TWI810466B - Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article - Google Patents

Abstract

The present invention obtains a hydrogenated block copolymer that provides excellent abrasion resistance and high MFR when formed into a resin composition with polyolefin. The hydrogenated block copolymer of the present invention satisfies the requirements (1) to (7). (1): Contains at least one (b) hydrogenated copolymer block comprising a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. (2): (a) The content of the polymer block mainly composed of vinyl aromatic compound monomer units is 40% by mass or less. (3): Mw is 200,000 or less. (4): The hydrogenation rate is above 20%. (5): In the GPC curve, the ratio of the area of the molecular weight range of 10,000 to 150,000 to the area of the molecular weight range of 10,000 to 1,000,000 exceeds 50%. (6): The amount of vinyl bonds is 20% by mass or more. (7): The content of the vinyl aromatic compound monomer unit in the (b) block is not less than 30% by mass and not more than 79% by mass.

Description

Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article

The present invention relates to a hydrogenated block copolymer, a hydrogenated block copolymer composition, and a shaped body.

Conventionally, a balance between abrasion resistance and mechanical strength has been required for automotive interior materials. As such a material, olefin-based resins are mainly used. On the other hand, in order to meet the requirements of environmental issues such as lightweight, reusable and incinerable parts for automobiles, as well as heat resistance, cold resistance, heat aging resistance, light resistance, low odor, and seek excellent appearance In recent years, styrene-based thermoplastic elastomer materials (hereinafter, sometimes simply referred to as "TPS materials") have been put into practical use to solve the feeling of cheapness.

Furthermore, in recent years, with the increase in demand for shared cars and self-driving cars, a TPS that maintains a high level of wear resistance and can achieve high-quality touch (low hardness) or mechanical strength is required for automotive interior materials Material. In response to this requirement, for example, a composition of a random copolymer styrene-based elastomer and a polypropylene resin with a vinyl aromatic hydrocarbon content of more than 40% by mass and less than 95% by mass is proposed in Patent Document 1 and the A molded body of the composition, and it is revealed that the molded body is excellent in abrasion resistance. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 03/035705

[Problem to be solved by the invention]

However, the random copolymer styrene-based elastomer described in Patent Document 1 has low dispersibility to polypropylene resin, so when it is formed into a composition with polypropylene resin, sufficient processability cannot be obtained. question. In addition, the strands were broken rapidly during extrusion, so there was a problem that the extrusion formability was not sufficient. Furthermore, in recent years, along with the above-mentioned increase in demand for shared cars and self-driving cars, high designability is required for automotive interior materials, and in view of this designability, the production of molded objects with complex shapes is required. The main method of manufacturing molded objects with complex shapes is injection molding, but in this case, the material of the molded objects must have a high melt flow rate (hereinafter referred to as MFR). Therefore, there is a demand for a resin composition that maintains required properties such as wear resistance and has a higher MFR.

In the present invention, an object thereof is to provide a hydrogenated block copolymer capable of providing a resin composition having excellent wear resistance and a high MFR, a resin composition containing the hydrogenated block copolymer, and a molded article. [Technical means to solve the problem]

The inventors of the present invention have devoted themselves to research in order to solve the above-mentioned problems in the prior art, and found that by having a specific structure, and specifying the content of polymer blocks mainly composed of vinyl aromatic compound monomer units, and the weight average molecular weight , the hydrogenation rate, the area in the GPC curve of a specific range of molecular weight, the amount of vinyl bonds, and the content of vinyl aromatic compound monomer units in a specific polymer block. Hydrogenated block copolymers can provide resistance The present invention has been accomplished by providing a resin composition with improved abrasion resistance and MFR. That is, the present invention is as follows.

[1] A hydrogenated block copolymer, which is a hydrogenated block copolymer containing vinyl aromatic compound monomer units and conjugated diene monomer units, and Satisfy the necessary conditions of (1) to (7) below; (1): Containing at least one (b) hydrogenated copolymer block comprising vinyl aromatic compound monomer units and conjugated diene monomer units; (2): It has (a) a polymer block mainly composed of vinyl aromatic compound monomer units, and the content of (a) polymer block mainly composed of vinyl aromatic compound monomer units is 40% by mass %the following; (3): The weight average molecular weight (Mw) is less than 200,000; (4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is more than 20%; (5): In the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the area with a molecular weight of 10,000 to 150,000 relative to the molecular weight range of 10,000 to 1,000,000 The area ratio exceeds 50%; (6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more; (7): The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above is 30% by mass or more and 79% by mass or less. [2] The hydrogenated block copolymer according to the above [1], wherein the amount of vinyl bonds in the hydrogenated block copolymer is 30% by mass or more. [3] The hydrogenated block copolymer of the above [1] or [2], wherein the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) is 45% by mass or more and 79% by mass or less. [4] The hydrogenated block copolymer according to any one of the above [1] to [3], wherein in the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the molecular weight is 200,000 to 200,000 The ratio of the area of the range of 1 million to the area of the range of the molecular weight of 10,000 to 1,000,000 is 10% or more. [5] The hydrogenated block copolymer according to any one of the above [1] to [4], wherein the content of the total vinyl aromatic compound monomer units is 40% by mass or more and 80% by mass or less. [6] The hydrogenated block copolymer according to any one of the above-mentioned [1] to [5], wherein the content of the above-mentioned (a) polymer block mainly composed of vinyl aromatic compound monomer units is 1% by mass or more and 20% by mass %the following. [7] The hydrogenated block copolymer according to any one of the above [1] to [6], which contains 1% by mass or more of (c) a hydrogenated polymer block mainly composed of conjugated diene monomer units. [8] The hydrogenated block copolymer according to any one of the above-mentioned [1] to [7], wherein at least one peak of tan δ in the viscoelasticity measurement chart exists at 0°C to 30°C. [9] A hydrogenated block copolymer composition comprising the hydrogenated block copolymer (1) according to any one of the above [1] to [8]: 1% by mass to 95% by mass, and At least one olefin-based resin (2): 5% by mass or more and 99% by mass or less. [10] The hydrogenated block copolymer composition according to the above [9], wherein the olefin-based resin (2) contains at least one kind of polypropylene-based resin. [11] A molded article which is a molded article of the hydrogenated block copolymer composition according to the above-mentioned [9] or [10]. [Effect of Invention]

According to the present invention, it is possible to obtain a hydrogenated block copolymer that provides excellent abrasion resistance and high MFR when formed into a resin composition with polyolefin.

Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. In addition, the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited to the following contents, and the present invention can be implemented with various changes within the scope of the gist.

[Hydrogenated Block Copolymer] The hydrogenated block copolymer of this embodiment (hereinafter sometimes referred to as hydrogenated block copolymer (1)) is a hydrogenated block copolymer containing a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. The material satisfies the following (1) to (7). (1): Contains at least one (b) hydrogenated copolymer block comprising a vinyl aromatic compound monomer unit and a conjugated diene monomer unit (hereinafter, sometimes referred to as copolymer block (b)). (2): Having (a) a polymer block mainly composed of a vinyl aromatic compound monomer unit (hereinafter, sometimes referred to as a polymer block (a)), the content of the polymer block (a) 40% by mass or less. (3): The weight average molecular weight (Mw) is 200,000 or less. (4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is 20% or more. (5): In the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the area with a molecular weight of 10,000 to 150,000 relative to the molecular weight range of 10,000 to 1,000,000 The area ratio exceeds 50%. (6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more. (7): The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above is 30% by mass or more and 79% by mass or less.

(vinyl aromatic compound monomer unit) The hydrogenated block copolymer (1) of this embodiment contains vinyl aromatic monomer units. The vinyl aromatic compound monomer unit is not limited to the following, and examples thereof include: derived from styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, and 1,1-diphenylethylene , N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and other monomer units. In particular, styrene is preferred from the viewpoint of the balance between price and mechanical strength. These may be used alone or in combination of two or more.

(conjugated diene monomer unit) The hydrogenated block copolymer (1) of this embodiment contains a conjugated diene monomer unit. The so-called conjugated diene monomer unit refers to a monomer unit derived from a diene having one pair of conjugated double bonds. Such dienes are not limited to the following, for example, 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. In particular, 1,3-butadiene and isoprene are preferred from the viewpoint of a balance between good formability and mechanical strength. These may be used alone or in combination of two or more.

In the hydrogenated block copolymer (1) of this embodiment, the vinyl bond amount in the conjugated diene monomer unit is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, Furthermore, it is more preferable that it is 35 mass % or more. If the amount of vinyl bonds in the conjugated diene monomer unit of the hydrogenated block copolymer (1) is 20% by mass or more, when combining the hydrogenated block copolymer (1) with the following olefin resin (2) In the hydrogenated block copolymer composition of this embodiment, there exists a tendency for hardness and extrusion formability to improve, and when it is 30 mass % or more, especially MFR and abrasion resistance tend to become favorable. The higher the amount of vinyl bonds, the more the above-mentioned physical properties are improved. In addition, the amount of vinyl bonds in the hydrogenated block copolymer (1) can be controlled, for example, by using regulators such as the following tertiary amine compounds and ether compounds.

In the hydrogenated block copolymer (1) of this embodiment, the content of the total vinyl aromatic compound monomer units is preferably from 40% by mass to 80% by mass, more preferably from 45% by mass to 80% by mass, and further Preferably it is 47 mass % or more and 78 mass % or less, More preferably, it is 50 mass % or more and 75 mass % or less. When the content of the total vinyl aromatic compound monomer units is within the above range, the balance of hardness, extrusion moldability, and abrasion resistance tends to be favorable. Furthermore, in this embodiment, the content of the total vinyl aromatic compound monomer units in the hydrogenated block copolymer (1) can be detected by using the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation. body, measured using an ultraviolet spectrophotometer. Also, the content of the total vinyl aromatic compound monomer units of the hydrogenated block copolymer (1) can be controlled as above range of values.

Furthermore, in this specification, in the composition of the hydrogenated block copolymer, the term "mainly" means that the ratio in a specific block polymer or in a polymer block is 85% by mass or more, preferably 90% by mass % or more, more preferably more than 95% by mass. Furthermore, since the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 30% by mass or more and 79% by mass or less, it is possible to clearly distinguish the above polymer block (a) from the hydrogenated polymer block (a) Object block (b).

(Polymer block (a) mainly composed of vinyl aromatic compounds) The hydrogenated block copolymer (1) of this embodiment contains at least one polymer block (a) mainly composed of vinyl aromatic compound monomer units from the viewpoint of preventing particle blocking. In addition, in the hydrogenated block copolymer (1) of the present embodiment, the content of (a) polymer block is 40 mass % or less, preferably 1 mass % or more and 40 mass % or less, more preferably 1 mass % or more 20 mass % or less, and more preferably 5 mass % or more and 15 mass % or less. By setting the content of (a) polymer block in the hydrogenated block copolymer (1) of this embodiment to be 40% by mass or less, the following hydrogenated block copolymer composition of this embodiment has abrasion resistance Good balance with hardness.

The content of the above-mentioned polymer block (a) can be determined by using the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation as a sample by using a method with a nuclear magnetic resonance device (NMR) (Y.Tanaka, et al. al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as "NMR method"). Also, the content of the polymer block (a) in the hydrogenated block copolymer (1) can be controlled to the above-mentioned range of values.

(hydrogenated copolymer block (b)) The hydrogenated block copolymer (1) of this embodiment contains a hydrogenated copolymer block (b) comprising a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is not less than 30% by mass and not more than 79% by mass, preferably not less than 40% by mass and not more than 79% by mass, more preferably not less than 45% by mass79 % by mass or less, more preferably not less than 45% by mass and not more than 70% by mass.

If the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is not less than 30% by mass and not more than 79% by mass, the following hydrogenated block copolymer composition of the present embodiment exhibits good wear resistance consumption. Furthermore, if it is 45 mass % or more and 79 mass % or less, higher abrasion resistance will be shown, and it can be used for the use which requires stricter abrasion resistance. In addition, when the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 79% by mass or less, the extrusion moldability of the hydrogenated block copolymer composition of the present embodiment is improved as follows There is a tendency for the hardness to decrease. Furthermore, in this embodiment, the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) in the hydrogenated block copolymer (1) can be determined by a nuclear magnetic resonance device (NMR) or the like. Determination. Also, the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) can be adjusted mainly by adjusting the amount of the vinyl aromatic compound added to the reactor, the amount of the conjugated diene, and the reaction temperature, and The control is within the above numerical range.

