorporated with 1,2-bonds, 3,4-bonds and 1,4-bonds before hydrogenation. Furthermore, after hydrogenation, the ratio of the total molar amount of conjugated diene monomer units incorporated with 1,2-bonds before hydrogenation, 1,2-bonds after hydrogenation, 3,4-bonds before hydrogenation, 3,4-bonds after hydrogenation, 1,4-bonds before hydrogenation, and 3,4-bonds after hydrogenation to the total molar amount of conjugated diene monomer units incorporated with 1,2-bonds before hydrogenation, 1,2-bonds after hydrogenation, 3,4-bonds before hydrogenation, 3,4-bonds after hydrogenation, 1,4-bonds before hydrogenation, and 1,4-bonds after hydrogenation is equal to the amount of vinyl bonds in the conjugated diene monomer units before hydrogenation. Therefore, the amount of vinyl bonds in the conjugated diene monomer units before hydrogenation can be measured by nuclear magnetic resonance spectroscopy (NMR) using the block copolymer after hydrogenation, and specifically by the method described in the examples below.

[0038] <Condition (e)> The hydrogenation rate of the aliphatic double bonds derived from the conjugated diene compound in the polymer hydrogenated block copolymer (I), i.e., the double bonds of the conjugated diene monomer unit, is 50 mol% or more and 90 mol% or less, preferably 60 mol% or more and 90 mol% or less, and more preferably 70 mol% or more and 90 mol% or less. By having a hydrogenation rate of 50 mol% or more, the thermoplastic elastomer composition of this embodiment tends to more effectively suppress the deterioration of mechanical properties due to thermal degradation (oxidative degradation). Furthermore, by having a hydrogenation rate of 90 mol% or less, the thermoplastic elastomer composition of this embodiment tends to exhibit high fluidity and excellent heat-sealing properties to the base resin. The hydrogenation rate of the double bonds of the conjugated diene monomer units in the polymer hydrogenated block copolymer (I) can be controlled within the above numerical range by adjusting the type and amount of hydrogenation catalyst used and the hydrogenation conditions, and can be measured by the method described in the examples below.

[0039] By incorporating the organic peroxide described later into the thermoplastic elastomer composition of this embodiment, partial crosslinking becomes possible during the process of melt-kneading the thermoplastic elastomer composition in an extruder. The thermoplastic elastomer composition layer constituting the multilayer molded body of this embodiment, described later, does not necessarily need to be crosslinked, but it may be crosslinked in applications where there is a high demand for suppressing permanent deformation. When partially crosslinking the thermoplastic elastomer composition of this embodiment using an organic peroxide, from the viewpoint of heat resistance, the hydrogenation rate of the aliphatic double bond derived from the conjugated diene compound in the polymer hydrogenated block copolymer (I) must be 50 mol% or more, preferably 60 mol% or more, and more preferably 70 mol% or more. Furthermore, from the viewpoint of processability and crosslinking reactivity, it should be 90 mol% or less, and preferably 85 mol% or less.

[0040] The hydrogenation rate of aromatic double bonds based on vinyl aromatic monomer units in the polymer hydrogenated block copolymer (I) is not particularly limited, but is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0041] <Condition (f)> The weight-average molecular weight Mw of the polymer hydrogenated block copolymer (I) is 150,000 or more and 300,000 or less. Preferably it is 155,000 or more, more preferably 160,000 or more, and even more preferably 165,000 or more. Also preferably 280,000 or less, more preferably 5,260,000 or less, and even more preferably 250,000 or less. When the weight-average molecular weight of the polymer hydrogenated block copolymer (I) is 150,000 or higher, the thermoplastic elastomer composition of this embodiment tends to have good softener retention, heat deformation resistance, and recovery properties. When the weight-average molecular weight of the polymer hydrogenated block copolymer (I) is 300,000 or lower, the thermoplastic elastomer composition of this embodiment exhibits good fluidity and sufficient moldability.

[0042] The molecular weight distribution (Mw / Mn) of the polymer hydrogenated block copolymer (I) is not particularly limited, but is preferably 1.01 to 5.0, more preferably 1.01 to 4.0, and even more preferably 1.01 to 3.0. A molecular weight distribution of polymer hydrogenated block copolymer (I) between 1.01 and 5.0 tends to yield better mechanical strength.

[0043] The shape of the molecular weight distribution curve of a polymer hydrogenated block copolymer (I) measured by gel permeation chromatography (hereinafter sometimes referred to as GPC) is not particularly limited. It may have a polymodal molecular weight distribution with two or more peaks, or a monomodal molecular weight distribution with one peak. Furthermore, the weight-average molecular weight (Mw) and molecular weight distribution [Mw / Mn; ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)] of the polymer hydrogenated block copolymer (I) can be determined based on the molecular weight of the peaks in the chromatogram measured by gel permeation chromatography (GPC) using the method described in the examples below, using a calibration curve obtained from measurements of commercially available standard polystyrene (created using the peak molecular weight of standard polystyrene).

[0044] <Condition (g)> The polymer hydrogenated block copolymer (I) has at least one functional group selected from the group consisting of amino groups, amide groups, hydroxyl groups, acid anhydride groups, epoxy groups, silanol groups, and alkoxysilyl groups in its molecule. Among these, amino groups and amide groups are preferred. The polymer hydrogenated block copolymer (I) more preferably contains 2 moles or more of amino groups and amide groups per mole of its molecule. Because the polymer hydrogenated block copolymer (I) has the aforementioned functional groups, the thermoplastic elastomer composition of this embodiment tends to exhibit excellent adhesion to the base resin. In particular, when the base resin contains polar groups in its molecule, the interaction between these polar groups and the functional groups of the polymer hydrogenated block copolymer (I) tends to increase the adhesive strength.

[0045] The thermoplastic elastomer composition of this embodiment contains one or more polymer hydrogenated block copolymers (I) that satisfy the above-described conditions (a) to (g), and may contain two or more.

[0046] (Non-aromatic softener (II)) The thermoplastic elastomer composition of this embodiment contains a non-aromatic softener (II). The non-aromatic softener (II) is not particularly limited as long as it does not exhibit aromaticity and can soften the thermoplastic elastomer composition of this embodiment; known non-aromatic softeners can be used. The non-aromatic softener (II) is not limited to the following, but examples include paraffinic oils, naphthenic oils, paraffin waxes, liquid paraffin, white mineral oil, and plant-based softeners. Among these, paraffinic oils, liquid paraffin, and white mineral oil are preferred from the viewpoint of low-temperature properties, elution resistance, and hygiene of the molded article containing the thermoplastic elastomer composition of this embodiment. Non-aromatic softeners (II) may be used alone or in combination of two or more types.

[0047] The kinematic viscosity of the non-aromatic softener (II) at 40°C is preferably 10 to 500 mm². 2 The kinematic viscosity of the non-aromatic softener (II) at 40°C is 10 mm² / second. 2 When the kinematic viscosity is 500 mm / second or higher, the heat deformation resistance and softener retention of the thermoplastic elastomer composition of this embodiment tend to be further improved. The kinematic viscosity of the non-aromatic softener (II) at 40°C is 500 mm. 2 By having a value of less than / second, the fluidity of the thermoplastic elastomer composition of this embodiment tends to be further improved, and the moldability tends to be further improved. The kinematic viscosity of non-aromatic softeners (II) can be measured using a glass capillary viscometer.

[0048] In the thermoplastic elastomer composition of this embodiment, the content of the non-aromatic softener (II) is 20 to 400 parts by mass, preferably 35 parts by mass or more, and more preferably 45 parts by mass or more, per 100 parts by mass of the polymer hydrogenated block copolymer (I) described above. The upper limit is 400 parts by mass or less, preferably 370 parts by mass or less, and more preferably 350 parts by mass or less. By having a non-aromatic softener (II) content within the aforementioned numerical range, the retention of the non-aromatic softener (II), i.e., the effect of suppressing bleed-out, can be further improved, and a thermoplastic elastomer composition with superior moldability, flexibility, and recovery properties tends to be obtained.

[0049] (Olefin resin (III)) The thermoplastic elastomer composition of this embodiment contains an olefin resin (III). Examples of olefin resins (III) include, but are not limited to, polyethylene, polypropylene, and ethylene vinyl alcohol (EVA). Among these, polypropylene is preferred from the viewpoint of the heat resistance of the thermoplastic elastomer composition. Olefin resin (III) may be used alone or in combination of two or more types.

[0050] The types of polypropylene are not particularly limited, but examples include homopolypropylene, random polypropylene, and block polypropylene. Homopolypropylene is a polymer composed solely of propylene monomer. In random polypropylene, "random" refers to a copolymer of propylene and monomers other than propylene, in which the monomers other than propylene are randomly incorporated into the propylene chain, and substantially no monomers other than propylene are linked together. Random polypropylene is not particularly limited as long as the propylene unit content is less than 99% by mass. Examples of random polypropylene include random copolymers of propylene and ethylene, or random copolymers of propylene and α-olefins having 4 to 20 carbon atoms. Examples of α-olefins include, but are not limited to, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Preferably, the α-olefin has 2 to 8 carbon atoms, such as ethylene, 1-butene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1-pentene. These α-olefins can be used individually or in combination of two or more. Furthermore, homopolypropylene and random polypropylene can be used individually or in combination of two or more types. Block polypropylene is a type of polypropylene characterized by the formation of a sea-island morphology, where polyethylene is dispersed in homopolypropylene and the interface is covered with ethylene propylene rubber. In other words, block polypropylene is a mixture of propylene homopolymer (homopolypropylene) and propylene-ethylene copolymer. These polypropylene materials may consist of a single type or a mixture of two or more types.

[0051] The olefin resin (III) preferably has a melt flow rate (MFR) of 0.1 to 50 g / 10 min, determined under conditions of a temperature of 230°C and a load of 2.16 kg. The lower limit is more preferably 0.5 g / 10 min or more, and even more preferably 1.0 g / 10 min or more. The upper limit is more preferably 45 g / 10 min or less, and even more preferably 40 g / 10 min or less. If the MFR of the olefin resin (III) is within the above range, the moldability of the thermoplastic elastomer composition of this embodiment tends to improve.

[0052] The method for producing olefin resin (III) is not particularly limited, and conventionally known methods can be applied. When polypropylene is used as the olefin resin (III), the method for producing polypropylene is not limited to the following, but for example, a production method is used in which the above-mentioned monomer is polymerized using a Ziegler-Natta type catalyst that combines a titanium-containing solid transition metal component and an organometallic component. Examples of transition metal components used in Ziegler-Natta type catalysts include, but are not limited to, solid components having titanium, magnesium, and halogens as essential components and electron-donating compounds as optional components, or titanium trichloride. Examples of organometallic components include, but are not limited to, aluminum compounds.

