TW202436414A - Hydrogenated block copolymer, hydrogenated block copolymer composition, and formed article - Google Patents

Abstract

The present invention provides a hydrogenated block copolymer exhibiting excellent low resilience and wear resistance. The hydrogenated block copolymer (A) of the present invention satisfies conditions (1) to (3). ＜Condition (1)＞: It contains at least one hydrogenated copolymer block (b) comprising a vinyl aromatic monomer unit and a covalent diene monomer unit, and the content of the hydrogenated copolymer block (b) is 65 to 95% by mass. ＜Condition (2)＞: The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 40 to 75% by mass. ＜Condition (3)＞: The ratio g=P/P0 of the peak intensity P detected by a thermal decomposition gas chromatography mass spectrometer and P0 obtained according to (Formula I) is 0.75 or more. P0＝k×RS         (Formula I) (In (Formula I), RS is the content (mass %) of the vinyl aromatic monomer unit in the block (b) relative to the entire hydrogenated block copolymer (A). k represents the proportional constant when RS (mass %) is approximated by the peak intensity P)

Description

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

The present invention relates to a hydrogenated block copolymer, a hydrogenated block copolymer composition, and a formed article.

The hydrogenated block copolymers of covalent diene compounds and vinyl aromatic compounds have the same elasticity as vulcanized natural rubber or synthetic rubber at room temperature even without vulcanization, and have the same processability as thermoplastic resin at high temperature, so they are widely used in plastic modifiers, adhesives, automotive parts, and medical devices. Furthermore, the hydrogenated block copolymers are particularly widely used as materials for automotive parts or medical devices due to their excellent weather resistance and heat resistance.

However, hydrogenated products of block copolymers containing covalent diene compounds and vinyl aromatic compounds, such as hydrogenated styrene elastomers (hereinafter, sometimes referred to as "TPS materials"), have poor wear resistance, so there is a problem of limitations in their use. In response to the above problem, the industry has proposed a resin composition of a random copolymer styrene elastomer and a polypropylene resin having a vinyl aromatic monomer unit content of 40 mass % or more and less than 95 mass %, and a molded body of the resin composition, and disclosed that the molded body has excellent wear resistance (for example, refer to Patent Document 1).

In recent years, as a new direction of automobiles, autonomous driving or mobility services have attracted attention. Due to this trend, the performance required of automobile interior materials will also change. For example, it is predicted that with autonomous driving, the significance of automobiles as living spaces will be further enhanced. Therefore, in order to continuously construct spaces where passengers can live more comfortably, a high-end touch is produced, and low-rebound materials are required. In addition, from the perspective of mobility services, it is believed that with the penetration of car sharing, the industry is constantly pursuing the longevity and cleanliness of automobiles. Therefore, the number of times that automobile interior materials are cleaned has increased compared to before, and the resin composition used as the material for automobile interior materials needs to have higher wear resistance. As mentioned above, due to the penetration of autonomous driving or mobility services, in recent years, the polymers of the materials of the resin composition are required to have higher wear resistance and better touch than previous products.

In view of the above requirements, the industry has proposed a hydrogenated block copolymer having a tanδ (loss tangent) peak within a specific temperature range, and it is shown that the resin composition using the hydrogenated block copolymer has excellent energy absorption and can show low resilience (for example, refer to patent document 2). [Prior art document] [Patent document]

[Patent Document 1] International Publication No. 2003/035705 [Patent Document 2] International Publication No. 2010/018743

[The problem the invention is trying to solve]

However, the hydrogenated block copolymers previously proposed have the following problems: there is still room for improvement in terms of good touch, i.e., low resilience, and abrasion resistance.

Therefore, the purpose of the present invention is to provide a hydrogenated block copolymer that can exhibit excellent low resilience and wear resistance. [Technical means for solving the problem]

The inventors of the present invention have repeatedly conducted research to solve the above-mentioned problems of the prior art, and as a result, have found that a hydrogenated block copolymer can be provided, thereby completing the present invention. The hydrogenated block copolymer has a specific structure, and by specifying the content of the hydrogenated copolymer block (b) containing vinyl aromatic monomer units and covalent diene monomer units in the hydrogenated block copolymer, the content of the vinyl aromatic monomer units in the hydrogenated copolymer block (b), and the specified random parameter g, the low resilience and wear resistance are excellent. That is, the present invention is as follows.