The amount of vinyl bonds in the conjugated diene moiety in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) can be controlled, for example, by using an adjuster such as the following tertiary amine compound or ether compound. In the case of using 1,3-butadiene as the conjugated diene, in the hydrogenated block copolymer composition of the present embodiment described below, a good balance of abrasion resistance, MFR and hardness is obtained In other words, the 1,2-vinyl bond amount of the conjugated diene moiety in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) is preferably from 25 mass % to 95 mass %, more preferably It is 30 mass % or more and 90 mass % or less. When isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used together as the conjugated diene, the 1,2-vinyl bond and the 3,4-vinyl bond The total amount of bonds is preferably from 3% by mass to 75% by mass, more preferably from 5% by mass to 60% by mass. Furthermore, in this embodiment, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (here, when 1,3-butadiene is used as the conjugated diene is 1 , 2-vinyl bond amount) is called vinyl bond amount. The amount of vinyl bonds can be measured by measurement with an infrared spectrophotometer (for example, the Hampton method) using the copolymer before hydrogenation as a sample.

(Hydrogenated polymer block (c) mainly composed of conjugated diene monomer units) The hydrogenated block copolymer (1) of this embodiment preferably contains a hydrogenated polymer block (c) mainly composed of conjugated diene monomer units. In the hydrogenated block copolymer (1) of this embodiment, the content of the hydrogenated polymer block (c) depends on the MFR and hardness of the hydrogenated block copolymer (1) and the following hydrogenated block copolymer of this embodiment From the viewpoint of the balance of MFR, abrasion resistance, and hardness of the composition, it is preferably at least 1% by mass, more preferably at least 2% by mass and not more than 20% by mass, and still more preferably at least 2% by mass and not more than 15% by mass , and more preferably at least 2% by mass and not more than 8% by mass. Also, the content of the hydrogenated polymer block (c) in the hydrogenated block copolymer (1) can be controlled within the above numerical range by mainly controlling the amount of conjugated diene added to the reactor and the reaction temperature.

The vinyl bond of the hydrogenated conjugated diene monomer unit in the hydrogenated polymer block (c) has a chemical structure similar to that of the following olefin resin (2). Therefore, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation in the hydrogenated polymer block (c) affects the compatibility between the hydrogenated block copolymer (1) and the olefin resin (2), From the viewpoint of improving the compatibility and improving the wear resistance, MFR, and hardness of the hydrogenated block copolymer composition of the present embodiment described below, it is preferably 50% by mass or more, more preferably 55% by mass % or more, and more preferably 60% by mass or more.

(tanδ (loss tangent) in the viscoelasticity measurement chart of hydrogenated block copolymer (1)) In the hydrogenated block copolymer (1) of this embodiment, in the viscoelasticity measurement graph, it is preferable that at least one peak of tan δ (loss tangent) exists at -25°C or higher and 40°C or lower. More preferably, at least one is present at -15°C to 35°C, more preferably -10°C to 30°C, still more preferably 0°C to 30°C. This peak of tan δ originates from the peak of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (1). In order to maintain the hardness of the hydrogenated block copolymer, and the wear resistance and good touch of the hydrogenated block copolymer composition of the following embodiments, it is important that the peak is in the range of -25°C to 40°C There is at least 1 in memory. As described above, the hydrogenated copolymer block (b) is obtained by hydrogenating a copolymer block including a conjugated diene monomer unit and a vinyl aromatic monomer unit. In order to have at least one peak of tanδ (loss tangent) in the range of -25°C to 40°C, it is effective to control the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio). Conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio) is preferably 75/25 to 16/84, more preferably 70/30 to 18/82, further preferably 60/40 to 25/ 75. In order to have at least one peak of tanδ (loss tangent) in the range of 0°C to 30°C, it is effective to control the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio), conjugated Diene monomer unit/vinyl aromatic monomer unit (mass ratio) is preferably 65/35 to 16/84, more preferably 60/40 to 25/75, further preferably 55/45 to 30/70 . In addition, tan δ can be measured using a viscoelasticity measuring device (manufactured by TA Instruments Co., Ltd., ARES) under the conditions of a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3° C./min. Specifically, it can be measured by the method described in the following examples.

(weight average molecular weight of hydrogenated block copolymer (1)) The weight-average molecular weight (Mw) of the hydrogenated block copolymer (1) of this embodiment is 200,000 or less, in order to obtain good abrasion resistance, MFR, From the viewpoint of the balance between hardness and particle cohesion, it is preferably from 50,000 to 190,000, more preferably from 60,000 to 180,000, and still more preferably from 70,000 to 170,000. Furthermore, in this embodiment, the weight average molecular weight of the hydrogenated block copolymer (1) is measured by gel permeation chromatography (GPC), and obtained from the measurement of commercially available standard polystyrene The calibration curve (made using the peak molecular weight of standard polystyrene) was obtained.

(Distribution of Molecular Weight Curve of Hydrogenated Block Copolymer (1)) In the GPC curve of the hydrogenated block copolymer (1) of this embodiment, the ratio (%) of the area of the molecular weight range of 10,000 to 150,000 to the area of the molecular weight range of 10,000 to 1,000,000 exceeds 50%. From the viewpoint of obtaining a good balance between wear resistance, MFR, hardness, and particle adhesion, the content is more than 50%, preferably 60-99%, and more preferably 70-95%. The more the area ratio in the range of molecular weight 10,000 to 150,000, the more the MFR can be increased and the hardness can be lowered, and the lower the ratio, the more the wear resistance can be improved and the particle adhesion can be reduced. Furthermore, the area ratio of the molecular weight of the hydrogenated block copolymer (1) in the GPC curve of the present embodiment is 10,000 to 150,000 can be controlled by the amount of polymerization initiator and coupling agent, or have an appropriate The mixture of two or more polymers with molecular weight distribution is controlled within the above numerical range.

Also, in the GPC curve of the hydrogenated block copolymer (1) of the present embodiment, the ratio (%) of the area of the molecular weight range of 200,000 to 1,000,000 to the area of the molecular weight of 10,000 to 1,000,000 is obtained From the viewpoint of the balance between abrasion resistance and particle adhesion, it is preferably at least 10%, more preferably at least 20%. The more the ratio of the area of the molecular weight range of 200,000 to 1 million, the more the wear resistance can be improved and the particle adhesion can be reduced. In particular, in order to improve abrasion resistance and particle adhesion, it is preferable that the ratio of the area of the hydrogenated block copolymer (1) with a molecular weight of 200,000 or more is in the above numerical range, more preferably the area of the range of 220,000 or more The ratio is in the above numerical range, and more preferably the ratio of the area in the range above 240,000 is in the above numerical range. In order to increase the MFR, it is preferable that the ratio of the area of the hydrogenated block copolymer (1) with a molecular weight of 1 million or less is in the above numerical range, more preferably the area of the range of 700,000 or less is in the above numerical range, and even more preferably The area within the range of 500,000 or less is the above numerical range, and more preferably the area within the range of 300,000 or less is the above numerical range. Furthermore, the area ratio of the molecular weight of the hydrogenated block copolymer (1) in the GPC curve of the present embodiment is 200,000 to 1,000,000 can be adjusted by the amount of polymerization initiator and coupling agent, or have a suitable The mixture of two or more polymers with molecular weight distribution is controlled within the above numerical range.

(Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer (1)) As the hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (1) of this embodiment, good hardness is obtained in the following hydrogenated block copolymer composition of this embodiment, In view of MFR, it is 20% or more, Preferably it is 50% or more, More preferably, it is 85% or more, More preferably, it is 92% or more. The hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (1) can be controlled by adjusting the amount of hydrogenation to control the above numerical range.

(Hydrogenation rate of aromatic double bond of vinyl aromatic compound unit in hydrogenated block copolymer (1)) There is no particular limitation on the hydrogenation rate of the aromatic double bond of the vinyl aromatic compound unit in the hydrogenated block copolymer (1) of this embodiment, but it is preferably 50% or less, more preferably 30% or less, and further Preferably it is 20% or less. Here, the hydrogenation rate of the hydrogenated block copolymer (1) can be measured using a nuclear magnetic resonance apparatus (NMR) etc.

(Crystalization peak of hydrogenated block copolymer (1)) The hydrogenated block copolymer (1) of this embodiment is preferably in a differential scanning calorimetry (DSC) chart, within the range of -25 to 80°C, there is substantially no hydrogenated copolymer block (b) The hydride of the crystallization peak. Here, "there is substantially no crystallization peak due to the hydrogenated copolymer block (b) in the range of -25 to 80°C" means that within this temperature range, no crystallization peak due to the hydrogenated copolymer block (b) appears. b) Part of the crystallization peak, or even when it is confirmed that there is a peak caused by crystallization, the crystallization peak calorific value caused by the crystallization does not reach 3 J/g, preferably it does not reach 2 J/g g, more preferably less than 1 J/g, and still more preferably no crystallization peak calorific value.

As described above, if there is substantially no crystallization peak attributable to the hydrogenated copolymer block (b) in the range of -25 to 80°C, a favorable hydrogenated block copolymer (1) according to the present embodiment can be obtained. Flexibility is preferable because it can achieve softening of the hydrogenated block copolymer composition of the present embodiment described below. In order to obtain a hydrogenated block copolymer (1) in which there is substantially no crystallization peak attributable to the hydrogenated copolymer block (b) in the range of -25 to 80°C, it is only necessary to use vinyl bonded amount adjustment or ethylene As a specific regulator for adjusting the copolymerizability of an aromatic compound and a conjugated diene, the polymerization reaction is carried out under the following conditions, and the copolymer thus obtained is subjected to a hydrogenation reaction.

(Structure of Hydrogenated Block Copolymer (1)) The structure of the hydrogenated block copolymer (1) of this embodiment is not particularly limited, and examples thereof include structures represented by the following general formula. (bc) _n , c-(bc) _n , b-(cb) _n , (bc) _m -X, (cb) _m -X, c-(ba) _n , c-(ab) _n , c-( aba) _n , c-(bab) _n , c-(bca) _n , a-(cbca) _n , ac-(ba) _n , ac-(ab) _n , ac-(ba) _n -b, [( abc) _n ] _m -X, [a-(bc) _n ] _m -X, [(ab) _n -c] _m -X, [(aba) _n -c] _m -X, [(bab) _n - c] _m -X, [(cba) _n ] _m -X, [c-(ba) _n ] _m -X, [c-(aba) _n ] _m -X, [c-(bab) _n ] _m - X In addition, in each of the above general formulas, a represents a polymer block (a) mainly composed of vinyl aromatic compound monomer units, and b represents a polymer block (a) composed of vinyl aromatic compound monomer units and conjugated diene monomers. The hydrogenated copolymer block (b) of the monomer unit, c represents the hydrogenated polymer block (c) mainly composed of the conjugated diene monomer unit. n is an integer of 1 or more, preferably an integer of 1-5. m is an integer of 2 or more, preferably an integer of 2-11. X represents the residue of a coupler or the residue of a polyfunctional initiator.

(Other examples of the structure of the hydrogenated block copolymer (1)) The hydrogenated block copolymer (1) of this embodiment may be a modified block copolymer bonded with atomic groups having specific functional groups. Also, the modified block copolymer may be a secondary modified block copolymer.

[Manufacturing method of hydrogenated block copolymer (1)] The block copolymer in the state before hydrogenation of the hydrogenated block copolymer (1) of this embodiment is obtained, for example, by using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent to make a vinyl aromatic The compound is subjected to living anionic polymerization with a conjugated diene compound.

(solvent) The hydrocarbon solvent is not limited to the following, and examples include: aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptane, Alicyclic hydrocarbons such as methyl cycloheptane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

(polymerization initiator) The polymerization initiator is not particularly limited. For example, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amine groups known to have anionic polymerization activity for vinyl aromatic compounds and conjugated dienes are generally applicable. Organic alkali metal compounds such as alkali metal compounds. The organoalkali metal compound is not limited to the following. For example, aliphatic and aromatic hydrocarbon lithium compounds with 1 to 20 carbon atoms are preferred. Compounds containing one lithium in one molecule and multiple lithium in one molecule can be applied. Lithium dilithium compounds, trilithium compounds, and tetralithium compounds. Specifically, n-propyllithium, n-butyllithium, second-butyllithium, third-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropene The reaction product of phenylbenzene and second butyl lithium, the reaction product of divinylbenzene and second butyl lithium and a small amount of 1,3-butadiene, etc. Furthermore, organic alkali metal compounds disclosed in, for example, US Patent No. 5,708,092, UK Patent No. 2,241,239, and US Patent No. 5,527,753 can also be used.