[0053] Furthermore, the polymerization methods used to manufacture polypropylene are not limited to the following, but include, for example, slurry polymerization, gas-phase polymerization, bulk polymerization, solution polymerization, or multi-stage polymerization combining these methods. In these polymerization methods, when obtaining a propylene homopolymer, only propylene is polymerized, and when obtaining a copolymer, propylene and monomers other than propylene are polymerized.

[0054] In the thermoplastic elastomer composition of this embodiment, the content of the olefin resin (III) is 10 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the polymer hydrogenated block copolymer (I). The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 160 parts by mass or less, and more preferably 120 parts by mass or less. When the olefin resin (III) content is 10 parts by mass or more, good fluidity and excellent moldability tend to be obtained in the thermoplastic elastomer composition of this embodiment. When the content of olefin resin (III) is 200 parts by mass or less, the thermoplastic elastomer composition of this embodiment tends to yield good rebound elasticity and flexibility.

[0055] (Hydrogenated block copolymer (IV)) The thermoplastic elastomer composition of this embodiment preferably contains a hydrogenated block copolymer (IV) that satisfies the following conditions (h) to (m). <Condition (h)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A2 mainly composed of vinyl aromatic monomer units and a polymer block C2 mainly composed of conjugated diene monomer units. <Condition (i)> The total vinyl aromatic monomer content is 15% by mass or more and 70% by mass or less. <Condition (j)> The amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 30 moles or more. <Condition (k)> The hydrogenation rate of the double bond in the conjugated diene monomer unit is 50 ml or more. <Condition(l)> The weight-average molecular weight (Mw) is between 30,000 and 150,000. <Condition(m)> The MFR value measured at 230℃ and 2.16kg is 2.0g / 10min or higher.

[0056] <Condition (h)> Hydrogenated block copolymer (IV) is a hydrogenated block copolymer containing vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A2 mainly composed of vinyl aromatic monomer units and a polymer block C2 mainly composed of conjugated diene monomer units.

[0057] The polymer block A2 mainly composed of vinyl aromatic monomer units is a polymer block in which the content of vinyl aromatic monomer units in polymer block A2 exceeds 80% by mass, and from the viewpoint of mechanical strength and heat deformation resistance of the thermoplastic elastomer composition of this embodiment, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0058] The content of polymer block A2, which mainly consists of vinyl aromatic monomer units constituting the hydrogenated block copolymer (IV), is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 60% by mass or less, even more preferably 20% by mass or more and 50% by mass or less, and even more preferably 25% by mass or more and 40% by mass or less, relative to the hydrogenated block copolymer (IV). When the content of polymer block A2 constituting the hydrogenated block copolymer (IV) is within the aforementioned numerical range, the mechanical strength and adhesion to the base resin of the thermoplastic elastomer composition of this embodiment tend to be better. The content of polymer block A2 in the hydrogenated block copolymer (IV) can be controlled within the aforementioned numerical range by adjusting the amount of monomer added and the polymerization time during the polymerization process of the hydrogenated block copolymer (IV).

[0059] Hydrogenated block copolymer (IV) has a polymer block C2 mainly composed of conjugated diene monomer units. The polymer block C2 mainly composed of the conjugated diene monomer units is a polymer block in which the content of conjugated diene monomer units in polymer block C2 exceeds 80% by mass, and from the viewpoint of the flexibility and softener retention of the thermoplastic elastomer composition of this embodiment, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0060] The hydrogenated block copolymer (IV) may further have a polymer block B2 comprising vinyl aromatic monomer units and conjugated diene monomers. The polymer block B2 containing the vinyl aromatic monomer units and conjugated diene monomer units is a polymer block in which the content of vinyl aromatic monomer units in polymer block B2 is 15% by mass or more and 80% by mass or less, and from the viewpoint of the flexibility, softener retention, and adhesion to the base resin of the thermoplastic elastomer composition of this embodiment, it is preferably 15% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 70% by mass or less, even more preferably 15% by mass or more and 65% by mass or less, and even more preferably 15% by mass or more and 60% by mass or less.

[0061] The vinyl aromatic compounds used to form vinyl aromatic monomer units in polymer block A2 and polymer block B2 refer to compounds having a vinyl group and an aromatic ring. Examples of vinyl aromatic compounds include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, styrene, α-methylstyrene, and divinylbenzene are preferred from the viewpoint of polymerizability. These vinyl aromatic compounds may be used individually or in combination of two or more.

[0062] The conjugated diene compound used to form the conjugated diene monomer units in polymer block B2 and polymer block C2 is a diolefin having a pair of conjugated double bonds (two double bonds bonded in a conjugated manner). Examples of conjugated diene compounds include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) are preferred from the viewpoint of polymerizability. These conjugated diene compounds may be used individually or in combination of two or more.

[0063] <Condition (i)> The total vinyl aromatic monomer unit content of the hydrogenated block copolymer (IV) is 15% by mass or more and 70% by mass or less, preferably 20% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 40% by mass or less. When the content of total vinyl aromatic monomer units in the hydrogenated block copolymer (IV) is within the aforementioned numerical range, the transparency of the thermoplastic elastomer composition of this embodiment is further enhanced, and the affinity with the base resin described later is improved, resulting in a tendency to obtain sufficient thermal adhesion strength. The total vinyl aromatic monomer content in the hydrogenated block copolymer (IV) can be controlled to the above-mentioned range by adjusting the amount of monomer added during the polymerization process of the hydrogenated block copolymer (IV), and can be calculated using an ultraviolet spectrophotometer to determine the absorption intensity at a wavelength of 262 nm, as described in the examples below.

[0064] Hydrogenated block copolymer (IV) has a structure that is not limited to the following, but is represented by the following general formula. Furthermore, the hydrogenated block copolymer (IV) may be a mixture containing multiple types of copolymers having a structure represented by the following general formula, in any proportion. (A2-B2) n A2-(B2-A2) n A2-(C2-B2-A2) n , B2-(A2-B2) n (A2-C2) n , C2-(A2-C2) n , C2-(B2-A2) n、 [(B2-A2) n ] m -X, [(A2-B2)] n ] m -X, [(A2-C2)] n ] m -X, [(C2-A2)] n ] m -X, [(B2-A2)] n -B2] m -X, [(A2-B2)] n -A2] m -X, [(A2-C2)] n -A2] m -X, [(A2-B2-C2) n -A2] m -X

[0065] In the above general formula, A2 is a polymer block mainly composed of vinyl aromatic monomer units, B2 is a polymer block containing vinyl aromatic monomer units and conjugated diene monomer units, and C2 is a polymer block mainly composed of conjugated diene monomer units. The boundaries between polymer block A2, polymer block B2, and polymer block C2 do not necessarily need to be clearly distinguishable. Furthermore, n is an integer greater than or equal to 1, preferably an integer between 1 and 5. m is an integer greater than or equal to 2, preferably between 2 and 11, more preferably between 2 and 8. X represents a coupling agent residue. Here, a coupling residue refers to the residue after a coupling agent has been applied to bond multiple copolymers of conjugated diene monomer units and vinyl aromatic monomer units between polymer blocks A2 and A2, polymer blocks B2 and B2, polymer blocks C2 and C2, polymer blocks A2 and B2, and polymer blocks A2 and C2. Examples of coupling agents include, but are not limited to, silicon halide compounds and acid esters, as described later. In the general formula, the vinyl aromatic monomer units in polymer block A2, polymer block B2, and polymer block C2 may be uniformly distributed or tapered in distribution.

[0066] Furthermore, if polymer block A2, polymer block B2, and polymer block C2 are copolymer blocks of vinyl aromatic monomer units and conjugated diene monomer units, there may be multiple portions in the copolymer block where the vinyl aromatic monomer units are uniformly distributed and multiple portions where they are distributed in a tapered manner. In addition, multiple portions with different vinyl aromatic monomer unit content may coexist within the copolymer block.

[0067] <Condition (j)> The hydrogenated block copolymer (IV) has a pre-hydrogenation vinyl bond content of 30 mol% or more in the conjugated diene monomer units in polymer block B2 and polymer block C2. Preferably, it is 35 mol% to 90 mol%, more preferably 40 mol% to 80 mol%, and even more preferably 45 mol% to 75 mol%. When the amount of vinyl bonds in the conjugated diene monomer units in polymer blocks B2 and C2 of the hydrogenated block copolymer (IV) before hydrogenation is 30 mol% or more, the compatibility with the olefin resin (III) described later tends to improve, and the transparency and heat-sealability of the thermoplastic elastomer composition of this embodiment tend to be higher. Furthermore, when the hydrogenated block copolymer (IV) has a relatively small molecular weight and the amount of vinyl bonds is 30 mol% or more, the fluidity of the thermoplastic elastomer composition of this embodiment improves, resulting in good wettability that follows the fine irregularities on the surface of the adherend, and the heat-sealability of the thermoplastic elastomer composition of this embodiment tends to be higher. Furthermore, the fact that the amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 80 mol% or less tends to ensure the mechanical strength of the thermoplastic elastomer composition of this embodiment. The amount of vinyl bonding in a conjugated diene monomer unit can be measured using nuclear magnetic resonance spectroscopy (NMR) analysis with a block copolymer, and specifically, it can be measured by the method described in the examples below. The amount of vinyl bonding can be controlled to the above-mentioned numerical range by adjusting the type and amount of adjusting agents, such as tertiary amines, which will be described later.

[0068] <Condition (k)> The hydrogenation rate of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer (IV) is 50 mol% or more. Preferably it is 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. If the hydrogenation rate of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer (IV) is 50 mol% or more, the thermal degradation, i.e., the decrease in mechanical properties due to oxidative degradation, of the thermoplastic elastomer composition of this embodiment tends to be suppressed. Furthermore, by setting the hydrogenation rate of the double bonds of the conjugated diene monomer units to 50 mol% or more, the SP value becomes close to that of the olefin resin (III), improving the compatibility between the hydrogenated block copolymer (IV) and the olefin resin (III), and tending to yield higher transparency. There is no particular upper limit for the hydrogenation rate of the hydrogenated block copolymer (IV), but it is preferably 100% or less, and more preferably 99% or less. The hydrogenation rate of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer (IV) can be controlled within the aforementioned numerical range by adjusting the type, amount, and hydrogenation conditions of the hydrogenation catalyst, and can be measured by the method described in the examples below.

[0069] The hydrogenation rate of aromatic double bonds based on vinyl aromatic monomer units in the hydrogenated block copolymer (IV) is not particularly limited, but is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0070] <Condition(l)> The weight-average molecular weight of the hydrogenated block copolymer (IV) is between 30,000 and less than 150,000. When the weight-average molecular weight of the hydrogenated block copolymer (IV) is 30,000 or more, the heat deformation resistance and recovery properties of the thermoplastic elastomer composition of this embodiment tend to improve. When the weight-average molecular weight of the hydrogenated block copolymer (IV) is less than 150,000, the fluidity of the thermoplastic elastomer composition of this embodiment tends to improve, and the moldability and heat sealability of the thermoplastic elastomer composition of this embodiment tend to improve. From a similar viewpoint, the weight-average molecular weight of the hydrogenated block copolymer (IV) is preferably 40,000 to 130,000, and more preferably 50,000 to 110,000.