[1] A hydrogenated block copolymer (A) comprising vinyl aromatic monomer units and covalent diene monomer units, and containing at least one polymer block (a) mainly composed of vinyl aromatic monomer units, and satisfying the following <Condition (1)> to <Condition (3)>. <Condition (1)>: containing at least one hydrogenated copolymer block (b) comprising vinyl aromatic monomer units and covalent diene monomer units, and the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) is 65 mass % or more and 95 mass % or less. <Condition (2)>: the content of the vinyl aromatic monomer units in the hydrogenated copolymer block (b) is 40 mass % or more and 75 mass % or less. <Condition (3)>: The ratio g=P/P0 of the peak intensity P detected by the thermal decomposition gas chromatography mass spectrometry analyzer and P0 obtained according to the following (Formula I) is greater than 0.75. P0＝k×RS         (Formula I) (In (Formula I), RS is the content (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole. k represents the proportional constant when the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole is first approximated to the peak intensity P, which is obtained when the hydrogenated block copolymer (A) of homogeneous polymerization is analyzed using a thermal decomposition gas chromatography mass spectrometry analyzer) [2] The hydrogenated block copolymer described in [1] above, wherein the ratio g=P/P0 of the peak intensity P to P0 obtained using the above (Formula I) is 0.9 or more. [3] The hydrogenated block copolymer as described in [1] or [2] above, wherein the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 55% by mass or more and 65% by mass or less. [4] The hydrogenated block copolymer as described in any one of [1] to [3] above, wherein the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) is 75% by mass or more and 85% by mass or less. [5] A hydrogenated block copolymer composition comprising: 1 mass % or more and 50 mass % or less of the hydrogenated block copolymer (A) as described in any one of [1] to [4] above, 5 mass % or more and 90 mass % or less of at least one olefinic resin (B), 1 mass % or more and 50 mass % or less of at least one thermoplastic resin (C), and 5 mass % or more and 90 mass % or less of at least one softener (D). [6] The hydrogenated block copolymer composition as described in [5] above, wherein the olefinic resin (B) comprises at least one polypropylene resin. [7] A molded article, which is a molded article of the hydrogenated block copolymer composition as described in [5] above. [8] The molded article described in [5] above is a foamed article. [Effects of the invention]

According to the present invention, a hydrogenated block copolymer exhibiting excellent low resilience and abrasion resistance can be obtained.

The following is a detailed description of a form for implementing the present invention (hereinafter referred to as "this embodiment"). Furthermore, the following this embodiment is an example for explaining the present invention, and does not limit the present invention to the purpose of the following content. The present invention can be implemented in various ways within the scope of its purpose.

[Hydrogenated block copolymer] The hydrogenated block copolymer of the present embodiment (hereinafter, sometimes described as hydrogenated block copolymer (a)) is a hydrogenated product of a block copolymer comprising vinyl aromatic monomer units and covalent diene monomer units, and containing at least one polymer block (a) having vinyl aromatic monomer units as the main component, and satisfies the following <condition (1)> to <condition (3)>.

<Condition (1)>: Contains at least one hydrogenated copolymer block (b) comprising a vinyl aromatic monomer unit and a covalent diene monomer unit, and the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) of the present embodiment is 65 mass % or more and 95 mass % or less. <Condition (2)>: The content of the vinyl aromatic monomer unit in the above hydrogenated copolymer block (b) is 40 mass % or more and 75 mass % or less. <Condition (3)>: The ratio g=P/P0 of the peak intensity P detected by a thermal decomposition gas chromatography mass spectrometer and P0 determined according to the following (Formula I) is 0.75 or more. P0＝k×RS    …  (Formula I) (RS is the content (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole. k represents the proportional constant when the content RS of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole is first approximated to the peak intensity P, which is obtained when the hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization method) is analyzed using a thermal decomposition gas chromatography mass spectrometer))

By having the above-mentioned structure, a hydrogenated block copolymer exhibiting excellent low resilience and wear resistance can be obtained. In addition, in this specification, the state before being incorporated into the polymer is described as "compound", and the state after being incorporated into the polymer is described as "monomer unit".