(Adjuster) For example, when using an organic alkali metal compound as a polymerization initiator to copolymerize a vinyl aromatic compound with a conjugated diene, by using a specific modifier, the ethylene originating from the conjugated diene incorporated into the polymer can be adjusted. The content of radical bonds (1,2 bonds or 3,4 bonds) or the random copolymerization of vinyl aromatic compounds and conjugated dienes. Such an adjuster is not limited to the following, and examples thereof include tertiary amine compounds, ether compounds, metal alkoxides, and the like. The regulator may be used alone or in combination of two or more.

The tertiary amine compound is not limited to the following, for example, a compound represented by the general formula R1R2R3N (where R1, R2, and R3 represent a hydrocarbon group having 1 to 20 carbons or a hydrocarbon group having a tertiary amine group) can be used. Specific examples include: trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethyl ethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperone, N,N,N',N' ',N''-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, etc.

As an ether compound, it is not limited to the following, For example, a linear ether compound, a cyclic ether compound, etc. are applicable. The linear ether compound is not limited to the following, and examples thereof include ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Dialkyl ether compounds of alcohols, dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. The cyclic ether compound is not limited to the following, for example, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane Alkanes, 2,2-bis(2-oxolane)propane, alkyl ethers of furanmethanol, etc.

The metal alkoxide is not limited to the following, and examples thereof include sodium tert-pentoxide, sodium tert-butoxide, potassium tert-pentoxide, potassium tert-butoxide, and the like.

(aggregation method) Also, for example, as a method of polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be applied. It is not limited to the following, For example, any one of batch polymerization, continuous polymerization, or a combination thereof may be used. In particular, batch polymerization is preferred in order to obtain a copolymer excellent in heat resistance. The polymerization temperature is preferably from 0°C to 180°C, more preferably from 30°C to 150°C. The polymerization time varies depending on conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. Also, as the environment of the polymerization system, an inert gas environment such as nitrogen is preferable. The polymerization pressure may be set to a pressure range in which the monomer and the solvent can be maintained in the liquid phase in the above temperature range, and is not particularly limited. Furthermore, it is preferable to prevent impurities such as water, oxygen, and carbon dioxide, which deactivate the catalyst and the active polymer, from being mixed into the polymerization system.

Also, at the end of the above-mentioned polymerization step, a necessary amount of a bifunctional or higher-functional coupling agent may be added to carry out a coupling reaction. Known ones can be used as the bifunctional coupling agent, and it is not particularly limited. Examples include: trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane Alkoxysilane compounds such as dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyl Dihalide compounds such as dibromosilane, esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. In addition, conventionally known ones can be used as the trifunctional or higher multifunctional coupling agent, and are not particularly limited. Examples include polyhydric alcohols with three or more valences, epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane and other polycyclic rings. Oxygen compounds, silicon halide compounds represented by the general formula R ₄ -nSiX _n (here, R represents a hydrocarbon group with 1 to 20 carbons, X represents a halogen, and n represents an integer of 3 to 4), such as methyl trichlorosilane , tertiary butyl trichlorosilane, silicon tetrachloride and their bromides, etc., general formula R ₄ -nSnX _n (here, R represents a hydrocarbon group with 1 to 20 carbons, X represents a halogen, and n represents 3 The tin halide compound represented by an integer of ~4), for example, polyhalogen compounds such as methyl tin trichloride, tertiary butyl tin trichloride, and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.

(modification step) As mentioned above, the hydrogenated block copolymer (1) of this embodiment may be a modified block copolymer bonded with an atomic group having a functional group. The atomic group having a functional group is preferably bonded as a step preceding the hydrogenation step described below. The above-mentioned "atomic group having a functional group" is not particularly limited, and examples include: containing at least one selected from the group consisting of hydroxyl, carboxyl, carbonyl, thiocarbonyl, acyl halide, acid anhydride, carboxylic acid, thiocarboxylic acid, Aldehyde, Thialdehyde, Carboxylate, Amide, Sulfonate, Sulfonate, Phosphate, Phosphate, Amino, Imino, Nitrile, Pyridyl, Quinolinyl, Cyclic Oxygen, thioepoxy, thio, isocyanate, isothiocyanate, silicon halide, silanol, alkoxy silicon, tin halide, boronic acid, boron-containing, borate The atomic group of the functional group in the group, the alkoxytin group, the phenyl tin group, etc. Especially preferably, it is an atomic group having at least one functional group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilyl group. The above-mentioned "atomic group having a functional group" is bonded by a modifier. The modifier is not particularly limited, and examples thereof include tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ- Valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl dimethyl phenylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidine Ketone, N,N'-dimethylpropylidene urea, N-methylpyrrolidone, etc.

The modified block copolymer is not particularly limited, and it can be obtained, for example, by anionic living polymerization, using a polymerization initiator with a functional group or an unsaturated monomer with a functional group to carry out polymerization, or at an active terminal Form a functional group, or make an addition reaction of a modifier containing a functional group. As another method, it can be obtained by reacting an organoalkali metal compound such as an organolithium compound with a block copolymer (metallation reaction), and making a modifier having a functional group react with a block copolymer to which an organoalkali metal has been added. The polymer undergoes an addition reaction. However, in the case of the latter method, a modified hydrogenated block copolymer can also be produced by performing a metallization reaction after obtaining the hydrogenated block copolymer (1), and then reacting a modifying agent. The temperature for the modification reaction is preferably 0-150°C, more preferably 20-120°C. The time required for the modification reaction varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours. Depending on the type of modifying agent used, there is also the case where the amino group etc. are converted into an organic metal salt at the stage of reacting the modifying agent. For processing, and conversion to amine groups, etc. In addition, in such a modified copolymer, a part of unmodified copolymer may be mixed in the modified copolymer.

In addition, the above-mentioned modified block copolymer may be a secondary modified block copolymer. The secondary modified block copolymer can be obtained by reacting a secondary modifier reactive with the functional group of the modified block copolymer with the modified block copolymer. The secondary modifier is not particularly limited, and examples include: modifiers having functional groups selected from carboxyl groups, acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilyl groups. Those having at least 2 functional groups selected from these functional groups. Among them, when the functional group is an acid anhydride group, one having one acid anhydride group may be used.

As described above, when the secondary modifier is reacted with the modified block copolymer, the amount of the secondary modifier used is relatively small relative to 1 equivalent of the functional group bonded to the modified block copolymer. Preferably, it is 0.3-10 mol, More preferably, it is 0.4-5 mol, More preferably, it is 0.5-4 mol. A known method can be applied to the method of reacting the modified block copolymer with the secondary modifier, and it is not particularly limited. For example, the following melt-kneading method, or the method of dissolving or dispersing-mixing each component in a solvent etc., and making it react, etc. are mentioned. Furthermore, the secondary modification is preferably performed after the hydrogenation step.

As the secondary modifier, specifically, maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, tolyl diisocyanate, tetraglycidyl -1,3-bisaminomethylcyclohexane, bis-(3-triethoxysilylpropyl)-tetrasulfide, etc.

In addition, the hydrogenated block copolymer (1) of this embodiment can be graft-modified with α,β-unsaturated carboxylic acid or its derivatives, such as its anhydride, esterified product, amidated product, and amidated product modified block copolymers. Specific examples of α,β-unsaturated carboxylic acids or derivatives thereof are not particularly limited, for example, maleic anhydride, maleic anhydride imide, acrylic acid or its esters, methacrylic acid or Its ester, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydride, etc. The added amount of the α,β-unsaturated carboxylic acid or its derivative is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass per 100 parts by mass of the hydrogenated block copolymer (1). In the case of graft modification, the reaction temperature is preferably from 100 to 300°C, more preferably from 120 to 280°C. The specific method of graft modification is not particularly limited, and for example, the method described in JP-A-62-79211 can be applied.

(hydrogenation reaction step) The hydrogenated block copolymer (1) of this embodiment is obtained by subjecting the above-mentioned non-hydrogenated non-modified or modified block copolymer to a hydrogenation reaction using a specific hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and for example, known catalysts can be used, that is, (1) metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. (2) The so-called Ziegler type hydrogenation catalyst using organic acid salts such as Ni, Co, Fe, Cr or transition metal salts such as acetylacetonate and reducing agents such as organoaluminum , (3) Homogeneous hydrogenation catalysts such as organometallic compounds of Ti, Ru, Rh, Zr, etc., such as so-called organometallic complexes. Specifically, it is not limited to the following, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1- Hydrogenation catalysts described in Publication No. 37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041. As a preferable hydrogenation catalyst, a titanocene compound, a reducing organometallic compound, or a mixture thereof may be mentioned. The titanocene compound is not limited to the following, and examples thereof include compounds described in JP-A-8-109219. Specifically, dicyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride, etc. have at least one (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fenene group. The compound of the ligand of the skeleton. The reducing organometallic compound is not limited to the following, and examples thereof include organoalkali metal compounds such as organolithium compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The hydrogenation reaction will be described. The reaction temperature is generally preferably in the temperature range of 0-200°C, more preferably in the temperature range of 30-150°C. The pressure of hydrogen used in the hydrogenation reaction is preferably from 0.1 to 15 MPa, more preferably from 0.2 to 10 MPa, and still more preferably from 0.3 to 5 MPa. The hydrogenation reaction time is usually preferably from 3 minutes to 10 hours, more preferably from 10 minutes to 5 hours. The hydrogenation reaction can be any one of a batch process, a continuous process, or a combination thereof. It is preferable to remove catalyst residue from the solution of the hydrogenated block copolymer obtained through the hydrogenation reaction as necessary, and to separate the hydrogenated block copolymer from the solution. The separation method is not limited to the following, and examples include: adding a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated modified copolymer, to the reaction liquid after hydrogenation to precipitate and recover the polymer; The method of putting the reaction liquid into hot water under stirring, removing the solvent by steam stripping and recovering it; the method of directly heating the polymer solution to distill and remove the solvent, etc. Furthermore, various stabilizers such as phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers can be added to the hydrogenated block copolymer (1) of this embodiment.

[Hydrogenated block copolymer composition] The hydrogenated block copolymer composition of the present embodiment contains the above-mentioned (1) hydrogenated block copolymer: 1 mass % to 95 mass %, and (2) at least one olefin resin: 5 mass % to 99 mass %.

((2) Olefin resin) The olefin-based resin (2) constituting the hydrogenated block copolymer composition of this embodiment will be described below. The olefin-based resin (2) is not limited to the following, for example, polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl- Homopolymers of α-olefins such as 1-butene, 4-methyl-1-pentene, and 1-octene. Further examples include: random copolymers or block copolymers containing combinations of olefins selected from ethylene, propylene, butene, pentene, hexene, octene, and the like. Specifically, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1 -hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer , propylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, propylene-1-octene-ethylene copolymer and other ethylene and /or propylene-α-olefin copolymers. In addition, copolymers with ethylene and/or propylene also include copolymers with other unsaturated monomers. The above-mentioned copolymers with other unsaturated monomers are not limited to the following, for example, ethylene and/or propylene and acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl Copolymers of methyl acrylate, maleic anhydride, arylmaleimide, alkylmaleimide and other unsaturated organic acids or their derivatives; ethylene and/or propylene and vinyl acetate Copolymers of vinyl esters such as esters; furthermore, ethylene and/or propylene with dicyclopentadiene, 4-ethylidene-2-northene, 4-methyl-1,4-hexadiene, 5-methanol Copolymers of non-conjugated dienes such as 1,4-hexadiene, etc. The (2) olefin-based resin preferably contains at least one polypropylene-based resin.

Also, the olefin-based resin (2) may be modified with a specific functional group. It does not specifically limit as a functional group, For example, an epoxy group, a carboxyl group, an acid anhydride, a hydroxyl group etc. are mentioned. Although it does not specifically limit as a functional group containing compound or modifier used for modifying olefin resin (2), For example, the following compounds are mentioned. For example, unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether, or maleic acid, fumaric acid, icon acid, unsaturated organic acids such as methylmaleic acid, allylsuccinic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, etc. Others are not particularly limited, and examples thereof include ionomers, chlorinated polyolefins, and the like.