[0071] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (IV) is not limited to the following, but is preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and even more preferably 1.01 to 5.0. Because the molecular weight distribution of the hydrogenated block copolymer (IV) is within the above numerical range, the thermoplastic elastomer composition of this embodiment tends to exhibit better recovery properties. Furthermore, the Mw and Mn of the hydrogenated block copolymer (IV) can be measured by GPC, specifically by the method described in the examples below.

[0072] The shape of the molecular weight distribution curve of the hydrogenated block copolymer (IV) is not particularly limited; it may have a polymodal molecular weight distribution with two or more peaks, or a monomodal molecular weight distribution with one peak.

[0073] <Condition(m)> The melt flow rate (MFR) of the hydrogenated block copolymer (IV), measured at 230°C and 2.16 kg, is 2.0 g / 10 min or higher, preferably 5 g / 10 min or higher, and more preferably 10 g / 10 min or higher. An MFR of 2.0 g / 10 min or higher for the hydrogenated block copolymer (IV) increases the fluidity of the thermoplastic elastomer composition of this embodiment, which tends to improve the molded appearance of injection-molded articles. The upper limit of the MFR of the hydrogenated block copolymer (IV) is not particularly limited, but it is preferably 100 g / 10 min or less from the viewpoint of finishability (handling in the process of processing into pellet shape after polymerization).

[0074] Hydrogenated block copolymer (IV) may have at least one functional group selected from the group consisting of amino groups, amide groups, hydroxyl groups, acid anhydride groups, epoxy groups, silanol groups, and alkoxysilyl groups in its molecule. Among these, amino groups and amide groups are preferred. More preferably, hydrogenated block copolymer (IV) contains 2 moles or more of amino groups and amide groups per mole of its molecule. Because the hydrogenated block copolymer (IV) has the aforementioned functional groups, the thermoplastic elastomer composition of this embodiment tends to exhibit excellent adhesion to the base resin. In particular, when the base resin contains polar groups in its molecule, the interaction between these polar groups and the functional groups of the polymeric hydrogenated block copolymer (I) tends to increase the adhesive strength.

[0075] The thermoplastic elastomer composition of this embodiment preferably contains 50 to 200 parts by mass of hydrogenated block copolymer (IV) per 100 parts by mass of polymer hydrogenated block copolymer (I), more preferably 50 to 180 parts by mass, even more preferably 50 to 160 parts by mass, even more preferably 50 to 130 parts by mass, and particularly preferably 50 to 100 parts by mass. By including 50 parts by mass or more of hydrogenated block copolymer (IV) per 100 parts by mass of polymeric hydrogenated block copolymer (I), the thermoplastic elastomer composition of this embodiment tends to achieve higher transparency and higher heat-sealing strength to the base resin. Furthermore, by including 200 parts by mass or less of hydrogenated block copolymer (IV), the thermoplastic elastomer composition of this embodiment tends to have higher fluidity and good moldability. In addition, the heat deformation resistance of the thermoplastic elastomer composition of this embodiment tends to improve.

[0076] (Method for producing high polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV)) The methods for producing polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) are not limited to the following, but include, for example, the methods described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 51-49567, Japanese Patent Publication No. 59-166518, etc.

[0077] The polymer hydrogenated block copolymers (I) and hydrogenated block copolymers (IV), which include conjugated diene monomer units and vinyl aromatic monomer units before hydrogenation, are not limited to the following but can be obtained, for example, by anionic living polymerization using a polymerization initiator such as an organoalkali metal compound in a hydrocarbon solvent.

[0078] Examples of hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0079] While there are no particular limitations on the polymerization initiator, organoalkali metal compounds known to exhibit anionic polymerization activity towards conjugated diene compounds and vinyl aromatic compounds can generally be used. Examples of the aforementioned organic alkali metal compounds include, but are not limited to, aliphatic hydrocarbon alkali metal compounds having 1 to 20 carbon atoms, aromatic hydrocarbon alkali metal compounds having 1 to 20 carbon atoms, and organic amino alkali metal compounds having 1 to 20 carbon atoms. The alkali metals included in the polymerization initiator are not limited to those listed below, but examples include lithium, sodium, potassium, etc. Note that one or more alkali metals may be present in a single molecule.

[0080] Polymerization initiators include, but are not limited to, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, reaction products of diisopropenylbenzene and sec-butyllithium, and reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene. Furthermore, lithium compounds containing 1-(t-butoxy)propyllithium and a few isoprene monomers inserted therein to improve solubility, as disclosed in U.S. Patent No. 5,708,092, siloxy group-containing alkyllithiums such as 1-(t-butyldimethylsiloxy)hexyllithium disclosed in British Patent No. 2,241,239, amino group-containing alkyllithiums disclosed in U.S. Patent No. 5,527,753, diisopropylamide lithium, and hexamethyldisilazidolithium, among other aminolithium compounds, can also be used as polymerization initiators.

[0081] When copolymerizing a conjugated diene compound and a vinyl aromatic compound using an organoalkali metal compound as a polymerization initiator, tertiary amine compounds, ether compounds, and metal alkoxide compounds can be added as modifiers to adjust the content of vinyl bonds (1,2- or 3,4- bonds) originating from the conjugated diene compound incorporated into the copolymer, and to adjust the random copolymerization properties between the conjugated diene compound and the vinyl aromatic compound. Adjusting agents may be used individually or in combination of two or more.

[0082] As for tertiary amine compounds used as regulators, the general formula is R 1 R 2 R 3 A compound represented by N can be used. Here, in the general formula, R 1 , R 2 , R 3 This indicates a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group. Examples of tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N”,N”-pentamethylethylenetriamine, and N,N'-dioctyl-p-phenylenediamine.

[0083] As the adjusting agent, linear ether compounds and cyclic ether compounds can be used. Examples of linear ether compounds include, but are not limited to, dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and other ethylene glycol dialkyl ether compounds, as well as diethylene glycol dialkyl ether compounds, such as diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and other diethylene glycol dialkyl ether compounds. Examples of cyclic ether compounds include, but are not limited to, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers of furfuryl alcohol.

[0084] Examples of metal alkoxide compounds used as modifiers include, but are not limited to, sodium t-pentoxide, sodium t-butoxide, potassium t-pentoxide, potassium t-butoxide, and the like.

[0085] The copolymerization method for conjugated diene compounds and vinyl aromatic compounds using an organoalkali metal compound as a polymerization initiator is not particularly limited and may be batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of adjusting the molecular weight distribution to a desirable and appropriate range, a batch polymerization method is preferred. The polymerization temperature is not particularly limited, but is usually 0 to 180°C, and preferably 30 to 150°C. The time required for polymerization varies depending on the conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. Furthermore, polymerization is preferably carried out under an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited and should be within a range sufficient to maintain the monomer and solvent in the liquid phase within the polymerization temperature range mentioned above.

[0086] Furthermore, a coupling reaction may be carried out by adding the necessary amount of a coupling agent with two or more functional groups at the end of polymerization. The coupling agent with two or more functional groups is not particularly limited, and known ones can be used. Examples of difunctional coupling agents include, but are not limited to, alkylalkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, silicon halide compounds such as dimethyldichlorosilane and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0087] Polyfunctional coupling agents with three or more functional groups are not limited to the following, but include, for example, polyalcohols with three or more valent groups, polyvalent epoxy compounds such as epoxidized soybean oil and diglycidylbisphenol A, alkylalkoxysilanes such as methyltrimethoxysilane, tetramethoxysilane, methyltriethoxysilane, and tetraethoxysilane, and those with the general formula R 1 (4-n) SiX n Examples of silicon halide compounds represented by [formula] include [formula]. Here, in the general formula, R 1 represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 or 4. Examples of silicon halide compounds include, but are not limited to, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and their brominated products.

[0088] The hydrogenation catalyst used to produce polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) is not particularly limited, and for example, hydrogenation catalysts described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-9041, etc., can be used. Preferred hydrogenation catalysts include titanocene compounds and mixtures of the titanocene compound with a reducing organometallic compound. The titanocene compounds are not particularly limited, but examples include the compounds described in Japanese Patent Publication No. 8-109219. Specifically, examples include compounds having at least one ligand having a substituted or unsubstituted cyclopentadienyl structure, an indenyl structure, and a fluorenyl structure, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Reducing organometallic compounds include, but are not limited to, organolithium and other organoalkali metal compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, organozinc compounds, and the like.

[0089] The reaction temperature for hydrogenation is typically 0 to 200°C, preferably 30 to 150°C. The pressure of the hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa. The reaction time for hydrogenation is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. Furthermore, the hydrogenation reaction can be carried out using a batch process, a continuous process, or a combination of both.

[0090] After the hydrogenation reaction is complete, catalyst residue may be removed from the reaction solution as needed. Methods for separating the hydrogenated block copolymer from the solvent include, but are not limited to, adding a polar solvent that is a poor solvent for the hydrogenated block copolymer, such as acetone or alcohol, to a solution of the hydrogenated block copolymer to precipitate and recover the hydrogenated block copolymer; adding a solution of the hydrogenated block copolymer to hot water under stirring and removing the solvent by steam stripping; or directly heating a solution of the hydrogenated block copolymer to remove the solvent by distillation.

[0091] Antioxidants may be added to the reaction solutions used to produce polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV). Antioxidants include, but are not limited to, phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like.

[0092] The aforementioned antioxidants are not limited to the following, but include, for example, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-butylidene-bis-(3-methyl-6-t-butylphenol), 3,9-bis[2-{3-(3-t-butyl [Tyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)1,3,5-triazine, pentaerythritol Tyl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t- A mixture of ethyl butyl-4-hydroxybenzylphosphonate and polyethylene wax (50%), octylated diphenylamine, 2,4-bis[(octylthio)methyl]-o-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, butyric acid, 3,3-bis(3-t-butyl-4-hydroxyphenyl)ethylene ester, 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,Examples include 6-dimethylbenzyl isocyanurate, 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, and 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)-ethyl]-4,6-di-t-pentylphenyl acrylate.