(Vinyl aromatic monomer units) The hydrogenated block copolymer (A) of the present embodiment contains vinyl aromatic monomer units. As the vinyl aromatic compound forming the vinyl aromatic monomer units, for example, monomer units derived from styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. can be cited, but it is not limited to the above. In particular, from the perspective of the balance between cost and the mechanical strength of the resin composition containing the hydrogenated block copolymer, styrene is preferred. These may be used alone or in combination of two or more.

(Conjugated diene monomer units) The hydrogenated block copolymer (A) of the present embodiment includes conjugated diene monomer units. The conjugated diene monomer units are monomer units derived from dienes having a pair of conjugated double bonds. Examples of such dienes include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. In particular, from the viewpoint of a good balance between molding processability and mechanical strength, 1,3-butadiene and isoprene are preferred. These may be used alone or in combination of two or more.

(Vinyl bond content in all conjugated diene monomer units) The hydrogenated block copolymer (A) of this embodiment has no particular limitation on the vinyl bond content in all conjugated diene monomer units, and is preferably 5% by mass or more. More preferably, it is 15% by mass or more, and further preferably, it is 20% by mass or more. If the vinyl bond content in all conjugated diene monomer units of the hydrogenated block copolymer (A) is 5% by mass or more, precipitation from the solution caused by crystallization of the hydrogenated conjugated diene block can be suppressed in the hydrogenation step. Furthermore, if the vinyl bond content is 5% by mass or more, the crystallization of the hydrogenated covalent diene block can be suppressed, and good flexibility can be obtained in the hydrogenated block copolymer of the present embodiment, its composition, and molded body. Furthermore, the vinyl bond content of all covalent diene monomer units in the hydrogenated block copolymer (A) of the present embodiment is preferably 60% by mass or less, and more preferably 50% by mass or less. If the vinyl bond content of all covalent diene monomer units in the hydrogenated block copolymer (A) is 60% by mass or less, good tensile strength can be obtained in the hydrogenated block copolymer of the present embodiment, its composition, and molded body. The vinyl bond content of all the conjugated diene monomer units of the hydrogenated block copolymer (A) can be controlled within the above numerical range by using, for example, a modifier (vinyl bond content modifier) such as the following tertiary amine compound or ether compound. In addition, the above vinyl bond content can be measured by the method described in the following examples.

(Content of all vinyl aromatic monomer units) The content of all vinyl aromatic monomer units of the hydrogenated block copolymer (A) of the present embodiment is preferably 50% by mass or more and 80% by mass or less, more preferably 55% by mass or more and 80% by mass or less, and further preferably 60% by mass or more and 80% by mass or less. If the content of all vinyl aromatic monomer units is 50% by mass or more, the hydrogenated block copolymer (A) of the present embodiment tends to have good oil resistance. If the oil resistance is good, it can be used for applications requiring more stringent oil resistance in automotive materials, etc. For applications requiring more stringent oil resistance, such as automotive interior materials, when molding thinner-walled molded bodies, or when molding more complex/large molded bodies, or when used for a longer period of time, the use of the hydrogenated block copolymer (A) of this embodiment tends to suppress deformation of the material or poor appearance. In addition, in this specification, "normal molded bodies" are defined as simple small molded bodies of about 150 mm square that are flat and have a thickness of about 2 mm. It has been confirmed that thin-walled molded bodies, or complex and large molded bodies tend to have reduced properties such as oil resistance, wear resistance, damage resistance, appearance, low temperature characteristics, touch, and shape retention compared to such "normal molded bodies". Furthermore, if the oil resistance is good, the upper limit of the amount of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of the present embodiment described below increases, and the degree of freedom in the formulation tends to be improved. Generally, the less the amount of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of the present embodiment described below is, the better the oil resistance tends to be, but the more the amount of the hydrogenated block copolymer (A) is, the better the wear resistance or touch tends to be, so the upper limit of the formulation amount is preferably higher. Furthermore, the content of all vinyl aromatic monomer units in the hydrogenated block copolymer (A) of the present embodiment can be measured by using a UV spectrophotometer with the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation as a specimen. In addition, the content of all vinyl aromatic monomer units of the hydrogenated block copolymer (A) can be controlled within the above numerical range by mainly adjusting the amount of vinyl aromatic compound added to the polymerization reactor, the reaction temperature, and the reaction time.