The olefin-based resin (2) is preferably a polypropylene homopolymer from the standpoint of economical efficiency, improved compatibility in the hydrogenated block copolymer composition of the present embodiment, and high transparency. Polypropylene-based resins such as ethylene-propylene random or block copolymers. In particular, an ethylene-propylene random copolymer is more preferable from the viewpoint of transparency and flexibility. The olefin-based resin (2) may contain only one kind of material alone, or two or more kinds may be used in combination.

The hydrogenated block copolymer composition of this embodiment is a hydrogenated block copolymer (1) and at least one olefin-based resin (2), and the content of the hydrogenated block copolymer (1) is 1% by mass to 95% by mass Below, more preferably 1 mass % or more and 90 mass % or less, More preferably, it is 1 mass % or more and 85 mass % or less. When the content of the hydrogenated block copolymer (1) is 1% by mass or more, the abrasion resistance of the hydrogenated block copolymer composition tends to increase and the hardness tends to decrease. On the other hand, when the content of the hydrogenated block copolymer (1) is 95% by mass or less, the abrasion resistance of the hydrogenated block copolymer composition tends to improve.

In addition to the hydrogenated block copolymer (1) and polyolefin resin (2) mentioned above, the hydrogenated block copolymer composition of this embodiment may also contain any rubber softener or modifier, additives, and the like. The softener for rubber softens the hydrogenated block copolymer composition of this embodiment and imparts fluidity (moldability). The softener for rubber is not limited to the following, for example, mineral oil or liquid or low molecular weight synthetic softener can be used, especially naphthenic and/or paraffinic processing oil or extender oil. Mineral oil-based softener for rubber is a mixture of aromatic rings, naphthenic rings and paraffin chains. Those whose carbon number in the paraffin chain accounts for more than 50% of the total carbons are called paraffin-based, and the carbon number of the naphthene ring is 30-45. % are called naphthenic series, and those with more than 30% aromatic carbons are called aromatic series. As the synthetic softener, for example, polybutene, low-molecular-weight polybutadiene, liquid paraffin, etc. can be used, and the above-mentioned softener for mineral oil-based rubber is more preferable. When the hydrogenated block copolymer composition of this embodiment is required to have high heat resistance and mechanical properties, it is preferable that the applied mineral oil-based rubber softener has a dynamic viscosity of 60 cst or more at 40°C, preferably It is above 120 cst. The rubber softener may be used alone or in combination of two or more. The modifier has the function of improving the damage resistance of the surface of the hydrogenated block copolymer composition of this embodiment or improving the adhesion. The modifying agent is not limited to the following, for example, organopolysiloxane can be used. It exerts the surface modification effect of the hydrogenated block copolymer composition and functions as an abrasion resistance improving auxiliary agent. As the form of the modifying agent, it can be any of low-viscosity liquid to high-viscosity liquid or solid, and it is necessary to ensure good dispersibility in the hydrogenated block copolymer composition of this embodiment. From the point of view, it is preferably a liquid, that is, silicone oil. Furthermore, the kinematic viscosity is preferably 90 cst or more, more preferably 1000 cst or more, from the viewpoint of suppressing exudation of polysiloxane itself. The specific examples of polysiloxane are not limited to the following. Modified, alcohol modified, amino modified, epoxy modified and other modified silicone oils. In terms of its high effect as an abrasion resistance improving auxiliary agent, dimethylpolysiloxane is preferred, but not particularly limited. These organopolysiloxanes may be used alone or in combination of two or more. As additives, fillers, lubricants, mold release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents, colorants, as long as they are thermoplastic There are no particular restrictions on the usual use in the formulation of resins or rubbery polymers. The filler is not limited to the following, for example, silicon dioxide, talc, mica, calcium silicate, aluminum magnesium carbonate, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, hydroxide Aluminum, calcium sulfate, barium sulfate and other inorganic fillers, carbon black and other organic fillers. The lubricant is not limited to the following, and examples thereof include stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylidenebisstearamide, and the like. It is not limited to the following as a plasticizer, For example, organopolysiloxane, mineral oil, etc. are mentioned. It is not limited to the following as an antioxidant, For example, a hindered phenol type antioxidant is mentioned. The heat stabilizer is not limited to the following, and examples thereof include phosphorus-based, sulfur-based, and amine-based heat stabilizers. It is not limited to the following as a light stabilizer, For example, a hindered amine light stabilizer is mentioned. The ultraviolet absorber is not limited to the following, and examples thereof include benzotriazole-based ultraviolet absorbers. The reinforcing agent is not limited to the following, and examples thereof include organic fibers, glass fibers, carbon fibers, metal whiskers, and the like. It is not limited to the following as a coloring agent, For example, titanium oxide, iron oxide, carbon black, etc. are mentioned. Other examples include those described in "Rubber-Plastic Compounded Drugs" (edited by Rubber Digest Co., Ltd.).

The hydrogenated block copolymer composition of the present embodiment can be produced by a previously known method. The production method of the hydrogenated block copolymer composition of this embodiment is not limited to the following, for example, it can be used: using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-way kneader, a multi-screw extruder A mixer such as a discharge machine, a method of melting and kneading each component (the above-mentioned hydrogenated block copolymer (1), polyolefin resin (2), and other additives); a method of removing the solvent by heating after dissolving or dispersing and mixing each component wait. In particular, the melt-kneading method with an extruder is preferable from the viewpoint of productivity and excellent kneading properties. The shape of the hydrogenated block copolymer composition of the present embodiment is not limited to the following, and may be in any shape such as granular, sheet, strand, or small sheet, for example. Also, molded products can be produced directly after melting and kneading.

[Molded article using hydrogenated block copolymer composition] Molding system of this embodiment is a molded body of the hydrogenated block copolymer composition of this embodiment. The hydrogenated block copolymer composition of this embodiment is not particularly limited, for example, it can be formed by extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder gel molding , foam molding, lamination molding, calender molding, blow molding, etc., and process them into practically useful moldings. The molded article of this embodiment is not particularly limited, and examples thereof include sheets, films, injection molded articles of various shapes, hollow molded articles, pressure molded articles, vacuum formed articles, extrusion molded articles, and foam molded articles. , non-woven fabric or fibrous shaped body, synthetic leather and other various shaped bodies. Such molded articles can be used, for example, in automotive parts, food packaging materials, medical devices, home appliance components, electronic device components, construction materials, industrial parts, household goods, toy materials, shoe materials, fiber materials, and the like.

The automotive parts are not limited to the following, and examples include: side moldings, gaskets, gear knobs, weather strips, window frames and their sealants, armrests, auxiliary grips, door handles, handles, and console boxes , Headrests, dashboards, bumpers, spoilers, airbag covers, etc. The medical equipment is not limited to the following, and examples include medical tubes, medical hoses, catheters, blood collection bags, transfusion bags, platelet storage bags, artificial dialysis bags, and the like. It is not limited to the following as a building material, For example, a wall material, a floor material, etc. are mentioned. Others are not particularly limited, and examples thereof include industrial hoses, food hoses, vacuum cleaner hoses, electric cooling seals, electric wires, and other various covering materials, covering materials for grips, soft dolls, and the like. Processes such as foaming, powdering, stretching, bonding, printing, painting, and plating can be appropriately applied to the molded body of this embodiment. The hydrogenated block copolymer composition of this embodiment exhibits excellent effects of flexibility, low rebound elasticity, transparency, and kink resistance, so it is extremely useful as a material for hollow molded objects such as hoses and tubes.

(reinforcing filler formulation) In the hydrogenated block copolymer or the hydrogenated block copolymer composition (hereinafter, sometimes referred to as component (A)) of this embodiment, a filler selected from silica-based inorganic fillers, metal oxides, and metal hydroxides can be formulated. At least one reinforcing filler (hereinafter, sometimes referred to as component (C)) among compound, metal carbonate, and carbon black to prepare a reinforcing filler formulation. The compounded amount of the component (C) in the reinforcing filler formulation is preferably 0.5-100 parts by mass, more preferably 5-100 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition , and more preferably 20 to 80 parts by mass. In the case of using the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)) of this embodiment to prepare the aforementioned reinforcing filler formulation, it is preferable to further include 100 mass of component (A) The parts are 0 to 500 parts by mass, preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass of a thermoplastic resin different from the hydrogenated block copolymer of the present embodiment and the olefin-based resin (2) above and /or a rubbery polymer (hereinafter, may be referred to as component (B)).

Examples of the above-mentioned thermoplastic resin and/or rubber-like polymer (component (B)) include a combination of a conjugated diene monomer and a vinyl aromatic monomer having a vinyl aromatic monomer unit content of more than 60% by mass. Segment copolymer resin and its hydrogenated product (but different from the hydrogenated block copolymer (A) of this embodiment); the polymer of the above-mentioned vinyl aromatic monomer; the above-mentioned vinyl aromatic monomer and other vinyl monomers ( For example, ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and methyl acrylate and other acrylates, methacrylic acid and methyl methacrylate and other methacrylates, acrylonitrile, methacrylic Nitrile, etc.) copolymer resin; rubber modified styrene resin (HIPS); acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resin (MBS); Polyethylene; ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolyzate, etc., containing ethylene and other copolymerizable monomers Copolymers with an ethylene content of more than 50% by mass; polyethylene-based resins such as ethylene-acrylic acid ionomers or chlorinated polyethylene; polypropylene; propylene-ethylene copolymers, propylene-ethyl acrylate copolymers or chlorinated poly Polypropylene-based resins such as propylene, cyclic olefin-based resins such as ethylene-northene resins, polybutene-based resins, polyvinyl chloride-based resins, polyvinyl acetate-based resins and their hydrolyzates, etc., including propylene and other copolymerizable resins Copolymers with a propylene content of 50 mass% or more of the monomers; polymers of acrylic acid and its esters or amides; polyacrylate resins; polymers of acrylonitrile and/or methacrylonitrile; containing acrylonitrile monomers Copolymers containing more than 50% by mass of acrylonitrile monomers with other copolymerizable monomers, i.e. nitrile resins; Nylon-46, Nylon-6, Nylon-66, Nylon-610, Nylon-11, Nylon-12 , nylon-6, nylon-12 copolymers and other polyamide resins; polyester resins; thermoplastic polyurethane resins; poly-4,4'-dioxydiphenyl-2,2' -Polycarbonate-based polymers such as propane carbonate; thermoplastic polymers such as polyether or polyarylene; polyoxymethylene-based resins; poly(2,6-dimethyl-1,4-phenylene) ether and other polycarbonates Phenyl ether resins; polyphenylene sulfide, polyphenylene sulfide, poly4,4'-diphenylene sulfide and other polyphenylene sulfide resins; polyarylate resins; polyetherketone polymers or copolymers; polyketone resins; Fluorine-based resins; polyoxybenzoyl-based polymers; polyimide-based resins; polybutadiene-based resins such as 1,2-polybutadiene and trans-polybutadiene, etc. These components (B) may be bonded with atomic groups containing polar groups such as hydroxyl groups, epoxy groups, amine groups, carboxylic acid groups, and acid anhydride groups.

The silica-based inorganic filler used as a reinforcing filler (ingredient (C)) is a solid particle with the chemical formula _SiO2 as the main component of the structural unit, for example: silica, clay, talc, kaolin, mica , Wollastonite, montmorillonite, zeolite, glass fiber and other inorganic fibrous substances. In addition, a silica-based inorganic filler that hydrophobizes the surface, or a mixture of a silica-based inorganic filler and an inorganic filler other than silica-based fillers may also be used. As the silica-based inorganic filler, silica and glass fiber are preferred. As silica, what is called dry-process white carbon, wet-process white carbon, synthetic silicate white carbon, colloidal silica, etc. can be used. The silica-based inorganic filler is preferably one with an average particle size of 0.01-150 μm. In order to disperse the silica-based inorganic filler in the reinforcing filler formulation and fully exert its addition effect, the average dispersed particle diameter is Preferably it is 0.05-1 μm, more preferably 0.05-0.5 μm.