[0093] <Method for modifying polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV)> As described above, the polymer hydrogenated block copolymer (I) has at least one functional group selected from the group consisting of amino groups, amide groups, hydroxyl groups, acid anhydride groups, epoxy groups, silanol groups, and alkoxysilyl groups in its molecule. Furthermore, it is preferable that the hydrogenated block copolymer (IV) has at least one functional group selected from the group consisting of an amino group, a hydroxyl group, an acid anhydride group, a silanol group, and an alkoxysilyl group in its molecule. The polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) are not limited to the functional group described above, but may also be modified hydrogenated block copolymers to which atomic groups having functional groups are bonded. It is preferable to bond the atomic groups having functional groups as a step before the hydrogenation step described later. Examples of the "atomic group having a functional group" include an atomic group containing at least one functional group selected from hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxysilicon group, tin halide group, boronic acid group, boron-containing group, boronic acid base, alkoxytin group, phenyltin group, and the like. In particular, atomic groups having at least one functional group selected from hydroxyl groups, epoxy groups, amino groups, amide groups, silanol groups, and alkoxysilane groups are preferred. The aforementioned "atomic group having a functional group" can be bonded by a denaturing agent.

[0094] Examples of denaturing agents include, but are not limited to, tetraglycidylmetoxylendiamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.

[0095] The modified hydrogenated block copolymer can be obtained, for example, by anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group, or by an addition reaction with a modifying agent that forms or contains a functional group at the living end. Another method involves reacting a block copolymer with an organolithium compound or other organolalkali metal compound (metallation reaction), and then adding a functional modifier to the block polymer to which the organolalkali metal has been added. In the latter method, a modified hydrogenated block copolymer can also be produced by first obtaining a hydrogenated block copolymer, then subjecting it to a metallation reaction, and finally reacting it with a modifying agent. The temperature at which the denaturation reaction is carried out is preferably 0 to 150°C, and more preferably 20 to 120°C. The time required for the denaturation reaction varies depending on other conditions, but is preferably within 24 hours, and more preferably 0.1 to 10 hours. Depending on the type of denaturing agent used, amino groups may generally be converted into organometallic salts at the stage of reaction with the denaturing agent. In such cases, they can be converted back to amino groups by treatment with a compound containing active hydrogen, such as water or alcohol. Furthermore, in such modified hydrogenated block copolymers, some unmodified hydrogenated block copolymers may be present.

[0096] Furthermore, the modified hydrogenated block copolymer described above may also be a secondary modified hydrogenated block copolymer. Secondary modified hydrogenated block copolymers are obtained by reacting a modified hydrogenated block copolymer with a secondary modifying agent that is reactive with the functional groups of the modified hydrogenated block copolymer. Examples of secondary modifying agents include, but are not limited to, modifying agents having functional groups selected from carboxyl groups, acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilane groups, and having at least two functional groups selected from these functional groups. However, if the functional group is an acid anhydride group, it may have one acid anhydride group.

[0097] As described above, when a secondary modifier is further reacted with a modified hydrogenated block copolymer, the amount of secondary modifier used per equivalent of functional groups bonded to the modified hydrogenated block copolymer is preferably 0.3 to 10 moles, more preferably 0.4 to 5 moles, and even more preferably 0.5 to 4 moles. The method for reacting the modified block copolymer with the secondary modifier is not particularly limited and any known method can be applied. For example, this could be the melt-kneading method described later, or a method in which each component is dissolved or dispersed in a solvent and mixed before reaction. It is preferable to carry out these secondary modifications after the hydrogenation step.

[0098] Suitable secondary modifiers include, but are not limited to, maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, and bis-(3-triethoxysilylpropyl)-tetrasulfan.

[0099] Furthermore, polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) can be modified hydrogenated block copolymers obtained by graft modification with α,β-unsaturated carboxylic acids or their derivatives, such as their anhydrides, esters, amids, or imids. Examples of α,β-unsaturated carboxylic acids or their derivatives include, but are not limited to, maleic anhydride, maleimide anhydride, acrylic acid or its esters, methacrylic acid or its esters, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydride. The amount of α,β-unsaturated carboxylic acid or its derivative added is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV). The reaction temperature for graft modification is preferably 100 to 300°C, and more preferably 120 to 280°C. As a specific method for graft modification, for example, the method described in Japanese Patent Publication No. 62-79211 can be applied.

[0100] (Inorganic fillers) The thermoplastic elastomer composition of this embodiment may contain inorganic fillers from the viewpoint of adjusting the molded appearance, surface texture, feel, and gloss.

[0101] Examples of inorganic fillers include, but are not limited to, talc, calcium carbonate, calcium oxide, zinc carbonate, wollastonite, zeolite, wollastonite, silica, alumina, clay, titanium dioxide, magnesium hydroxide, magnesium oxide, sodium silicate, calcium silicate, magnesium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, zinc oxide, potassium titanate, hydrotalcite, barium sulfate, titanium black, etc., as well as carbon blacks such as furnace black, thermal black, and acetylene black. These inorganic fillers may be used individually or in combination of two or more types. Furthermore, these inorganic fillers may be surface-treated to improve their dispersibility in the thermoplastic elastomer composition of this embodiment. Examples of surface treatment agents include fatty acids, resin acids, oils and fats, surfactants, and coupling agents (silane-based, titanium-based, phosphoric acid-based, carboxylic acid-based, etc.), but are not limited to these as long as they can act on the surface of the inorganic filler.

[0102] (organic peroxide) The thermoplastic elastomer composition of this embodiment may be partially crosslinked in the presence of an organic peroxide from the viewpoint of heat deformation resistance and recovery properties. Organic peroxides include, but are not limited to, the following: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxybenzoate, t-butylcumyl peroxide, diisopropylbenzene hydroxyperoxide, 1,3-bis(t-butylperoxyisopropyl)benzene, benzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexa Examples include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, 1,1-di-t-butylperoxycyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyn-3, n-butyl-4,4-bis(t-butylperoxy)valerate, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropylcarbonate. These may be used individually or in combination of two or more organic peroxides. The amount of organic peroxide used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and even more preferably 0.3 to 3 parts by mass, per 100 parts by mass of polymer hydrogenated block copolymer (I). If the amount of organic peroxide used is within the aforementioned numerical range, a thermoplastic elastomer composition with superior heat deformation resistance and recovery properties tends to be obtained without reducing processability.

[0103] (Cross-linking agent) Furthermore, when partially crosslinking the thermoplastic elastomer composition of this embodiment, a crosslinking aid can be used as needed to adjust the degree of crosslinking. Examples of crosslinking aids include, but are not limited to, trimethylolpropane triacrylate, triallyl isocyanurate, triallyl cyanurate, triallyl formal, triallyl trimellitate, N,N'-m-phenylene bismaleimide, dipropagyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, divinylbenzene, ethylene dimethacrylate, diallyl phthalate, quinone dioxime, ethylene glycol dimethacrylate, polyfunctional methacrylate monomers, polyhydric alcohol methacrylates and acrylates, and unsaturated silane compounds (e.g., vinyltrimethoxysilane, vinyltriethoxysilane, etc.). These can be used individually or in combination of two or more as needed. The amount of crosslinking aid used is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of polymer hydrogenated block copolymer (I). The preferred upper limit is 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less.

[0104] (Other ingredients) The thermoplastic elastomer composition of this embodiment may also contain other rubbery polymers or additives in addition to the components described above, as long as the purpose of this embodiment is not impaired.

[0105] Other rubbery polymers include butadiene rubber and its hydrogenated derivatives, styrene-butadiene rubber and its hydrogenated derivatives (however, different from the hydrogenated block copolymer of this embodiment), isoprene rubber, acrylonitrile-butadiene rubber and its hydrogenated derivatives, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethien-hexene rubber, ethylene-octene rubber and other olefin-based elastomers, butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α,β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and its hydrogenated derivatives, styrene-isoprene block copolymer and its hydrogenated derivatives and other styrene-based elastomers, natural rubber, and the like. These rubbery polymers may also be modified rubbers to which functional groups have been added. Other rubbery polymers that are particularly preferred include styrene-based elastomers and olefin-based elastomers.

[0106] Other additives include heat stabilizers, antioxidants, UV absorbers, anti-aging agents, plasticizers, light stabilizers, crystal nucleating agents, impact modifiers, pigments, lubricants, antistatic agents, flame retardants, flame retardant aids, compatibilizers, and tackifiers. In particular, adding silicone oil as a lubricant tends to improve scratch resistance and result in molded products with a non-sticky texture. Examples of silicone oils include common dimethylpolysiloxane and phenylmethylpolysiloxane, with dimethylpolysiloxane being particularly preferred. The amount of silicone oil to be added is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of polymer hydrogenated block copolymer (I). The upper limit is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less. There are no particular restrictions on the kinematic viscosity of the silicone oil, but 10 to 10,000 mm is recommended. 2A speed of 50-7000mm / second is preferred. 2 / second is more preferable, 100-5000mm 2 / second is even more preferable. The aforementioned other additives may be used individually or in combination of two or more.

[0107] [Method for producing thermoplastic elastomer compositions] The thermoplastic elastomer composition of this embodiment and the method for producing a molded article (e.g., pellets) made from the thermoplastic elastomer composition are not particularly limited, and conventionally known methods can be applied. Examples include melt-kneading methods using common mixers such as pressure kneaders, Banbury mixers, internal mixers, Laboplast mills, Mixlabs, single-screw extruders, twin-screw extruders, Conkneaders, and multi-screw extruders, as well as methods in which each component is dissolved or dispersed and mixed, and then the solvent is removed by heating.

[0108] When partially crosslinking the thermoplastic elastomer composition of this embodiment with the organic peroxide described above, the compounding of each component and partial crosslinking with the organic peroxide and, if necessary, a crosslinking aid may be performed simultaneously, or the organic peroxide and, if necessary, a crosslinking aid may be added after the compounding of each component to perform partial crosslinking. Alternatively, some of the components may be mixed with organic peroxides and, if necessary, crosslinking aids, and then the other components may be mixed after crosslinking. Partial crosslinking can be carried out under temperature conditions where the decomposition of the organic peroxide used occurs, generally between 150 and 250°C. When compounding some or all of the components and crosslinking with organic peroxides and crosslinking aids added as needed is performed simultaneously, compounding can be achieved by using the aforementioned melt kneader at a temperature at which the decomposition of the organic peroxides used occurs.

[0109] [Physical properties of thermoplastic elastomer compositions] (MFR of thermoplastic elastomer compositions) The MFR of the thermoplastic elastomer composition of this embodiment, measured at 230°C and 2.16 kg, is preferably 70 g / 10 min or more, more preferably 80 g / 10 min or more, and even more preferably 90 g / 10 min or more, from the viewpoint of improving the appearance of the injection molded product. While there is no upper limit, it is preferable that the amount be 150 g / 10 min or less from the viewpoint of the extrusion processability of the thermoplastic elastomer composition of this embodiment. Thermoplastic elastomer compositions in which the MFR is within the aforementioned numerical range can be obtained by adjusting the molecular weight, vinyl bond content, and hydrogenation rate of polymer hydrogenated block copolymers (I) and (IV) within an optimal range and blending them in an appropriate ratio, as well as by selecting an optimal non-aromatic softener (II) and olefin resin (III) and blending them in an optimal ratio.