Furthermore, in this specification, regarding the polymer block constituting the hydrogenated block copolymer (a), "as the main body" means that the ratio in the specified block polymer is 85 mass% or more, preferably 90 mass% or more, and more preferably 95 mass% or more. Furthermore, the content of the vinyl aromatic monomer unit in the above hydrogenated copolymer block (b) is 40 mass% or more and 75 mass% or less (the above <condition (2)>), so the above polymer block (a) and the hydrogenated polymer block (b) can be clearly distinguished.

(Polymer block (a) with vinyl aromatic monomer units as the main component) The hydrogenated block copolymer (A) of this embodiment contains at least one polymer block (a) with vinyl aromatic monomer units as the main component. Therefore, there is a tendency to prevent the particles from sticking together. In addition, the content of the above polymer block (a) of the hydrogenated block copolymer (A) of this embodiment is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. If the content of the polymer block (a) with vinyl aromatic monomer units as the main component is 5% by mass or more, the particles of the hydrogenated block copolymer (A) have good anti-sticking properties, and there is a tendency to show good tensile properties in the hydrogenated block copolymer of this embodiment, its composition, and molded body.

When the particles of the hydrogenated block copolymer (A) of the present embodiment show good anti-blocking properties, they tend to be less likely to stick even when transported for a longer time, under a higher load, or in a harsh temperature environment (e.g., in an area with a high external temperature or an area with a sharp temperature difference), and thus can be easily weighed or blended during composite molding. In addition, the amount of anti-sticking agent can be reduced, thereby avoiding device contamination, reducing environmental load, and suppressing unexpected reductions in physical properties, such as reductions in transparency and mechanical strength.

The content of the polymer block (a) in the hydrogenated block copolymer (A) of the present embodiment can be measured by using a nuclear magnetic resonance device (NMR) method (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Hereinafter referred to as "NMR method") using the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation as a sample. Specifically, it can be measured by the method described in the following examples. In addition, the content of the polymer block (a) in the hydrogenated block copolymer (A) can be controlled within the above numerical range by mainly adjusting the amount of the vinyl aromatic compound added to the polymerization reactor, the reaction temperature, and the reaction time.

(Hydrogenated copolymer block (b)) ＜Condition (1)＞ The hydrogenated block copolymer (A) of the present embodiment contains at least one hydrogenated copolymer block (b) comprising a vinyl aromatic monomer unit and a covalent diene monomer unit, and the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) is 65 mass % or more and 95 mass % or less.

The content of the above-mentioned hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) of the present embodiment is 65 mass % or more and 95 mass % or less, preferably 70 mass % or more and 90 mass % or less, and more preferably 75 mass % or more and 85 mass % or less. If the content of the above-mentioned hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) of the present embodiment is 65 mass % or more and 95 mass % or less, the hydrogenated block copolymer (A) of the present embodiment tends to show good wear resistance. Furthermore, if it is 70% by mass or more and 90% by mass or less, it shows higher wear resistance. If it is 75% by mass or more and 85% by mass or less, it can be used in the following situations: In applications where the requirements for wear resistance are more stringent, such as applications where excellent wear resistance is required in thinner-walled molded bodies in automotive interior materials, or applications where wear resistance due to higher loads or coarser mesh fabrics, such as fine white cloth No. 3, which is coarser than cotton fabrics, i.e., denim cotton fabrics, is required to maintain the appearance for a long time. Furthermore, if the wear resistance is good, the lower limit of the amount of the hydrogenated block copolymer (A) can be reduced in the hydrogenated block copolymer composition using the hydrogenated block copolymer (A) of the present embodiment, and there is a tendency to increase the degree of freedom in the formulation. Generally, the more the amount of the hydrogenated block copolymer (A) is formulated in the hydrogenated block copolymer composition described below, the better the wear resistance tends to be. However, since the less the amount of the hydrogenated block copolymer (A) is formulated, the better the oil resistance or material cost tends to be, the lower limit of the formulation amount is preferably lower. If the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) of the present embodiment is 65% by mass or more and 95% by mass or less, it exhibits excellent low resilience and tends to exhibit good tactile properties. Furthermore, if it is 70% by mass or more and 90% by mass or less, the low resilience is improved and can be used in applications with more stringent requirements for tactile properties. If it is 75% by mass or more and 85% by mass or less, it can be suitably used in applications with more stringent requirements for tactile properties, such as automotive interior materials, etc.