The metal oxide used as a reinforcing filler (ingredient (C)) is a solid particle with the chemical formula MxOy (M is a metal atom, and x and y are integers from 1 to 6) as the main component of the structural unit, such as alumina , titanium oxide, magnesium oxide, zinc oxide, etc. In addition, a mixture of a metal oxide and an inorganic filler other than the metal oxide can be used. Metal hydroxide aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, Hydrated inorganic fillers such as hydrates of tin oxide and hydrates of inorganic metal compounds such as borax, among which magnesium hydroxide and aluminum hydroxide are preferred. Calcium carbonate, magnesium carbonate, etc. are mentioned as a metal carbonate used as a reinforcing filler. Also, as a reinforcing filler, FT (Fine thermal, fine particle thermal cracking furnace black), SRF (semi-reinforcing furnace, semi-reinforcing furnace black), FEF (fast extrusion furnace, fast extrusion furnace black), HAF (high abrasion furnace, high wear-resistant furnace black), ISAF (Intermediate super abrasion furnace, super wear-resistant furnace black), SAF (super abrasion furnace, super wear-resistant furnace black) and other grades of carbon black, preferably nitrogen adsorption Carbon black with a specific surface area of 50 mg/g or more and a DBP (dibutyl phthalate) oil absorption of 80 mL/100 g.

A silane coupling agent (hereinafter sometimes referred to as component (D)) can be used in a reinforcing filler formulation using the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment. The silane coupling agent is used to make the interaction between the hydrogenated block copolymer and the reinforcing filler close, and it has affinity or bonding to one or both of the hydrogenated block copolymer and the reinforcing filler Compounds that are the basis of sex. As a preferred silane coupling agent, it can be listed: two or more mercapto groups and/or sulfur are linked together with silanol groups or alkoxysilanes and have polysulfide bonds. Specifically, bis-[3-(three Ethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl) -Ethyl]-tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-triethoxysilylpropyl-N,N-dimethylthioamidoformyl tetrasulfide, 3- Triethoxysilylpropylbenzothiazole tetrasulfide, etc. From the viewpoint of obtaining the desired effect, the blending amount of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass relative to the reinforcing filler formulation. quality%.

The reinforcing filler formulation containing the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment and the reinforcing filler can be vulcanized with a vulcanizing agent, that is, cross-linked to form a vulcanized composition. As the vulcanizing agent, free radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, sulfur compounds (sulfur monochloride, sulfur dichloride, disulfide ether compounds, polymer polysulfide compounds, etc.). The usage-amount of a vulcanizing agent is 0.01-20 mass parts normally with respect to 100 mass parts of hydrogenated block copolymers or a hydrogenated block copolymer composition, Preferably it is the ratio of 0.1-15 mass parts. As an organic peroxide used as a vulcanizing agent (hereinafter sometimes referred to as component (E)), in terms of odor or coking stability (it does not cross-link under the conditions when the components are mixed, but it is a cross-linking reaction From the point of view of rapid cross-linking characteristics under certain conditions), 2,5-dimethyl-2,5-bis-(tert-butylperoxy)hexane, 2,5-dimethyl- 2,5-bis-(tertiary butylperoxy)hexyne-3, 1,3-bis(tertiary butylperoxyisopropyl)benzene, 1,1-bis(tertiary butylperoxy Oxy)-3,3,5-trimethylcyclohexane, 4,4-bis(tert-butylperoxy)-n-butyl valerate, di-tert-butyl peroxide. In addition to the above, you can also use: dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, peroxide Oxidized tert-butyl benzoate, tert-butyl peroxy isopropyl carbonate, diacetyl peroxide, lauryl peroxide, tert-butyl cumyl peroxide, etc.

Also, during vulcanization, as a vulcanization accelerator (hereinafter, sometimes referred to as component (F)), sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based series, thiazole series, thiourea series, dithiocarbamate series compounds, etc. Moreover, zinc white, stearic acid, etc. can also be used as a vulcanization auxiliary agent in an optional amount. In addition, when using the above-mentioned organic peroxides to crosslink the reinforcing filler formulations, especially sulfur that can also be used as a vulcanization accelerator together with organic peroxides; p-quinonedioxime, p,p'-benzo Acyl quinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-phenylene butene Auxiliaries for peroxygen crosslinking such as diimide (hereinafter, sometimes referred to as component (G)); divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol di Multifunctional methacrylate monomers such as methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate; vinyl butyrate, stearin Polyfunctional vinyl monomers such as vinyl acid esters (hereinafter, may be referred to as component (H)) and the like. Such a vulcanization accelerator is usually used in a ratio of preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition. As a method of vulcanizing the reinforcing filler formulation using a vulcanizing agent, the previously implemented method can be applied, for example, vulcanizing at a temperature of 120-200°C, preferably 140-180°C. Vulcanized reinforcing filler formulations exhibit heat resistance, flex resistance, or oil resistance in the vulcanized state.

In order to improve the processability of the reinforcing filler formulation, a rubber softener (hereinafter sometimes referred to as component (I)) may be formulated. Mineral oil, or liquid or low-molecular-weight synthetic softeners are suitable among rubber softeners. Among them, naphthenic and/or paraffinic processing oils or extender oils generally used for softening, compatibilizing, and improving processability of rubber are preferred. Mineral oil-based softener for rubber is a mixture of aromatic rings, naphthenic rings and paraffin chains. Those whose carbon number in the paraffin chain accounts for more than 50% of the total carbons are called paraffin-based, and the carbon number of the naphthene ring is 30-45. % are called naphthenic series, and those with more than 30% aromatic carbons are called aromatic series. Synthetic softeners may be used in the reinforcing filler formulations, polybutene, low molecular weight polybutadiene, liquid paraffin, etc. may be used. However, the above-mentioned softener for mineral oil-based rubber is preferable. The compounding amount of the rubber softener (component (I)) in the reinforcing filler formulation is preferably 0 to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). 100 mass parts, More preferably, it is 1-90 mass parts, More preferably, it is 30-90 mass parts. When the amount of the softener for rubber exceeds 100 parts by mass, bleeding is likely to occur, and there is a possibility of stickiness on the surface of the composition.

The reinforcing filler formulation containing the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment can be suitably used as a building material, an electric wire covering material, a vibration damping material, and the like. Moreover, its vulcanized composition can exhibit its characteristics and is suitable for materials such as tires, anti-vibration rubber, belts, industrial products, shoes, and foams.

(cross-linked) The hydrogenated block copolymer or hydrogenated block copolymer composition of this embodiment can be cross-linked in the presence of a vulcanizing agent to form a cross-linked product, that is, a cross-linked hydrogenated block copolymer or a combination of cross-linked hydrogenated block copolymers thing. By crosslinking the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment, heat resistance [high temperature C-Set (compression set, compression set)] and bending resistance can be improved. In the case of preparing a cross-linked product of the above-mentioned reinforcing filler formulation containing the hydrogenated block copolymer composition of this embodiment, especially the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)) The compounding ratio of thermoplastic resin and/or rubber-like polymer (component (B)) is based on the mass ratio of component (A)/component (B), preferably 10/90 to 100/0, more preferably 20/ 80-90/10, more preferably 30/70-80/20.

In this embodiment, the method of cross-linking is not particularly limited, but it is preferable to perform so-called "dynamic cross-linking". The so-called dynamic crosslinking refers to the method of mixing various formulations under the temperature conditions of the vulcanizing agent reaction in the molten state, thereby causing dispersion and crosslinking to occur simultaneously. In the literature of A.Y. Coran et al. (Rub. Chem. and Technol. vol. 53. 141-(1980)) is described in detail. Dynamic crosslinking is usually carried out using a closed kneader such as a Banbury mixer or a pressurized kneader, or a single-screw or twin-screw extruder. The kneading temperature is usually 130-300°C, preferably 150-250°C, and the kneading time is usually 1-30 minutes. As a vulcanizing agent used in dynamic crosslinking, an organic peroxide or phenolic resin crosslinking agent can be used, and its usage is usually relative to the hydrogenated block copolymer or the hydrogenated block copolymer composition (ingredient (A)) 100 The mass parts are 0.01 to 15 mass parts, preferably 0.04 to 10 mass parts. As the organic peroxide used as a vulcanizing agent, the above-mentioned component (E) can be used. When performing crosslinking using an organic peroxide, the above-mentioned component (F) may be used as a vulcanization accelerator, and the above-mentioned component (G) or the above-mentioned component (H) may be used in combination. The usage-amount of these vulcanization accelerators is 0.01-20 mass parts normally with respect to 100 mass parts of hydrogenated block copolymers or a hydrogenated block copolymer composition (component (A)), Preferably it is 0.1-15 mass parts.

In the cross-linked product using the hydrogenated block copolymer of this embodiment or the hydrogenated block copolymer composition (component (A)), a softener and a heat-resistant stabilizer can be formulated as needed within the range that does not impair the purpose , antistatic agent, weather stabilizer, antiaging agent, filler, colorant, lubricant and other additives. The above-mentioned component (I) can be used as a softener formulated to adjust the hardness or fluidity of the final product. The softener may be added when kneading the components, or it may be contained in the copolymer in advance when the hydrogenated block copolymer is produced, that is, an oil-extended rubber can be prepared. The amount of the softener to be added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass. Moreover, as a filler, the above-mentioned component (C) which is a reinforcing filler can be used. The amount of the filler to be added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass. It is recommended that the above-mentioned cross-linked product has a gel content (excluding insoluble components such as inorganic fillers, etc.) of preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass. The dynamic cross-linking is carried out by mass %. Regarding the gel content, reflux 1 g of the cross-linked product with a Soxhlet extractor for 10 hours using boiling xylene, filter the residue with an 80-mesh wire mesh, and measure the dry mass (g) of the insoluble matter remaining on the mesh Then, the ratio (mass %) of the insoluble matter to 1 g of the sample was obtained, and this ratio was defined as the gel content. The gel content can be controlled by adjusting the type or amount of vulcanizing agent, and the conditions during vulcanization (temperature, residence time, shear, etc.). The above-mentioned cross-linked product can be applied to tires, anti-vibration rubber, belts, industrial products, footwear, foam, etc. like the vulcanized composition of the reinforcing filler formulation, and can also be used as a material for medical devices or food packaging materials. [Example]

Hereinafter, specific examples and comparative examples will be given to describe this embodiment in detail, but this embodiment is not limited to the following examples and comparative examples. Various physical properties were measured by the methods shown below.

[Specific methods for the structure of copolymers, and methods for measuring physical properties] ((1) Content of total vinyl aromatic compound (styrene) monomer units in hydrogenated block copolymer (1)) Using the block copolymer before hydrogenation, the content of the total vinyl aromatic compound (styrene) monomer unit was measured by an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).

((2) Content of polymer block (polystyrene block) mainly composed of vinyl aromatic compound monomer unit in hydrogenated block copolymer (1)) Using a block copolymer before hydrogenation, it was measured using a nuclear magnetic resonance apparatus (NMR) (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as "NMR method").

((3-1) Vinyl bond amount in hydrogenated block copolymer (1)) Using the block copolymer before hydrogenation, it measured using the infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-4100). The amount of vinyl bonds in the copolymer was calculated by the Hampton method.

((3-2) Amount of vinyl bonds in copolymer block (b)) Measurement was performed using an infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-4100) using a block copolymer before hydrogenation which was sampled immediately before polymerizing the polymer block (c). The amount of vinyl bonds in the copolymer block (b) was calculated by the Hampton method.

((3-3) Vinyl bond amount in polymer block (c)) Calculated from the value of the amount of vinyl bonds in (3-1) and (3-2) above.

((4) Weight average molecular weight of hydrogenated block copolymer (1)) The weight average molecular weight of the hydrogenated block copolymer (1) was measured by GPC [device: HLC-82209PC (manufactured by Tosoh Corporation), column: TSKgeguard column SuperHZ-L (4.6 mm×20 cm)×3 pieces]. As the solvent, tetrahydrofuran was used. The measurement is carried out at a temperature of 35°C. The weight-average molecular weight was determined by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene to obtain the molecular weight of the peak of the chromatogram. Furthermore, when there are multiple peaks in the chromatogram, the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram) is taken as the weight average molecular weight. Moreover, the weight average molecular weight immediately before adding ethyl benzoate was also measured. As a measurement method, for those without ethyl benzoate, it is calculated from the GPC of the polymer obtained by inactivating the polymer sampled immediately before the addition of ethyl benzoate with methanol, and for those with ethyl benzoate added, use The produced hydrogenated block copolymer (1) was measured by GPC. The molecular weight distribution was also measured by GPC in the same manner.