[0110] [Multilayer molded body] The multilayer molded body of this embodiment has a layer L1 of the thermoplastic elastomer composition of this embodiment and a thermoplastic resin substrate layer L2.

[0111] The multilayer molded article of this embodiment may also be a multilayer molded article having a thermoplastic resin base layer L2 and a layer L1 of the thermoplastic elastomer composition of this embodiment containing the above-mentioned polymer hydrogenated block copolymer (I), non-aromatic softener (II), and olefin resin (III), preferably hydrogenated block copolymer (IV). The layer L1 of the thermoplastic elastomer composition may be provided in contact with the thermoplastic resin substrate layer L2.

[0112] (Thermoplastic resin base material L2) As described above, the multilayer laminate of this embodiment has a thermoplastic resin substrate layer L2. The thermoplastic resin that constitutes the thermoplastic resin substrate layer L2 is a resin that softens and exhibits plasticity upon heating without undergoing any reaction (such as crosslinking or curing), allowing it to be molded, but solidifies upon cooling, and maintains its plasticity reversibly when the cooling and heating cycles are repeated.

[0113] The thermoplastic resin constituting the thermoplastic resin substrate L2 is not particularly limited as long as it is a commonly used type, but for example, at least one selected from the group consisting of olefin resins, styrene resins, polycarbonate, polyester, acrylic resins, polyamides, and mixtures thereof can be used.

[0114] Examples of the thermoplastic resins include ionomer resins, ethylene-ethyl acrylate copolymer resins, acrylonitrile-styrene-acrylate copolymer resins, acrylonitrile-styrene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, acrylonitrile-chlorinated polyethylene-styrene copolymer resins, acrylonitrile-ethylene-propylene-diene-styrene copolymer resins, silicone-based composite rubber-acrylonitrile-styrene copolymer resins, polyvinyl chloride / acrylonitrile-butadiene-styrene resins, polyamide / acrylonitrile-butadiene-styrene resins, polycarbonate / acrylonitrile-butadiene-styrene resins, polycarbonate / acrylonitrile-ethylene-propylene-diene-styrene resins, polymethyl methacrylate / acrylonitrile-butadiene-styrene / acrylonitrile-styrene resins, and the like.

[0115] In addition, vinyl chloride resin, chlorinated polyethylene, acetate cellulose resin, fluororesin, polyacetal resin, polyamide resin, polyarylate resin, thermoplastic polyurethane, polyether block amide copolymer resin, polyphenylene ether / polystyrene resin, polypropylene / ethylene-propylene-diene resin, vinyl chloride-nitrile elastomer, liquid crystal resin, polyether ether ketone resin, polysulfone resin, polyethersulfone resin, high-density polyethylene resin Low-density polyethylene resin, linear low-density polyethylene resin, polyethylene terephthalate resin, polyethylene terephthalate / polycarbonate resin, polyethylene terephthalate / polybutylene terephthalate resin, polycarbonate resin, polycarbonate / acrylonitrile-butadiene-styrene resin, polycarbonate / polyethylene terephthalate resin, polycarbonate / polybutylene terephthalate resin, polycarbonate / polyester resin, polycarbonate / polystyrene resin, polycarbonate / methyl-butadiene-styrene methacrylate resin, polycarbonate / polymethyl methacrylate resin, polycarbonate / high-impact polystyrene resin, methyl methacrylate-styrene Copolymer resins, polyphenylene ether resins, polyphenylene sulfide resins, polybutylene terephthalate resins, polybutylene terephthalate / acrylonitrile-styrene-acrylate resins, polybutylene terephthalate / polycarbonate resins, polypropylene resins, methacrylic resins, methylpentene resins, biodegradable resins, biomass resins, plant-derived polyamide resins, polylactic acid / acrylonitrile-butadiene-styrene resins, ethylene-butyl acrylate copolymer resins, ethylene-acrylic acid ester-glycidyl acrylate copolymer resins, ethylene-acrylic acid ester-maleic anhydride copolymer resins, polyolefin-maleic anhydride graft polymerization resins, copolyester resins, syndiotactic polystyrene resins, polyetherimide, thermoplastic polyimide resins, siloxane-modified polyetherimide resins, ethylene-methyl methacrylate copolymer resins, ethylene-glycidyl methacrylate copolymer resins, polycyclohexyleneExamples include methylene terephthalate resin, polyamide-imide resin, polyethylene naphthalate resin, polybutylene naphthalate resin, ethylene-vinyl acetate copolymer resin, polybutylene terephthalate resin, cycloolefin resin, cycloolefin copolymer, ethylene-(meth)acrylate methyl copolymer, polyetherketone, etherketone, ketone resin, and polyallyl etherketone resin.

[0116] Furthermore, polyvinyl chloride / acrylonitrile-butadiene-styrene resin, polyamide / acrylonitrile-butadiene-styrene resin, polycarbonate / acrylonitrile-butadi Examples include polystyrene resin, polycarbonate / acrylonitrile-ethylene-propylene-diene-styrene resin, polymethyl methacrylate / acrylonitrile-butadiene-styrene / acrylonitrile-styrene resin, polypropylene / ethylene-propylene-diene resin, polyethylene terephthalate / polycarbonate resin, polyethylene terephthalate / polybutylene terephthalate resin, polycarbonate / polybutylene terephthalate resin, polycarbonate / polybutylene terephthalate resin, polycarbonate / polypolycarbonate resin, polycarbonate / polypolystyrene resin, polycarbonate / methyl methacrylate-butadiene-styrene resin, polycarbonate / polymethyl methacrylate resin, polycarbonate / high-impact polystyrene resin, polybutylene terephthalate / acrylonitrile-styrene-acrylate resin, polybutylene terephthalate / polycarbonate resin, and polylactic acid / acrylonitrile-butadiene-styrene resin. In the above resins, the parts separated by a slash ( / ) indicate a mixture of two or more resins. These resins are available commercially.

[0117] Among these, preferred resins for the thermoplastic resin substrate layer L2 include olefin resins such as polypropylene resin, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and ethylene vinyl acetate; styrene resins such as polystyrene resin, syndiotactic polystyrene resin, acrylonitrile / styrene copolymer (AS resin), and acrylonitrile / butadiene / styrene copolymer (ABS resin); polyester resins such as polyethylene terephthalate and polybutylene terephthalate; acrylic resins such as polymethyl methacrylate; and polycarbonate and polyamide.

[0118] (Applications of multilayer molded products) The multilayer molded body of this embodiment can be suitably used in applications such as sealing members requiring flexibility and resilience, grips requiring a good fit and appropriate tactile feel when held by a person, and impact protection when it comes into contact with or collides with the human body or other objects, in home appliance parts, industrial goods, automobile parts and their interior materials, medical instruments and medical devices, building materials, tools, toys, general merchandise, etc. Furthermore, the molded articles of the thermoplastic elastomer composition of this embodiment are highly transparent and can be applied to components where visibility and design aesthetics are required.

[0119] (Method for manufacturing multilayer molded bodies) A method for manufacturing a multilayer molded article according to this embodiment includes the steps of: molding a thermoplastic resin for the thermoplastic resin base layer L2 to obtain a molded article; and placing the obtained molded article into a mold, injecting the thermoplastic elastomer composition of this embodiment into the gap between the mold and the molded article, and heat-sealing it to form a layer L1 of the thermoplastic elastomer composition. Generally, a preferred method involves producing a molded body constituting the thermoplastic resin base layer L2, inserting the molded body into a mold, and filling the gaps in the mold with pellets of the thermoplastic elastomer composition of this embodiment and heat-sealing them. Furthermore, a preferred method for manufacturing the multilayer molded article of this embodiment is an insert molding method, which involves first molding a thermoplastic resin molded article constituting the thermoplastic resin base layer L2, then fitting it into another mold, injecting the thermoplastic elastomer composition of this embodiment into the gap, and heat-sealing it. Furthermore, a two-color molding method is also preferred, in which a single injection molding machine has a configuration with two or more cylinders, in which a thermoplastic resin is first molded, and then a part of the mold is changed to create a gap between the thermoplastic resin and the mold, and the thermoplastic elastomer composition of this embodiment is injected into this gap from another cylinder. The multilayer molded article of this embodiment, having a layer L1 of the thermoplastic elastomer composition and a thermoplastic resin substrate layer L2, can be manufactured by any molding method. The molding temperature is not particularly limited, but 150°C to 280°C is preferred. [Examples]

[0120] The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited in any way by the following examples and comparative examples. First, the evaluation methods and physical property measurement methods applied to the examples and comparative examples are shown below. In the following examples, "high polymer hydrogenated block copolymer (I)" may be written as "hydrogenated block copolymer (I)".

[0121] [Method for measuring the physical properties of polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV)] ((1) Weight average molecular weight, number average molecular weight, molecular weight distribution) The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) were determined based on the molecular weight of the peaks in the chromatogram, using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from measurements of commercially available standard polystyrene. For measurement, we used HLC-8320ECOSEC acquisition software, and for analysis, we used HLC-8320ECOSEC analysis software. (Measurement conditions) GPC; HLC-8320GPC (manufactured by Tosoh Corporation) Detector; RI Detection sensitivity: 3 MV / min Sampling pitch: 600 MSEC Columns: TSKGEL SUPERHZM-N (6MMI.D x 15CM) 4 pieces (manufactured by Tosoh Corporation) Solvent; THF Flow rate ;0.6ML / min Concentration ;0.5MG / ML Column temperature: 40°C Injection volume: 20ML

[0122] ((2) Total vinyl aromatic monomer content (total styrene content)) A certain amount of polymeric hydrogenated block copolymer and hydrogenated block copolymer were dissolved in chloroform and measured using an ultraviolet spectrophotometer (Shimadzu Corporation, UV-2450). The styrene content was calculated using a calibration curve based on the peak intensity at the absorption wavelength (262 nm) at which styrene was responsible.

[0123] (3) Content of polystyrene blocks A1 and A2 constituting polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) Using block copolymers before hydrogenation, the content of polystyrene blocks A1 and A2 constituting polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) was measured using nuclear magnetic resonance (NMR) spectroscopy (as described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereafter referred to as "NMR method").

[0124] (4) Content of copolymer blocks B1 and B2 constituting polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV), and content of vinyl aromatic monomer units in B1 and B2) Using the block copolymer before hydrogenation, the content (mass%) of copolymer blocks B1 and B2, which have aromatic vinyl monomer units and conjugated diene monomer units, and the content (mass%) within B1 and B2 were measured by the same NMR method as described above.