<Condition (2)> The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) (100% by mass) of the hydrogenated block copolymer (A) of this embodiment is 40% by mass or more and 75% by mass or less.

The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less, preferably 45% by mass or more and 70% by mass or less, and more preferably 55% by mass or more and 65% by mass or less If the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less, the hydrogenated block copolymer (A) of the present embodiment tends to show good wear resistance. Furthermore, if it is 45% by mass or more and 70% by mass or less, it shows higher wear resistance, and if it is 55% by mass or more and 65% by mass or less, it tends to be used in the following situations: In applications where the requirements for wear resistance are even more stringent, such as in automotive interior materials, applications where excellent wear resistance is required in thinner-walled molded bodies, or in automotive interior materials applications, applications where a higher load is required when riding in a car, or where coarser mesh fabrics are required, such as coarser mesh fabrics such as fine calico No. 3, which are denim twill cotton fabrics, and wear resistance is required to maintain the appearance for a long time. If the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less, it exhibits excellent low resilience and tends to exhibit good tactile properties. Furthermore, if it is 45% by mass or more and 70% by mass or less, the low resilience is improved and it can be used in applications with more stringent requirements for tactile properties. If it is 55% by mass or more and 65% by mass or less, it can be used in applications with more stringent requirements for tactile properties, such as automotive interior materials.

Furthermore, the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) can be measured by a nuclear magnetic resonance device (NMR) or the like. In addition, the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) can be controlled within the above numerical range by adjusting the amount or supply rate of the vinyl aromatic compound and the covalent diene compound added to the polymerization reactor, the reaction temperature, etc.

(Weight average molecular weight of hydrogenated block copolymer (A)) From the viewpoint of extrusion moldability during pellet production of the hydrogenated block copolymer of this embodiment and obtaining good mechanical strength, the weight average molecular weight (Mw) of the hydrogenated block copolymer (A) of this embodiment is preferably 10,000 or more and 500,000 or less, more preferably 50,000 or more and 450,000 or less, and further preferably 100,000 or more and 400,000 or less. If the weight average molecular weight (Mw) is 10,000 or more, the hydrogenated block copolymer composition using the hydrogenated block copolymer of this embodiment tends to show good mechanical strength. In addition, if the weight average molecular weight (Mw) is 500,000 or less, the hydrogenated block copolymer (A) tends to be easy to melt during the preparation of the hydrogenated block copolymer pellets (during extrusion molding), the strands are more stable, and the extrusion molding properties tend to be improved. Furthermore, the weight average molecular weight of the hydrogenated block copolymer (A) of this embodiment can be measured by gel permeation chromatography (GPC) and obtained using a calibration curve obtained by measuring commercially available standard polystyrene (prepared using the peak molecular weight of standard polystyrene).

(Molecular weight distribution (Mw/Mn) of hydrogenated block copolymer (A)) The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (A) of the present embodiment is preferably 10 or less, more preferably 1 to 8, and further preferably 1.01 to 1.10. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated block copolymer (A) are measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is obtained using a calibration curve obtained by measuring commercially available standard polystyrene (prepared using the peak molecular weight of standard polystyrene). The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (A) is obtained based on the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

(Hydrogenation rate of double bonds of conjugated diene monomer units in hydrogenated block copolymer (A)) In the hydrogenated block copolymer composition using the hydrogenated block copolymer of the present embodiment, from the viewpoint of obtaining good weather resistance and low temperature properties, the hydrogenation rate of double bonds of conjugated diene monomer units in the hydrogenated block copolymer (A) of the present embodiment is preferably 25 mol% or more, more preferably 70 mol% or more, further preferably 85 mol% or more, further preferably 92 mol% or more. The hydrogenation rate of double bonds of conjugated diene monomer units in the hydrogenated block copolymer (A) can be controlled within the above numerical range by adjusting the hydrogenation amount. The hydrogenation rate of the hydrogenated block copolymer (A) can be measured using a nuclear magnetic resonance device (NMR) or the like.