(5) The ratio (%) of the area of the molecular weight range of 10,000 to 150,000 to the area of the molecular weight range of 10,000 to 1 million in the GPC curve of the hydrogenated block copolymer (1), 200,000 to 100 The ratio of the area of the following range to the area of the range of molecular weight 10,000 to 1,000,000 (%)) Measurement was carried out by GPC [device: HLC-82209PC (manufactured by Tosoh), column: TSKgeguard column SuperHZ-L (4.6 mm×20 cm)×3]. As the solvent, tetrahydrofuran was used. The measurement is carried out at a temperature of 35°C. The area value (%) of the molecular weight of the hydrogenated block copolymer (1) in the range of 10,000 to 150,000 is the area value (%) of the hydrogenated block copolymer (1) with a molecular weight of 10,000 to 150,000 in the GPC curve. The value obtained from the ratio of the area value of the range to the area value of the range of molecular weight from 10,000 to 1,000,000. The area value (%) of the molecular weight in the range of 200,000 to 1 million of the hydrogenated block copolymer (1) refers to the range of the molecular weight of the hydrogenated block copolymer (1) from 200,000 to 1 million in the GPC curve The value obtained from the ratio of the area value of the molecular weight to the area value of the molecular weight range of 10,000 to 1,000,000.

((6) Hydrogenation rate of the double bond of the conjugated diene monomer unit of the hydrogenated block copolymer (1)) Using the hydrogenated block copolymer, the hydrogenation rate of the double bond of the conjugated diene monomer unit was measured using a nuclear magnetic resonance apparatus (manufactured by JEOL RESONANCE, ECS400).

((7) Content of vinyl aromatic compound monomer unit in copolymer block (b)) Using the block copolymer before hydrogenation as a sample, the method described in using a nuclear magnetic resonance apparatus (NMR) (Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as "NMR method ") measured hydrogenated block copolymer (one) in the total vinyl aromatic compound (styrene) monomer unit content and hydrogenated block copolymer (one) in the vinyl aromatic compound monomer unit The difference in the content of the polymer block in the main body was calculated.

[Measurement method of characteristics] ((1) tanδ peak temperature) First, the "press-molded sheet" manufactured as follows was cut into a size of 12.5 mm in width and 40 mm in length, and used as a sample for measurement. Next, set the sample for measurement in the torsional geometry of the device ARES (manufactured by TA Instruments Co., Ltd., trade name), at an effective measurement length of 25 mm, a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3°C/min. Obtained under the conditions. The tan δ peak temperature is a value obtained from the peak detected by automatic measurement by RSI Orchestrator (manufactured by TA Instruments Co., Ltd., trade name).

((2) Hardness) According to JIS K6253, the instant value and the value after 10 seconds were measured with a type A hardness tester. Measure the hardness value at the moment when the probe of the hardness tester is lowered onto the sample, and the hardness value 10 seconds after it is lowered. In the following Tables 1 and 2, they are described as hardness (JIS-A, instant) and hardness (JIS-A, 10 s), respectively. The hardness value is preferably 96 or less.

((3) Melt flow rate (MFR, unit: g/10 minutes)) According to JIS K7210, the measurement was carried out under the conditions of a temperature of 230°C and a load of 2.16 kg. In addition, the score is described as follows: MFR value less than 25 (g/10 minutes) is set as 0 point, less than 25-35 (g/10 minutes) is set as 1 point, less than 35-45 (g/10 minutes) ) was set as 2 points, and 45 (g/10 minutes or more) was set as 3 points.

((4) Abrasion resistance) Using a Gakushin-type friction tester (manufactured by TESTER SANGYO Co., Ltd., AB-301 type), rubbing cloth No. 3 (canequim No. 3) cotton with a load of 500 g is applied to the sheet formed by the following [injection molding] Production] and the surface of the formed sheet (textured surface) is rubbed, and the volume reduction after rubbing is judged according to the following criteria. ◎(3 points): After rubbing 10,000 times, the volume loss is 0.01 ml or less ○ (2 points): After rubbing 10,000 times, the amount of volume loss is more than 0.01 ml and less than 0.1 ml △(1 point): After rubbing 10,000 times, the volume loss is more than 0.1 ml and less than 0.2 ml × (0 points): After rubbing 10,000 times, the volume reduction is more than 0.2 ml

((5) Ease of drawing strands (extrusion formability)) Using the following hydrogenated block copolymer composition, the draw wire of the strand extruded through the die nozzle of the single-screw extruder TEX-30 type vent hole manufactured by Nippon Steel Works Co., Ltd. was visually evaluated on a 3-point scale ease. Those who can stretch the strands at a high speed are evaluated as "3", those who are easily broken when stretched at a high speed but not broken when stretched at a low speed are rated as "2", and those who stretch the strands at a low speed are rated as "3". The case where the thread was easily broken was rated as "1". The larger the number of the three grade evaluations, the better the extrusion formability.

((6) Blocking resistance of particles) Blocking resistance was measured by the following method. Put 60 g of sample particles of the same shape (cylindrical shape with a diameter of about 3 mm×3 mm) containing hydrogenated block copolymer into a metal cylinder with a diameter of 5 cm, and place a weight of 1160 g on it. In this state, after heating for 20 hours in a Gell oven heated to 42° C., the adhesion state of the particles in the cylinder was observed. Specifically, since the pellets taken out from the cylinder disintegrated (among them, those with poor blocking resistance remained in the form of pellets and did not collapse), so the weight of the pellets containing more than three pellets was measured to obtain the weight of the pellets. The ratio (%) of the weight relative to the total weight of the pellet (60 g). Whether the blocking resistance is excellent or not is evaluated based on the following criteria. In addition, the evaluation was performed after adding calcium stearate equivalent to 1500 ppm to each sample granule. 3: Disintegration, the block containing more than 3 particles does not reach 50% of the total mass 2: Disintegration, the block containing more than 3 particles is more than 50% of the total mass 1: Tightened, not collapsed at all

[Manufacture of hydrogenated block copolymer] (Preparation of hydrogenation catalyst) The hydrogenation catalyst used in the production of the hydrogenated block copolymer in the following Examples and Comparative Examples was prepared by the following method. The reaction vessel equipped with a stirring device was replaced with nitrogen in advance, and 1 liter of dry and purified cyclohexane was added thereto. Next, 100 millimoles of bis(η5-cyclopentadienyl)titanium dichloride was added. While fully stirring it, a n-hexane solution containing 200 mmoles of trimethylaluminum was added, and the reaction was allowed to take place at room temperature for about 3 days. Thereby a hydrogenation catalyst is obtained.

＜Hydrogenated block copolymer＞ The hydrogenated block copolymers (1)-1 to (1)-30, (1)-A to (1)-G constituting the hydrogenated block copolymer composition were prepared in the following manner.

[Example 1] (Hydrogenated block copolymer (1)-1) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-1. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-1 was 98%. Other properties are shown in Table 1.

[Example 2] (Hydrogenated block copolymer (1)-2) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, 0.097 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 0.9 moles of N,N,N',N'-tetramethylethylenedioxide per 1 mole of n-butyllithium were added. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.048 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 21% by mass, and a weight average molecular weight of 131,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-2. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-2 was 96%. Other properties are shown in Table 1.

[Example 3] (Hydrogenated block copolymer (1)-3) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 0.9 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 21% by mass, and a weight average molecular weight of 120,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-3. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-3 was 98%. Other properties are shown in Table 1.

[Example 4] (Hydrogenated block copolymer (1)-4) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide were added to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-4. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-4 was 97%. Other properties are shown in Table 1.

[Example 5] (Hydrogenated block copolymer (1)-5) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 39 parts by mass of butadiene and 57 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 61% by mass, a polystyrene block content of 4% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-5. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-5 was 97%. Other properties are shown in Table 1.

[Example 6] (Hydrogenated block copolymer (1)-6) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 41 parts by mass of butadiene and 59 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol 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 0% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-6. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-6 was 97%. Other properties are shown in Table 1.

[Example 7] (Hydrogenated block copolymer (1)-7) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 36 parts by mass of butadiene and 51 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added, and polymerization was carried out at 60° C. for 10 minutes. 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. Regarding the block copolymer obtained as described above, the styrene content is 61% by mass, the polystyrene block content is 10% by mass, and the vinyl bond amount is 52% by mass (the vinyl group of the copolymer block (b) The bonding amount is 51% by mass, the vinyl bonding amount of the polymer block (c) is 70% by mass), and the weight average molecular weight is 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-7. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-7 was 95%. Other properties are shown in Table 1.

[Example 8] (Hydrogenated block copolymer (1)-8) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.099 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of butadiene was added and polymerized at 60° C. for 2 hours. 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. Regarding the block copolymer obtained as described above, the styrene content is 57% by mass, the polystyrene block content is 10% by mass, and the vinyl bond amount is 53% by mass (the vinyl group of the copolymer block (b) The bonding amount is 51% by mass, the vinyl bonding amount of the polymer block (c) is 70% by mass), and the weight average molecular weight is 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the copolymer to obtain a hydrogenated block copolymer Object (1)-8. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-8 was 98%. Other properties are shown in Table 1.

[Example 9] (Hydrogenated block copolymer (1)-9) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.101 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of butadiene was added and polymerized at 60° C. for 2 hours. 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. Regarding the block copolymer obtained as described above, the styrene content is 51% by mass, the polystyrene block content is 10% by mass, and the vinyl bond amount is 55% by mass (the vinyl group of the copolymer block (b) The bonding amount is 51% by mass, the vinyl bonding amount of the polymer block (c) is 70% by mass), and the weight average molecular weight is 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-9. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-9 was 97%. Other properties are shown in Table 1.

[Example 10] (Hydrogenated block copolymer (1)-10) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide were added to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 126,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-10. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-10 was 96%. Other properties are shown in Table 1.

[Example 11] (Hydrogenated block copolymer (1)-11) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide were added to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.225 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 152,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-11. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-11 was 98%. Other properties are shown in Table 2.

[Example 12] (Hydrogenated block copolymer (1)-12) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.2 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.02 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 29% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-12. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-12 was 95%. Other properties are shown in Table 2.

[Example 13] (Hydrogenated block copolymer (1)-13) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.5 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.06 mol of sodium pentapentoxide relative to 1 mol of n-butyl lithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 40% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-13. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-13 was 95%. Other properties are shown in Table 2.

[Example 14] (Hydrogenated block copolymer (1)-14) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-14. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-14 was 86%. Other properties are shown in Table 2.

[Example 15] (Hydrogenated block copolymer (1)-15) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-15. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-15 was 90%. Other properties are shown in Table 2.

[Example 16] (Hydrogenated block copolymer (1)-16) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-16. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-16 was 60%. Other properties are shown in Table 2.

[Example 17] (Hydrogenated block copolymer (1)-17) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-17. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-17 was 40%. Other properties are shown in Table 2.

[Example 18] (Hydrogenated block copolymer (1)-18) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.102 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 52 parts by mass of butadiene and 38 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 48% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 60% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-18. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-18 was 97%. Other properties are shown in Table 2.

[Example 19] (Hydrogenated block copolymer (1)-19) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 19 parts by mass of butadiene and 71 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 81% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 40% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-19. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-19 was 96%. Other properties are shown in Table 2.

[Example 20] (Hydrogenated block copolymer (1)-20) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 39.6 parts by mass of butadiene and 50.4 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol 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 10% by mass, a vinyl bond amount of 55% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-20. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-20 was 96%. Other properties are shown in Table 2.

[Example 21] (Hydrogenated block copolymer (1)-21) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 42.3 parts by mass of butadiene and 47.7 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 52% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-21. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-21 was 96%. Other properties are shown in Table 3.

[Example 22] (Hydrogenated block copolymer (1)-22) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.045 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 136,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-22. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-22 was 96%. Other properties are shown in Table 3.

[Example 23] (Hydrogenated block copolymer (1)-23) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.06 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 140,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-23. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-23 was 96%. Other properties are shown in Table 3.

[Example 24] (Hydrogenated block copolymer (1)-24) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 33% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-24. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-24 was 96%. Other properties are shown in Table 3.

[Example 25] (Hydrogenated block copolymer (1)-25) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 30 parts by mass of styrene was charged. Next, add 0.102 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 71% by mass, a polystyrene block content of 30% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 133,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-25. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-25 was 96%. Other properties are shown in Table 3.

[Example 26] (Hydrogenated block copolymer (1)-26) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 57 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-26. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-26 was 96%. Other properties are shown in Table 3.