[0125] ((5) Amount of vinyl binding) The amount of vinyl bonds in the polybutadiene block constituting the block copolymer before hydrogenation was measured using nuclear magnetic resonance (NMR) under the following conditions. In the table below, B1 or B2 indicates a polybutadiene block. The block copolymer was precipitated and recovered by adding a large amount of methanol to the reaction solution after the polymerization reaction was complete. Next, the block copolymer is extracted with acetone, and the extract is vacuum-dried. 1 Used as a sample for H-NMR measurement. 1 The conditions for H-NMR measurement are described below. (Measurement conditions) Measuring instrument: JNM-LA400 (manufactured by JEOL) Solvent: Deuterated chloroform Sample concentration: 50 mg / ml Observation frequency: 400MHz Chemical shift standard: TMS (tetramethylsilane) Pulse delay: 2.904 seconds Number of scans: 64 Pulse width: 45° Measurement temperature: 26℃ The amount of vinyl bond was determined by the ratio of the total area of ​​the 1,2-bond and 3,4-bond peaks to the total area of ​​all peaks related to conjugated diene monomer units (1,2-bond, 3,4-bond, 1,4-bond) in the obtained peaks.

[0126] (6) Hydrogenation rate The hydrogenation rate of double bonds in conjugated diene monomer units in block copolymers was measured using nuclear magnetic resonance (NMR) under the same conditions as described above for (5) vinyl bond amount. The hydrogenation rate was determined by calculating the ratio of the total area of ​​the hydrogenated 1,2-bond, hydrogenated 3,4-bond, and hydrogenated 1,4-bond peaks to the total area of ​​all peaks related to double bonds in the conjugated diene monomer unit (1,2-bond, 3,4-bond, 1,4-bond) in the obtained peaks.

[0127] ((7) Content of polymer blocks C1 and C2 constituting polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV)) The content of polymer blocks C1 and C2 in the block copolymer was determined by the amount of monomer added during production and by confirming the polymerization reaction rate of each block using gas chromatography (GC). <Confirmation of polymerization reaction rates of each polymer block in block copolymers> Samples were prepared by sampling polymer solutions at each step of the polymerization process of the block copolymer before hydrogenation, and then adding approximately 20 mL of each sample to a sealed 100 mL bottle containing 0.50 mL of n-propylbenzene and approximately 20 mL of toluene as internal standards. The sample was measured using a gas chromatograph (Shimadzu Corporation: GC-14B) equipped with a backed column supported with apiezon grease. The amount of residual monomer in the polymer solution was determined from the calibration curves for butadiene monomer and styrene monomer obtained in advance, and it was confirmed that the polymerization rate of butadiene monomer and styrene monomer was 100%. The polymerization rate of butadiene was measured at a constant temperature of 90°C, while the polymerization rate of styrene was measured under conditions of heating from 90°C (hold for 10 minutes) to 150°C (10°C / min).

[0128] (8) Confirmation of mutated species Using a block copolymer sample after hydrogenation, 1 ¹H-NMR measurements were performed, and the spectra of the modified copolymer were compared with those of known individuals. A nuclear magnetic resonance spectrometer (ECS400, JEOL RESONANCE) was used for the measurements.

[0129] (9) Melt Flow Rate (hereinafter also referred to as MFR, unit: g / 10 min) MFR measurements were performed in accordance with JIS K7210, under conditions of a temperature of 230°C and a load of 2.16 kg.

[0130] [Production of High Polymer Hydrogenated Block Copolymer (I) and Hydrogenated Block Copolymer (IV)] The following describes in detail the preparation of polymer hydrogenated block copolymers (I) and hydrogenated block copolymers (IV) used in thermoplastic elastomer compositions.

[0131] (Preparation of hydrogenated catalyst) The hydrogenation catalyst used in the preparation of polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV), described later, was prepared by the following method. A reaction vessel equipped with a stirring device was purged with nitrogen, and 1 liter of dried and purified cyclohexane was charged into it. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While stirring thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for approximately 3 days to obtain a hydrogenated catalyst.

[0132] (Preparation of polymer hydrogenated block copolymer (I)) <Manufacturing Example 1: High Polymer Hydrogenated Block Copolymer (I)-1> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 15.4 mL of n-butyllithium (2.4 mol / L), 1.4 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.5 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Subsequently, 1.6 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 45% by mass in the block copolymer, and a weight-average molecular weight of 180,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated polymeric hydrogenated block copolymer (I)-1. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-1 was 75 ml.

[0133] <Manufacturing Example 2: High Polymer Hydrogenated Block Copolymer (I)-2> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 9 parts by mass of styrene was added. Next, 14.2 mL of n-butyllithium (2.4 mol / L), 0.7 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.4 mL of sodium t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 5 minutes. Next, a cyclohexane solution (20% by mass) containing 21 parts by mass of styrene and 61 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 9 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. After that, 1.3 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was carried out. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 39% by mass, a polystyrene block content of 18% by mass, a total vinyl bond content of 35% by mass in the block copolymer, and a weight-average molecular weight of 220,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated polymeric hydrogenated block copolymer (I)-2. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-2 was 65 ml.

[0134] <Manufacturing Example 3: High Polymer Hydrogenated Block Copolymer (I)-3> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 14.4 mL of n-butyllithium (2.4 mol / L), 0.7 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.4 mL of sodium t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 8 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Subsequently, 1.4 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a total vinyl bond content of 32% by mass in the block copolymer, and a weight-average molecular weight of 210,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated polymeric hydrogenated block copolymer (I)-3. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-3 was 64 ml.

[0135] <Manufacturing Example 4: High Polymer Hydrogenated Block Copolymer (I)-4> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 17 parts by mass of styrene was added. Next, 13.7 mL of n-butyllithium (2.4 mol / L), 0.6 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 17 parts by mass of styrene and 49 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Then, a cyclohexane solution (20% by mass) containing 17 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. Subsequently, 1.2 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 51% by mass, a polystyrene block content of 34% by mass, a total vinyl bond content of 32% by mass in the block copolymer, and a weight-average molecular weight of 240,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated polymeric hydrogenated block copolymer (I)-4. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-4 was 68 ml.

[0136] <Manufacturing Example 5: High Polymer Hydrogenated Block Copolymer (I)-5> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 20 parts by mass of styrene was added. Next, 14.2 mL of n-butyllithium (2.4 mol / L), 0.6 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene and 45 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Then, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. Subsequently, 1.3 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 55% by mass, a polystyrene block content of 40% by mass, a total vinyl bond content of 33% by mass in the block copolymer, and a weight-average molecular weight of 220,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated polymeric hydrogenated block copolymer (I)-5. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-5 was 66 ml.

[0137] <Manufacturing Example 6: High Polymer Hydrogenated Block Copolymer (I)-6> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 14.4 mL of n-butyllithium (2.4 mol / L), 0.7 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Then, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a total vinyl bond content of 33% by mass in the block copolymer, and a weight-average molecular weight of 210,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass per 100 parts by mass of the block copolymer. 100 parts by mass of this block copolymer and 1.7 parts by mass of maleic anhydride were supplied from the throat of a twin-screw extruder set to a temperature of 150-200°C throughout the entire length of the extruder, and 0.12 parts by mass of organic peroxide (peroxide 25B (manufactured by NOF Corporation)) were supplied from the feed port downstream of the twin-screw extruder to compound the mixture. The strands discharged from the extruder's discharge port were then pelletized. The pellets obtained as described above were dried in a dry oven at approximately 80°C for 3 hours to obtain modified polymer hydrogenated block copolymer (I)-6. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-6 was 65 ml.

[0138] <Manufacturing Example 7: High Polymer Hydrogenated Block Copolymer (I)-7> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 16.8 mL of n-butyllithium (2.4 mol / L), 0.9 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.6 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 8 minutes. Next, a cyclohexane solution (20% by mass) containing 30 parts by mass of styrene and 60 parts by mass of butadiene was added, and polymerization was carried out at 65°C for 80 minutes. Then, tetraglycyl-1,3-bisaminomethylcyclohexane (TED) was added to initiate a coupling reaction. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 10% by mass, a total vinyl bond content of 30% by mass in the block copolymer, and a weight-average molecular weight (before coupling) of 150,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated polymeric hydrogenated block copolymer (I)-7. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-7 was 63 ml. Note that polymer hydrogenated block copolymer (I)-7 has a 3-4 branched star structure formed by coupling diblock polymers, but it is shown in a simplified form in Table 1.

[0139] <Comparative Manufacturing Example 1: High Polymer Hydrogenated Block Copolymer (I)-8> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 12.6 mL of n-butyllithium (2.4 mol / L), 0.4 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and further 0.3 mL of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 70 parts by mass of butadiene was added, and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (concentration 20% by mass) containing 15 parts by mass of styrene was added, and polymerization was carried out at 65°C for 10 minutes. Finally, heptanol was added to terminate the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond amount of 32% by mass in the block copolymer, and a weight average molecular weight of 310,000. Furthermore, to the obtained block copolymer, the hydrogenation catalyst prepared as described above was added at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, as a stabilizer, 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain a hydrogenated polymer hydrogenated block copolymer (I)-8. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-8 was 98 mol%.

[0140] <Comparative Production Example 2: Polymer Hydrogenated Block Copolymer (I)-9> Batch polymerization was carried out using a tank-type reactor (internal volume 20 L) equipped with a stirrer and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was charged. Next, 14.4 mL of n-butyllithium (2.4 mol / L), 0.6 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and further 0.4 mL of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 65°C for 5 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 5 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a total vinyl bond amount in the block copolymer of 32% by mass, and a weight average molecular weight of 210,000. Furthermore, to the obtained block copolymer, the hydrogenation catalyst prepared as described above was added at 100 ppm on a Ti basis per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, as a stabilizer, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added per 100 parts by mass of the block copolymer to obtain a hydrogenated polymer hydrogenated block copolymer (I)-9. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-9 was 65 mol%.

[0141] <Comparative Production Example 3: Polymer Hydrogenated Block Copolymer (I)-10> Batch polymerization was carried out using a tank reactor (internal volume 20 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 22.5 parts by mass of styrene was charged. Next, 14.4 mL of n-butyllithium (2.4 mol / L), 0.7 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and further 0.4 mL of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 65°C for 20 minutes. Next, a cyclohexane solution (20% by mass) containing 14 parts by mass of styrene and 41 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Then, a cyclohexane solution (20% by mass) containing 22.5 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. Subsequently, 1.4 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 59% by mass, a polystyrene block content of 45% by mass, a total vinyl bond content of 35% by mass in the block copolymer, and a weight-average molecular weight of 210,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain the hydrogenated polymer hydrogenated block copolymer (I)-10. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-10 was 64 mol%.