[Example 27] (Hydrogenated block copolymer (1)-27) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 36 parts by mass of butadiene and 42 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol 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 3% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-27. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-27 was 96%. Other properties are shown in Table 3.

[Example 28] (Hydrogenated block copolymer (1)-28) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.112 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 32 parts by mass of butadiene and 58 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 42% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 60% by mass, and a weight average molecular weight of 135,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-28. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-28 was 97%. Other properties are shown in Table 3.

[Example 29] (Hydrogenated block copolymer (1)-29) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 16.7 parts by mass of styrene was charged. Next, add 0.112 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol 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 13.7% by mass, a vinyl bond amount of 75% by mass, and a weight average molecular weight of 137,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-29. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-29 was 97%. Other properties are shown in Table 3.

[Example 30] (Hydrogenated block copolymer (1)-30) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was charged. Next, add 0.075 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 65% by mass, a polystyrene block content of 15% by mass, a vinyl bond amount of 23% by mass, and a weight average molecular weight of 150,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (I)-30. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-30 was 97%. Other properties are shown in Table 3.

[Comparative example 1] (Hydrogenated block copolymer (1)-A) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 45 parts by mass of styrene was charged. Next, add 0.092 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 23 parts by mass of butadiene and 32 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 77% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-A. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-A was 98%. Other properties are shown in Table 4.

[Comparative example 2] (Hydrogenated block copolymer (1)-B) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.116 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.15 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 162,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-B. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-B was 96%. Other properties are shown in Table 4.

[Comparative example 3] (Hydrogenated block copolymer (1)-C) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.080 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.25 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 210,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-C. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-C was 95%. Other properties are shown in Table 4.

[Comparative example 4] (Hydrogenated block copolymer (1)-D) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 0.2 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 10% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-D. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-D was 98%. Other properties are shown in Table 4.

[Comparative Example 5] (Hydrogenated block copolymer (1)-E) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-E. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-E was 15%. Other properties are shown in Table 4.

[Comparative Example 6] (Hydrogenated block copolymer (1)-F) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 72 parts by mass of butadiene and 18 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 28% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 66% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-F. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-F was 97%. Other properties are shown in Table 4.

[Comparative Example 7] (Hydrogenated block copolymer (1)-G) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.09 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 17 parts by mass of butadiene and 73 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 83% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 36% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-G. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-G was 97%. Other properties are shown in Table 4.

[Preparation of press-formed sheet] Use a 4-inch roll to separate the hydrogenated block copolymers (1)-1～(1)-30 and (1)-A～( 1)-G is rolled out at 160°C, and then pressurized by hydraulic pressure at 200°C and 100 kg/cm ² to make a 2 mm thick press-formed sheet.

The values of the following items were measured for the hydrogenated block copolymers (1)-1-30 and (1)-A-G of the above-mentioned [Examples 1-30] and [Comparative Examples 1-7]. (physical value) ・Content of total vinyl aromatic compound monomer units (mass%) ・(a) Content of polymer block mainly composed of vinyl aromatic compound monomer units (mass%) ・(b) Content of hydrogenated copolymer block containing vinyl aromatic compound monomer unit and conjugated diene monomer unit (mass%) ・(c) Content of hydrogenated polymer block mainly composed of conjugated diene monomer units (mass%) ・Vinyl bond amount (mass %) of the above (b) hydrogenated copolymer block ・Vinyl bond amount (mass %) of hydrogenated polymer block (c) above ・Weight average molecular weight immediately before adding ethyl benzoate (10,000) ·The molecular weight distribution (Molecular weight distribution immediately before addition of ethyl benzoate) ・(1) Weight average molecular weight (10,000) ・The value of the area of the molecular weight range of 10,000 to 150,000 relative to the area of the molecular weight range of 10,000 to 1,000,000 in the GPC chart (%) ・The value of the area of the molecular weight range of 200,000 to 1 million relative to the area of the molecular weight range of 10,000 to 1,000,000 in the GPC chart (%) ・Vinyl bond amount in conjugated diene monomer unit (mass%) ・Hydrogenation rate of double bond of conjugated diene monomer unit (%) ・Content (% by mass) of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above ・The content of the conjugated diene monomer unit in the hydrogenated copolymer block of (b) above (mass %) (characteristic) ・Melt flow rate (230°C, 2.16 kg) ・The peak temperature of tanδ (loss tangent) in the viscoelasticity measurement chart ・A hardness (momentary, 10 s) ・Particle adhesion

In addition, the polymer blocks (a) to (c) respectively represent the following polymer blocks. Polymer block (a): a polymer block mainly composed of vinyl aromatic compound monomer units Copolymer block (b): a hydrogenated copolymer block comprising vinyl aromatic compound monomer units and conjugated diene monomer units Polymer block (c): a hydrogenated polymer block mainly composed of conjugated diene monomer units

[Manufacture of Hydrogenated Block Copolymer Composition] A hydrogenated block copolymer composition was produced using the above-mentioned hydrogenated block copolymers (1)-1 to 30, (1)-A to G and the following olefin resin (2).

(Olefin resin (2)) As the olefin-based resin (2), PM900C (manufactured by PP/SunAllomer; MFR=30) was used.

[Manufacturing of Injection Molded Sheet] [Example 31] Prepare the granular hydrogenated block copolymer (1)-1 and olefin resin (2) according to the ratio (mass %) shown in the following Table 5, and knead with a twin-screw extruder (TEX-30). Pelletization, whereby a hydrogenated block copolymer composition is obtained. The extrusion conditions are cylinder temperature 230°C and screw speed 300 rpm. Using the obtained composition, injection molding was carried out at 210° C. to produce a sheet with a thickness of 2 mm to obtain a physical property measurement sheet. The results of physical property measurement are shown in the table.

[Examples 31-62, Comparative Examples 8-14] Except that each component was changed as shown in Table 5 to Table 8, a hydrogenated block copolymer composition was produced in the same manner as in Example 31 above, and its physical properties were measured. The results of the physical property measurement are shown in Tables 5 to 8.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 hydrogenated block copolymer (One 1 (minus 2 (1)-3 (1)-4 (1)-5 (1)-6 (1)-7 (1)-8 (1)-9 (1) -10 Total vinyl aromatic compound content (mass%) 63 67 67 67 61 59 61 57 51 63 Content of polymer block (a) (mass %) 10 20 20 20 4 0 10 10 10 10 Content of hydrogenated copolymer block (b) (mass %) 90 80 80 80 96 100 87 80 70 90 Content of hydrogenated polymer block (c) (mass %) 0 0 0 0 0 0 3 10 20 0 Vinyl bond amount of hydrogenated copolymer block (b) (mass %) 51 twenty one twenty one 51 51 51 51 51 51 51 Vinyl bond amount of hydrogenated polymer block (c) (mass %) - - - - - - 70 70 70 - Weight average molecular weight before adding ethyl benzoate (10,000) 12.5 12.5 - 12.5 12.5 12.5 12.5 12.5 12.5 10.5 Molecular weight distribution (molecular weight distribution immediately before addition of ethyl benzoate) 1.06 1.05 1.06 1.06 1.06 1.06 1.06 1.06 1.06 1.06 Weight average molecular weight (10,000) 15.1 13.1 12.0 15.1 15.1 15.1 15.1 15.1 15.1 12.6 The area value (%) of the molecular weight distribution in the range of 10,000 to 150,000 in the GPC chart 79 95 100 79 79 79 79 79 79 80 The area value (%) of the molecular weight distribution in the range of 200,000 to 1 million in the GPC chart twenty one 5 0 twenty one twenty one twenty one twenty one twenty one twenty one 15 Vinyl bond amount in conjugated diene monomer unit (mass%) 51 twenty one twenty one 51 51 51 52 53 55 51 Hydrogenation rate of double bond of conjugated diene monomer unit (%) 98 96 98 97 97 97 95 98 97 96 Vinyl aromatic compound content in hydrogenated copolymer block (b) (mass %) 59 59 59 59 59 59 59 59 59 59 Content of vinyl aromatic compound in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 53 47 47 47 57 59 51 47 41 53 Content of conjugated diene in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 37 33 33 33 39 41 36 33 29 37 MFR (230°C, 2.16 kg) 45 25 30 35 60 80 48 50 60 100 MFR score 3 1 1 2 3 3 3 3 3 3 tanδ peak temperature (℃) twenty four 20 20 twenty three twenty three twenty three twenty two 20 14 28 Hardness (JIS-A, instant) 80 65 64 86 71 60 74 71 61 72 Hardness (JIS-A, 10 s) 55 58 57 61 50 47 50 47 53 49 stickiness of particles 3 2 2 3 2 1 3 2 1 2

[Table 2] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 hydrogenated block copolymer (1) -11 (1)-12 (1)-13 (1)-14 (1) -15 (1) -16 (1)-17 (1)-18 (1)-19 (1) -20 Total vinyl aromatic compound content (mass%) 63 63 63 63 63 63 63 48 81 50 Content of polymer block (a) (mass %) 10 10 10 10 10 10 10 10 10 10 Content of hydrogenated copolymer block (b) (mass %) 90 90 90 90 90 90 90 90 90 90 Content of hydrogenated polymer block (c) (mass %) 0 0 0 0 0 0 0 0 0 0 Vinyl bond amount of hydrogenated copolymer block (b) (mass %) 51 29 40 51 51 51 51 60 40 55 Vinyl bond amount of hydrogenated polymer block (c) (mass %) - - - - - - - - - - Weight average molecular weight before adding ethyl benzoate (10,000) 10.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 Molecular weight distribution (molecular weight distribution immediately before addition of ethyl benzoate) 1.06 1.05 1.06 1.06 1.06 1.07 1.06 1.05 1.06 1.05 Weight average molecular weight (10,000) 15.2 15.1 15.1 15.1 15.1 15.1 15.1 15.1 15.1 15.1 The area value (%) of the molecular weight distribution in the range of 10,000 to 150,000 in the GPC chart 55 79 79 79 79 79 79 79 79 79 The area value (%) of the molecular weight distribution in the range of 200,000 to 1 million in the GPC chart 35 twenty one twenty one twenty one twenty one twenty one twenty one twenty one twenty one twenty one Vinyl bond amount in conjugated diene monomer unit (mass%) 51 29 40 51 51 51 51 60 40 55 Hydrogenation rate of double bond of conjugated diene monomer unit (%) 98 95 95 86 90 60 40 97 96 96 Vinyl aromatic compound content in hydrogenated copolymer block (b) (mass %) 59 59 59 59 59 59 59 42 79 44 Content of vinyl aromatic compound in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 53 53 53 53 53 53 53 38 71 39.6 Content of conjugated diene in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 37 37 37 37 37 37 37 52 19 50.4 MFR (230°C, 2.16 kg) 35 33 42 46 47 55 50 52 35 50 MFR score 2 1 2 3 3 3 3 3 2 3 tanδ peak temperature (℃) 20 19 20 20 twenty one twenty three twenty three 5 40 10 Hardness (JIS-A, instant) 78 85 83 78 79 76 74 60 88 75 Hardness (JIS-A, 10 s) 53 60 57 54 54 52 51 50 80 62 stickiness of particles 3 3 3 3 3 3 3 3 3 3