[0142] <Comparative Manufacturing Example 4: High Polymer Hydrogenated Block Copolymer (I)-11> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 5 parts by mass of styrene was added. Next, 14.2 mL of n-butyllithium (2.4 mol / L), 0.6 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 23 parts by mass of styrene and 67 parts by mass of butadiene was added and polymerization was carried out at 65°C for 80 minutes. Then, a cyclohexane solution (20% by mass) containing 5 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. Subsequently, 1.3 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 33% by mass, a polystyrene block content of 10% by mass, a total vinyl bond content of 33% by mass in the block copolymer, and a weight-average molecular weight of 220,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain the hydrogenated polymer hydrogenated block copolymer (I)-11. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-11 was 63 ml.

[0143] <Comparative Manufacturing Example 5: High Polymer Hydrogenated Block Copolymer (I)-12> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 14.2 mL of n-butyllithium (2.4 mol / L) and 0.2 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 8 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 70 minutes. Then, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 8 minutes. Subsequently, 1.3 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a total vinyl bond content of 24% by mass in the block copolymer, and a weight-average molecular weight of 220,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain the hydrogenated polymer hydrogenated block copolymer (I)-12. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-12 was 62 ml.

[0144] <Comparative Manufacturing Example 6: High Polymer Hydrogenated Block Copolymer (I)-13> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 13.7 mL of n-butyllithium (2.4 mol / L) and 0.6 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 8 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 70 minutes. Then, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 8 minutes. Subsequently, 1.2 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a total vinyl bond content of 35% by mass in the block copolymer, and a weight-average molecular weight of 240,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain the hydrogenated polymer hydrogenated block copolymer (I)-13. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-13 was 45 ml.

[0145] <Comparative Manufacturing Example 7: High Polymer Hydrogenated Block Copolymer (I)-14> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 20.8 mL of n-butyllithium (2.4 mol / L) and 1.3 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 8 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added, and polymerization was carried out at 65 °C for 70 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added, and polymerization was carried out at 65 °C for 8 minutes. Then, 3.0 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and reacted. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 20% by mass, a total vinyl bond amount in the block copolymer of 24% by mass, and a weight average molecular weight of 100,000. Furthermore, to the obtained block copolymer, the hydrogenation catalyst prepared as described above was added at 100 ppm on a Ti basis per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 °C. Next, as a stabilizer, 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain a hydrogenated polymer hydrogenated block copolymer (I)-14. The hydrogenation rate of the obtained polymer hydrogenated block copolymer (I)-14 was 65 mol%.

[0146] (Production of hydrogenated block copolymer (IV)) (Production Example 8: Hydrogenated block copolymer (IV)-1) Batch polymerization was carried out using a tank reactor (internal volume 20 L) equipped with a stirrer and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was charged. Next, 27.4 mL of n-butyllithium (2.4 mol / L), 2.0 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and further 1.3 mL of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 65 °C for 8 minutes. Next, a cyclohexane solution (20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 65°C for 70 minutes. Then, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 8 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 20% by mass, a polystyrene block content of 20% by mass, a total vinyl bond content of 35% by mass in the block copolymer, and a weight-average molecular weight of 65,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-1. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-1 was 98 ml.

[0147] <Manufacturing Example 9: Hydrogenated Block Copolymer (IV)-2> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 28.4 mL of n-butyllithium (2.4 mol / L), 1.8 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 33% by mass in the block copolymer, and a weight-average molecular weight of 62,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-2. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-2 was 96 ml.

[0148] <Manufacturing Example 10: Hydrogenated Block Copolymer (IV)-3> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 20 parts by mass of styrene was added. Next, 28.6 mL of n-butyllithium (2.4 mol / L), 2.3 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 2.3 mL of sodium t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Then, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 40% by mass, a total vinyl bond content of 36% by mass in the block copolymer, and a weight-average molecular weight of 62,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-3. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-3 was 97 ml.

[0149] <Manufacturing Example 11: Hydrogenated Block Copolymer (IV)-4> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added. Next, 22.0 mL of n-butyllithium (2.4 mol / L), 1.4 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.0 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 8 minutes. Next, a cyclohexane solution (20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 65°C for 70 minutes. Then, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 65°C for 8 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 20% by mass, a polystyrene block content of 20% by mass, a total vinyl bond content of 32% by mass in the block copolymer, and a weight-average molecular weight of 90,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-4. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-4 was 75 ml.

[0150] <Production Example 12: Hydrogenated Block Copolymer (IV)-5> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 22.5 mL of n-butyllithium (2.4 mol / L) and 1.5 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 34% by mass in the block copolymer, and a weight-average molecular weight of 88,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-5. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-5 was 77 ml.

[0151] <Manufacturing Example 13: Hydrogenated Block Copolymer (IV)-6> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 25.4 mL of n-butyllithium (2.4 mol / L), 2.0 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.2 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Subsequently, 4.1 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 36% by mass in the block copolymer, and a weight-average molecular weight of 73,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-6. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-6 was 88 mol%.

[0152] <Production Example 14: Hydrogenated Block Copolymer (IV)-7> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 29.0 mL of n-butyllithium (2.4 mol / L), 2.4 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Subsequently, 5.0 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was continued. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 36% by mass in the block copolymer, and a weight-average molecular weight of 60,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-7. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-7 was 87 ml.

[0153] <Manufacturing Example 15: Hydrogenated Block Copolymer (IV)-8> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 28.7 mL of n-butyllithium (2.4 mol / L), 2.4 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 36% by mass in the block copolymer, and a weight-average molecular weight of 61,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass per 100 parts by mass of the block copolymer. 100 parts by mass of this block copolymer and 1.7 parts by mass of maleic anhydride were supplied from the throat of a twin-screw extruder set to a temperature of 150-200°C throughout the entire length of the extruder, and 0.12 parts by mass of organic peroxide (peroxide 25B (manufactured by NOF Corporation)) were supplied from the feed port downstream of the twin-screw extruder to compound the mixture. The strands discharged from the extruder's discharge port were then pelletized. The pellets obtained as described above were dried in a dry oven at approximately 80°C for 3 hours to obtain modified polymer hydrogenated block copolymer (I)-8. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-8 was 96 ml.

[0154] <Manufacturing Example 16: Hydrogenated Block Copolymer (IV)-9> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 28.7 mL of n-butyllithium (2.4 mol / L), 2.2 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.4 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 60 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. After that, a cyclohexane solution (20% by mass) containing 10 parts by mass of butadiene was added and polymerization was carried out for 8 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 35% by mass in the block copolymer, and a weight-average molecular weight of 61,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-9. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-9 was 96 ml.

[0155] <Production Example 17: Hydrogenated Block Copolymer (IV)-10> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 20 parts by mass of styrene was added. Next, 25.8 mL of n-butyllithium (2.4 mol / L), 2.1 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 1.2 mL of sodium-t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 50 parts by mass of butadiene was added and polymerization was carried out at 65°C for 40 minutes. Then, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. After that, a cyclohexane solution (20% by mass) containing 10 parts by mass of butadiene was added and polymerization was carried out for 8 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 40% by mass, a total vinyl bond content of 37% by mass in the block copolymer, and a weight-average molecular weight of 71,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-10. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-10 was 98 ml.

[0156] <Production Example 18: Hydrogenated Block Copolymer (IV)-11> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 20 parts by mass of styrene was added. Next, 20.0 mL of n-butyllithium (2.4 mol / L), 7.3 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L), and 0.8 mL of sodium t-pentoxide per mole of n-butyllithium were added, and polymerization was carried out at 65°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 50 parts by mass of butadiene was added and polymerization was carried out at 65°C for 40 minutes. Then, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene was added and polymerization was carried out at 65°C for 15 minutes. After that, a cyclohexane solution (20% by mass) containing 10 parts by mass of butadiene was added and polymerization was carried out for 8 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 40% by mass, a polystyrene block content of 40% by mass, a total vinyl bond content of 78% by mass in the block copolymer, and a weight-average molecular weight of 107,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-11. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-11 was 99 ml.

[0157] <Manufacturing Example 19: Hydrogenated Block Copolymer (IV)-12> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 18.3 mL of n-butyllithium (2.4 mol / L) and 0.9 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 50 parts by mass of butadiene was added and polymerization was carried out at 65°C for 60 minutes. Then, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 50% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 30% by mass in the block copolymer, and a weight-average molecular weight of 130,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-12. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-12 was 95 ml.

[0158] <Production Example 20: Hydrogenated Block Copolymer (IV)-13> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 24.5 mL of n-butyllithium (2.4 mol / L) and 5.8 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 6 parts by mass of butadiene was added and polymerization was carried out at 55°C for 5 minutes. Then, a cyclohexane solution (20% by mass) containing 34 parts by mass of styrene and 24 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Next, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Furthermore, a cyclohexane solution (20% by mass) containing 6 parts by mass of butadiene was added and polymerization was carried out at 55°C for 5 minutes. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 64% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 67% by mass in the block copolymer, and a weight-average molecular weight of 80,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-13. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-13 was 98 ml.

[0159] <Production Example 21: Hydrogenated Block Copolymer (IV)-14> Batch polymerization was carried out using a tank-type reactor (internal volume 20L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 24.5 mL of n-butyllithium (2.4 mol / L) and 5.8 mL of N,N,N',N'-tetramethylethylenediamine (6.7 mol / L) were added, and polymerization was carried out at 65°C for 10 minutes. Next, a cyclohexane solution (20% by mass) containing 6 parts by mass of butadiene was added and polymerization was carried out at 55°C for 5 minutes. Then, a cyclohexane solution (20% by mass) containing 34 parts by mass of styrene and 24 parts by mass of butadiene was added and polymerization was carried out at 65°C for 50 minutes. Next, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 65°C for 10 minutes. Furthermore, a cyclohexane solution (20% by mass) containing 6 parts by mass of butadiene was added and polymerization was carried out at 55°C for 5 minutes. After that, 3.8 mL of 1,3-dimethyl-2-imidazolidinone (9.3 mol / L) was added and the reaction was carried out. Finally, heptanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 64% by mass, a polystyrene block content of 30% by mass, a total vinyl bond content of 67% by mass in the block copolymer, and a weight-average molecular weight of 80,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (IV)-14. The hydrogenation rate of the obtained hydrogenated block copolymer (IV)-14 was 88 ml.

[0160] The composition and properties of hydrogenated block copolymer (I) are shown in Tables 1 and 2, and the composition and properties of hydrogenated block copolymer (IV) are shown in Tables 3 and 4.

[0161] [Table 1]

[0162] [Table 2]

[0163] [Table 3]

[0164] [Table 4]

[0165] [Manufacturing and property evaluation of thermoplastic elastomer compositions] Next, thermoplastic elastomer compositions were prepared using the polymer hydrogenated block copolymer (I) and hydrogenated block copolymer (IV) prepared as described above. This document provides a detailed explanation of methods for preparing and evaluating thermoplastic elastomer compositions.

[0166] First, we will explain each component used in the preparation of the thermoplastic elastomer composition. (Hydrogenated polymer block copolymer (I)) The polymer hydrogenated block copolymers (I)-1 to 14 produced in the above-mentioned production examples 1 to 7 and comparative production examples 1 to 7 were used.