[table 3] Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 hydrogenated block copolymer (1)-21 (1)-22 (1)-23 (1)-24 (1) -25 (1)-26 (1)-27 (1)-28 (1)-29 (1) -30 Total vinyl aromatic compound content (mass%) 52 63 63 63 71 67 39 42 50 65 Content of polymer block (a) (mass %) 10 10 10 10 30 10 3 10 16.7 15 Content of hydrogenated copolymer block (b) (mass %) 90 90 90 90 70 90 78 90 83.3 85 Content of hydrogenated polymer block (c) (mass %) 0 0 0 0 0 0 20 0 0 0 Vinyl bond amount of hydrogenated copolymer block (b) (mass %) 51 51 51 33 60 60 60 60 75 twenty three Vinyl bond amount of hydrogenated polymer block (c) (mass %) - - - - - - - - - - Weight average molecular weight before adding ethyl benzoate (10,000) 12.5 12.5 12.5 12.5 11 12.5 12.5 - - - Molecular weight distribution (molecular weight distribution immediately before addition of ethyl benzoate) 1.07 1.07 1.06 1.07 1.06 1.06 1.06 1.07 1.06 1.2 Weight average molecular weight (10,000) 15.1 13.6 14.0 15.1 13.3 15.1 15.1 13.5 13.7 15.0 The area value (%) of the molecular weight distribution in the range of 10,000 to 150,000 in the GPC chart 79 91 88 79 79 79 79 100 100 55 The area value (%) of the molecular weight distribution in the range of 200,000 to 1 million in the GPC chart twenty one 9 12 twenty one twenty one twenty one twenty one 0 0 0 Vinyl bond amount in conjugated diene monomer unit (mass%) 51 51 51 33 51 51 51 60 75 twenty three Hydrogenation rate of double bond of conjugated diene monomer unit (%) 96 96 96 96 96 96 96 97 97 97 Vinyl aromatic compound content in hydrogenated copolymer block (b) (mass %) 47 59 59 59 59 63 46 36 40 59 Content of vinyl aromatic compound in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 42.3 53 53 53 41 57 36 32 33.3 50 Content of conjugated diene in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 47.7 37 37 37 29 33 42 58 50.0 35 MFR (230°C, 2.16kg) 43 60 55 35 35 46 46 60 61 33 MFR score 2 3 3 2 2 3 3 3 3 1 tanδ peak temperature (℃) 10 twenty two twenty three 20 25 33 8 -5 19 10 Hardness (JIS-A, instant) 77 79 77 84 75 85 65 54 75 76 Hardness (JIS-A, 10 s) 63 55 54 58 70 79 54 47 63 65 stickiness of particles 3 3 3 3 3 3 3 2 3 3

[Table 4] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 Comparative Example 7 hydrogenated block copolymer (1)-A (1)-B (1)-C (1)-D (1)-E (1)-F (1)-G Total vinyl aromatic compound content (mass%) 77 63 63 63 63 28 83 Content of polymer block (a) (mass %) 45 10 10 10 10 10 10 Content of hydrogenated copolymer block (b) (mass %) 55 90 90 90 90 90 90 Content of hydrogenated polymer block (c) (mass %) 0 0 0 0 0 0 0 Vinyl bond amount of hydrogenated copolymer block (b) (mass %) 51 51 51 10 51 66 35 Vinyl bond amount of hydrogenated polymer block (c) (mass %) - - - - - - - Weight average molecular weight before adding ethyl benzoate (10,000) 12.5 9.5 14 12.5 12.5 12.5 12.5 Molecular weight distribution (molecular weight distribution immediately before addition of ethyl benzoate) 1.06 1.06 1.05 1.06 1.06 1.06 1.06 (1) Weight average molecular weight (10,000) 15.1 16.2 21.0 15.1 15.1 15.1 15.1 The area value (%) of the molecular weight distribution in the range of 10,000 to 150,000 in the GPC chart 79 30 50 79 79 79 79 The area value (%) of the molecular weight distribution in the range of 200,000 to 1 million in the GPC chart twenty one 20 50 twenty one twenty one twenty one twenty one Vinyl bond amount in conjugated diene monomer unit (mass%) 51 51 51 10 51 66 36 Hydrogenation rate of double bond of conjugated diene monomer unit (%) 98 96 95 98 15 97 97 Vinyl aromatic compound content in hydrogenated copolymer block (b) (mass %) 59 59 59 59 59 20 81 Content of vinyl aromatic compound in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) 32 53 53 53 53 18 73 Content of conjugated diene in the hydrogenated copolymer block (b) relative to the whole polymer (mass %) twenty three 37 37 37 37 72 17 MFR (230°C, 2.16kg) 5 5 10 15 55 50 30 MFR score 0 0 0 0 3 3 1 tanδ peak temperature (℃) twenty three twenty three twenty three twenty three twenty three -10 52 Hardness (JIS-A, instant) 85 81 83 86 75 50 92 Hardness (JIS-A, 10 s) 61 57 61 62 52 45 86 stickiness of particles 3 3 2 3 3 1 3

[table 5] (quality%) Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Hydrogenated block polymer (1)-1 80 - - - - - - - - - - - Hydrogenated block polymer (1)-2 - 80 - - - - - - - - - - Hydrogenated block polymer (1)-3 - - 80 - - - - - - - - - Hydrogenated block polymer (1)-4 - - - 80 - - - - - - - - Hydrogenated block polymer (1)-5 - - - - 80 - - - - - - - Hydrogenated block polymer (1)-6 - - - - - 80 - - - - - - Hydrogenated block polymer (1)-7 - - - - - - 80 - - - - - Hydrogenated block polymer (1)-8 - - - - - - - 80 - - - - Hydrogenated block polymer (1)-9 - - - - - - - - 80 - - - Hydrogenated block polymer (1)-10 - - - - - - - - - 80 - - Hydrogenated block polymer (1)-11 - - - - - - - - - - 80 - Hydrogenated block polymer (1)-12 - - - - - - - - - - - 80 Olefin resin (2) 20 20 20 20 20 20 20 20 20 20 20 20 MFR (230°C, 2.16kg) 42 20 twenty four 30 45 55 50 48 65 95 31 twenty four wear resistance ◎ 〇 〇 ◎ 〇 〇 ◎ 〇 〇 〇 ◎ 〇 Abrasion Resistance Score 3 2 2 3 2 2 3 2 2 2 3 2 extrusion formability 3 2 2 3 3 3 3 3 3 3 3 2

[Table 6] (quality%) Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 Hydrogenated block polymer (1)-1 - - - - - - - - - - Hydrogenated block polymer (1)-13 80 - - - - - - - - - Hydrogenated block polymer (1)-14 - 80 - - - - - - - - Hydrogenated block polymer (1)-15 - - 80 - - - - - - - Hydrogenated block polymer (1)-16 - - - 80 - - - - - - Hydrogenated block polymer (1)-17 - - - - 80 - - - - - Hydrogenated block polymer (1)-18 - - - - - 80 - - - - Hydrogenated block polymer (1)-19 - - - - - - 80 - - - Hydrogenated block polymer (1)-20 - - - - - - - 80 - - Hydrogenated block polymer (1)-21 - - - - - - - - 80 - Hydrogenated block polymer (1)-22 - - - - - - - - - 80 Hydrogenated block polymer (1)-23 - - - - - - - - - - Hydrogenated block polymer (1)-24 - - - - - - - - - - Hydrogenated block polymer (1)-25 - - - - - - - - - - Hydrogenated block polymer (1)-26 - - - - - - - - - - Hydrogenated block polymer (1)-27 - - - - - - - - - - Hydrogenated block polymer (1)-28 Hydrogenated block polymer (1)-29 Hydrogenated block polymer (1)-30 Olefin resin (2) 20 20 20 20 20 20 20 20 20 20 MFR (230°C, 2.16kg) 33 40 43 45 41 41 31 42 32 45 wear resistance ◎ ◎ ◎ 〇 〇 △ ◎ △ ◎ △ Abrasion Resistance Score 3 3 3 2 2 1 3 1 3 1 extrusion formability 3 2 3 2 1 3 2 2 3 3

[Table 7] (quality%) Example 53 Example 54 Example 55 Example 56 Example 57 Example 58 Example 59 Example 60 Example 61 Example 62 Hydrogenated block polymer (1)-1 - - - - - - - 50 20 Hydrogenated block polymer (1)-13 - - - - - - - - - - Hydrogenated block polymer (1)-14 - - - - - - - - - - Hydrogenated block polymer (1)-15 - - - - - - - - - - Hydrogenated block polymer (1)-16 - - - - - - - - - - Hydrogenated block polymer (1)-17 - - - - - - - - - - Hydrogenated block polymer (1)-18 - - - - - - - - - - Hydrogenated block polymer (1)-19 - - - - - - - - - - Hydrogenated block polymer (1)-20 - - - - - - - - - - Hydrogenated block polymer (1)-21 - - - - - - - - - - Hydrogenated block polymer (1)-22 - - - - - - - - - - Hydrogenated block polymer (1)-23 80 - - - - - - - - - Hydrogenated block polymer (1)-24 - 80 - - - - - - - - Hydrogenated block polymer (1)-25 - - 80 - - - - - - - Hydrogenated block polymer (1)-26 - - - 80 - - - - - - Hydrogenated block polymer (1)-27 - - 80 - - - - - Hydrogenated block polymer (1)-28 80 - - Hydrogenated block polymer (1)-29 - 80 - Hydrogenated block polymer (1)-30 - - 80 Olefin resin (2) 20 20 20 20 20 20 20 20 50 80 MFR (230°C, 2.16 kg) 44 33 34 41 40 45 45 27 40 38 wear resistance ◎ ◎ ◎ ◎ △ △ △ 〇 ◎ ◎ Abrasion Resistance Score 3 3 3 3 1 1 1 2 3 3 extrusion formability 3 3 3 3 3 3 3 2 3 3

[Table 8] (quality%) Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Hydrogenated block polymer (1)-A 80 - - - - - - Hydrogenated block polymer (1)-B - 80 - - - - - Hydrogenated block polymer (1)-C - - 80 - - - - Hydrogenated block polymer (1)-D - - - 80 - - - Hydrogenated block polymer (1)-E - - - - 80 - - Hydrogenated block polymer (1)-F - - - - - 80 - Hydrogenated block polymer (1)-G - - - - - - - Hydrogenated block polymer (1)-H - - - - - - - Hydrogenated block polymer (1)-I - - - - - - - Hydrogenated Block Polymer (1)-J - - - - - - 80 Olefin resin (2) 20 20 20 20 20 20 20 MFR (230°C, 2.16kg) 7 13 15 15 40 40 27 wear resistance 〇 ◎ ◎ x x x x Abrasion Resistance Score 2 3 3 0 0 0 0 extrusion formability 3 3 3 1 1 3 1

The hydrogenated block copolymers of Examples 1 to 30 and the hydrogenated block copolymer compositions of Examples 31 to 62 had an excellent balance between wear resistance and MFR, and had good hardness and formability. [Industrial availability]

The hydrogenated block copolymer of the present invention and its composition have industrial potential in the fields of automobile parts (automobile interior materials, automobile exterior materials), medical equipment materials, various containers such as food packaging containers, home appliances, industrial parts, toys, etc. above availability.

Claims (9)

A hydrogenated block copolymer, which is a hydrogenated product of a block copolymer containing a vinyl aromatic compound monomer unit and a conjugated diene monomer unit, and satisfies the following necessary conditions (1) to (7); (1): containing at least one (b) hydrogenated copolymer block comprising vinyl aromatic compound monomer units and conjugated diene monomer units; (2): having (a) vinyl aromatic compound monomer units The monomer unit is the main polymer block, the content of (a) the polymer block mainly based on the vinyl aromatic compound monomer unit is 40% by mass or less; (3): the weight average molecular weight (Mw) is 20 (4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is more than 20%; (5): The molecular weight of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC) In the curve, the ratio of the area with a molecular weight of 10,000 to 150,000 to the area with a molecular weight of 10,000 to 1 million exceeds 50%; (6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more; (7): The content of vinyl aromatic compound monomer units in the hydrogenated copolymer block of (b) above is 45% by mass or more and 70% by mass or less; and the total vinyl group of the hydrogenated block copolymer The content of the aromatic compound monomer unit is not less than 45% by mass and not more than 80% by mass. The hydrogenated block copolymer according to claim 1, wherein the amount of vinyl bonds in the hydrogenated block copolymer is 30% by mass or more. Such as the hydrogenated block copolymer of claim 1 or 2, wherein in the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the area with a molecular weight of 200,000 to 1,000,000 is relative to The ratio of the area in the molecular weight range of 10,000 to 1,000,000 is 10% or more. The hydrogenated block copolymer according to claim 1 or 2, wherein the content of the above (a) polymer block mainly composed of vinyl aromatic compound monomer units is 1% by mass or more and 20% by mass or less. The hydrogenated block copolymer according to claim 1 or 2, which contains 1% by mass or more of (c) a hydrogenated polymer block mainly composed of conjugated diene monomer units. The hydrogenated block copolymer according to claim 1 or 2, wherein there is at least one peak of tanδ in the viscoelasticity measurement chart above 0°C and below 30°C. A hydrogenated block copolymer composition, which contains the hydrogenated block copolymer (1) according to any one of claims 1 to 6: not less than 1% by mass and not more than 95% by mass, and at least one olefin-based resin (2): 5 mass % or more and 99 mass % or less. The hydrogenated block copolymer composition according to claim 7, wherein the olefin-based resin (2) contains at least one polypropylene-based resin. A shaped body, which is a shaped body of the hydrogenated block copolymer composition according to claim 7 or 8.