[0167] (Non-aromatic softener (II)) The following commercially available non-aromatic softeners (II) were used. Non-aromatic softener: Diana Process Oil PW90 manufactured by Idemitsu Kosan Co., Ltd., paraffin-based oil, weight-average molecular weight 530, kinematic viscosity (40℃) = 90.5 mmHg 2 / sec

[0168] (Olefin resin (III)) The following commercially available olefin resin (III) was used. Polypropylene: Sun Allomer Co., Ltd. PM801A, propylene homopolymer, MFR (230℃, 2.16kg) 13g / 10min

[0169] (Hydrogenated block copolymer (IV)) Hydrogenated block copolymers (IV)-1 to 14, prepared in production examples 8 to 21, were used.

[0170] [Examples 1-24], [Comparative Examples 1-11] A method for preparing thermoplastic elastomer compositions will be described. Based on the mixing ratios (parts by mass) shown in the table below, the above-mentioned components were mixed and melt-kneaded at a set temperature of 230°C using a twin-screw extruder (TEX-30αII, manufactured by Japan Steel Works, Ltd., cylinder bore diameter 30 mm) to obtain pellets of thermoplastic elastomer composition. The resulting pellets were dried in an oven at 50°C.

[0171] Next, we will describe the molding and evaluation methods for thermoplastic elastomer compositions. (Creating the sheet) Using the pellets of the thermoplastic elastomer composition obtained in the above [Manufacturing of Thermoplastic Elastomer], a sheet measuring 95 mm x 145 mm x 2 mm thick was molded using an injection molding machine FNX110III-18A (manufactured by Nissei Plastic Industrial Co., Ltd.). The obtained sheets were used to measure their physical properties according to the measurement method described below.

[0172] (Method for evaluating sheets) <Flexibility> Tensile tests were conducted using a No. 3 dumbbell and a crosshead speed of 500 mm / min, in accordance with JIS K6251. The strength at fracture was used as an indicator of toughness and was evaluated according to the following criteria. A: Breaking strength exceeds 6.0 MPa B: Breaking strength exceeding 5.0 MPa and 6.0 MPa or less. C: Breaking strength exceeding 4.0 MPa but not exceeding 5.0 MPa D: Breaking strength is 4.0 MPa or less

[0173] <Flexibility> The hardness was measured using a Type A durometer in accordance with JIS K6253. Flexibility was determined according to the following criteria. A: Shore A hardness (10s) is 60 or less B: Shore A hardness (10s) is between 60 and 70. C: Shore A hardness (10s) is between 70 and 80. D: Shore A hardness (10s) exceeds 80

[0174] <Liquidity> MFR measurements were performed in accordance with JIS K7210, under conditions of a temperature of 230°C and a load of 2.16 kg. Liquidity was determined according to the following criteria. A: MFR value exceeds 110g / 10min B: MFR value greater than 90g / 10min and less than or equal to 110g / 10min C:MFR value greater than 70g / 10min and less than or equal to 90g / 10min D: MFR value is 70g / 10min or less

[0175] <Transparency> In accordance with JIS K7136, the haze value of a 2 mm thick press sheet of the thermoplastic elastomer composition obtained in the above-mentioned [manufacturing of thermoplastic elastomer] was measured using a haze meter [manufactured by Suga Test Instruments Co., Ltd., product name HZ-V3]. Transparency was assessed according to the following criteria. A: Haze Value 25 or less B: Haze value between 25 and 40 C: Haze value is between 40 and 55. D: Haze value exceeds 55

[0176] <Molded appearance> The sheets were visually inspected and determined as follows. ○: No flow marks (waveforms) were observed on the sheet surface. ×: Sheets on which flow marks (waveforms) were observed on the surface.

[0177] Next, we will explain the method for creating and evaluating multilayer molded articles using thermoplastic elastomer compositions. (Fabrication of multilayer molded bodies) Using the pellets of the thermoplastic elastomer composition obtained in the above [Manufacturing of Thermoplastic Elastomer], a pre-molded product of a polar group-containing thermoplastic resin, described later, measuring 95 mm x 145 mm x 2 mm thick, was inserted into the mold cavity of an injection molding machine FNX110III-18A (manufactured by Nissei Plastic Industrial Co., Ltd.), and a thermoplastic elastomer composition measuring 100 mm x 150 mm x 2 mm thick was injection molded onto its surface. The injection molding conditions were as follows: resin temperature: 240°C, injection speed: 40 mm / second, injection time: 10 seconds, mold temperature: 40°C, and cooling time: 30 seconds.

[0178] <Molded product of thermoplastic resin used as the base material> PP molded plate: Kyoei Resin Co., Ltd., Dialight PX-2, 95mm x 145mm x 2mm thick flat plate PC molded plate: Takiron CI Co., Ltd. PC1600, 95mm x 145mm x 2mm thick flat plate ABS molded plate: Sumitomo Bakelite Co., Ltd. EAR003, 95mm x 145mm x 2mm thick flat plate PC / ABS molded plate: Sumitomo Bakelite Co., Ltd., ROAR EFN800-04 (black), 95mm x 145mm x 2mm thick flat plate PMMA molded plate: Mitsubishi Chemical Corporation Acrylite L-001, 95mm x 145mm x 2mm thick flat plate PET molded plate: Takiron CI Co., Ltd. PET-6010, 95mm x 145mm x 2mm thick flat plate PA molded plate: Toray Plastics Precision Co., Ltd., TPS-N66, 95mm x 145mm x 2mm thick flat plate

[0179] (Evaluation method for multilayer molded bodies) <Adhesion to the substrate (thermal fusion strength)> The thermal fusion strength between the thermoplastic elastomer composition and the polar group-containing thermoplastic resin was measured by a 90-degree peel test using the multilayer molded product described above. A 10 mm wide cut was made on the thermoplastic elastomer composition side of the multilayer molded body, and several centimeters of the end were peeled off beforehand. At the peeled portion, the layer made of the thermoplastic elastomer composition and the layer made of the polar group-containing thermoplastic resin were fixed separately to the chucks of a tensile testing machine [MinebeaMitsumi Inc., TGE-500N (product name)]. The two layers were separated by pulling the thermoplastic elastomer composition layer and the polar group-containing thermoplastic resin layer at 300 mm / min in the 90° direction. The tensile force applied during peeling was defined as the thermal fusion strength (N / cm) of the multilayer molded body of the thermoplastic elastomer composition and the polar group-containing thermoplastic resin, and was evaluated according to the following evaluation criteria. The evaluation was made according to the following criteria A to D. A: Peel strength of 30 N / 10 mm or more B: Peel strength of 20N / 10mm or more and less than 30N / 10mm C: Peel strength of 10N / 10mm or more and less than 20N / 10mm D: Peel strength less than 10N / 10mm

[0180] Tables 5 to 10 show the blending ratios and properties of the thermoplastic elastomer compositions of Examples 1 to 24 and Comparative Examples 1 to 11.

[0181] [Table 5]

[0182] [Table 6]

[0183] [Table 7]

[0184] [Table 8]

[0185] [Table 9]

[0186] [Table 10]

[0187] The thermoplastic elastomer composition and multilayer laminate of the present invention exhibit excellent transparency, fluidity, thermal adhesion, and flexibility, and have been found to be excellent as a surface material for base resins (olefin resins and polar resins) and as various sealing materials. [Industrial applicability]

[0188] The thermoplastic elastomer composition and molded articles of the present invention have industrial potential as surface materials for base resins (olefin resins and polar resins), various sealing materials, and toys.

Claims

1. High polymer hydrogenated block copolymer (I), Non-aromatic softener (II), Olefin resin (III) and A thermoplastic elastomer composition containing, The polymer hydrogenated block copolymer (I) satisfies the following conditions (a) to (g): The product contains 20 to 400 parts by mass of the non-aromatic softener (II) and 10 to 200 parts by mass of the olefin resin (III) per 100 parts by mass of the polymer hydrogenated block copolymer (I). Thermoplastic elastomer composition. <Condition (a)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A1 mainly composed of vinyl aromatic monomer units, and polymer block B1 and / or polymer block C1 mainly composed of conjugated diene monomers, comprising vinyl aromatic monomer units and conjugated diene monomer units. <Condition (b)> The total content of vinyl aromatic monomer units is 20 to 60% by mass. <Condition (c)> The content of the polymer block A1 is 15 to 40% by mass. <Condition (d)> The amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 25 mol% or more. <Condition (e)> The hydrogenation rate of the double bond in the conjugated diene monomer unit is between 50 mol% and 90 mol%. <Condition (f)> The weight-average molecular weight Mw is between 150,000 and 300,000. <Condition (g)> The molecule contains at least one functional group selected from the group consisting of amino groups, amide groups, hydroxyl groups, acid anhydride groups, epoxy groups, silanol groups, and alkoxysilyl groups.

2. The thermoplastic elastomer composition further contains a hydrogenated block copolymer (IV) that satisfies the following conditions (h) to (m): The thermoplastic elastomer composition according to claim 1. <Condition (h)> A hydrogenated block copolymer comprising vinyl aromatic monomer units and conjugated diene monomer units, comprising at least one polymer block A2 mainly composed of vinyl aromatic monomer units and a polymer block C2 mainly composed of conjugated diene monomer units. <Condition (i)> The total content of vinyl aromatic monomer units is 15% by mass or more and 70% by mass or less. <Condition (j)> The amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation is 30 mol% or more. <Condition (k)> The hydrogenation rate of the double bond in the conjugated diene monomer unit is 50 mol% or more. <Condition (l)> The weight-average molecular weight Mw is between 30,000 and 150,000. <Condition (m)> The MFR value measured at 230°C and 2.16 kg is 2.0 g / 10 min or higher.

3. The hydrogenated block copolymer (IV) has at least one functional group selected from the group consisting of an amino group, a hydroxyl group, an acid anhydride group, a silanol group, and an alkoxysilyl group in its molecule. The thermoplastic elastomer composition according to claim 2.

4. The hydrogenated block copolymer (IV) is contained in an amount of 50 to 200 parts by mass relative to 100 parts by mass of the polymer hydrogenated block copolymer (I). The thermoplastic elastomer composition according to claim 2.

5. The MFR value measured at 230°C and 2.16 kg is 70 g / 10 min or higher. The thermoplastic elastomer composition according to claim 1.

6. A layer L1 of the thermoplastic elastomer composition according to any one of claims 1 to 5, Thermoplastic resin substrate layer L2, A multilayer molded body having the following characteristics.

7. The thermoplastic resin constituting the thermoplastic resin substrate layer L2 is It is at least one selected from the group consisting of olefin resins, styrene resins, polycarbonates, polyesters, acrylic resins, polyamides, and mixtures thereof. The multilayer molded body according to claim 6.

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