(Hydrogenation rate of aromatic double bonds of vinyl aromatic monomer units in hydrogenated block copolymer (A)) Regarding the hydrogenation rate of aromatic double bonds of vinyl aromatic monomer units in the hydrogenated block copolymer (A) of the present embodiment, in the hydrogenated block copolymer composition of the present embodiment described below, from the viewpoint of obtaining good weather resistance, it is preferably 50 mol% or less, more preferably 30 mol% or less, and further preferably 10 mol% or less. The hydrogenation rate of aromatic double bonds of vinyl aromatic monomer units in the hydrogenated block copolymer (A) can be measured using a nuclear magnetic resonance device (NMR) or the like.

(Crystallization peak of hydrogenated block copolymer (A)) The hydrogenated block copolymer (A) of the present embodiment is preferably a hydrogenated product having a crystallization peak caused by the hydrogenated copolymer block (b) in the range of -25 to 80°C in the differential scanning calorimetry (DSC) diagram. Here, "there is substantially no crystallization peak caused by the hydrogenated copolymer block (b) in the range of -25 to 80°C" means that within the temperature range, there is no peak caused by the crystallization of the hydrogenated copolymer block (b), or even if a peak caused by crystallization is confirmed, the crystallization peak heat generated by the crystallization is less than 3 J/g, preferably less than 2 J/g, more preferably less than 1 J/g, and more preferably no crystallization peak heat. As described above, if there is substantially no crystallization peak caused by the hydrogenated copolymer block (b) in the range of -25 to 80°C, good flexibility can be obtained in the hydrogenated block copolymer (A) of the present embodiment, and it is more appropriate to seek softening of the hydrogenated block copolymer composition described below. In order to obtain a hydrogenated block copolymer (A) having substantially no crystallization peak caused by the hydrogenated copolymer block (b) in the range of -25 to 80°C, it is sufficient to subject the copolymer to a hydrogenation reaction. The copolymer is obtained by using a prescribed regulator for adjusting the vinyl bond weight or the copolymerizability of the vinyl aromatic compound and the co-polymerized diene, and conducting a polymerization reaction under the following conditions.

(Tanδ (loss tangent) peak in the viscoelasticity measurement graph of the hydrogenated block copolymer (A)) The hydrogenated block copolymer (A) of the present embodiment preferably has at least one tanδ (loss tangent) peak above -25°C and below 45°C in the viscoelasticity measurement graph. More preferably, it is above -5°C and below 40°C, further preferably, it is above 10°C and below 35°C, further preferably, it is above 15°C and below 30°C. The tanδ peak is a peak caused by the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A). By having at least one peak in the range of -25°C to 60°C, the hydrogenated block copolymer (A) of the present embodiment exhibits low resilience, thereby showing a tendency to have a good touch. Furthermore, the tanδ of the hydrogenated block copolymer (A) can be measured using a viscoelasticity measuring device (ARES, manufactured by TA Instrument Co., Ltd.) under the conditions of a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3°C/min. Specifically, the measurement can be performed by the method described in the following embodiment.

(Randomness parameter g of hydrogenated block copolymer (A)) ＜Condition (3)＞ The ratio of the peak intensity P detected by the thermal decomposition gas chromatography mass spectrometry analysis device of the hydrogenated block copolymer (A) of this embodiment to P0 obtained according to the following (Formula I): g = P/P0 is 0.75 or more. P0＝k×RS         (Formula I) (In (Formula I), RS is the content (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole. k represents the proportional constant when the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole is first approximated with the peak intensity P, which is obtained when the homogeneously polymerized hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization method) is analyzed using a thermal decomposition gas chromatography mass spectrometer))

The above g=P/P0 can be calculated from the specific peak intensity obtained by thermal decomposition gas chromatography mass spectrometry analysis of the hydrogenated block copolymer (A) (hereinafter, sometimes referred to as py-GC/MS measurement), and is a random parameter of the hydrogenated block copolymer (A). The above random parameter g (the reason for evaluating randomness is described below) indicates how uniformly the vinyl aromatic monomer units and the covalent diene monomer units in the hydrogenated copolymer block (b) are arranged. The larger the value of the above g, the more uniformly the vinyl aromatic monomer units and the covalent diene monomer units are arranged. The reason why the randomness can be evaluated using the above randomness parameter g is that, as described below, P represents the total intensity of the peak of the decomposition product of the (vinyl aromatic monomer)-(covalent diene monomer)-(vinyl aromatic monomer) 3-linked structure in the hydrogenated copolymer block (b). That is, P represents how uniformly the vinyl aromatic monomer and the covalent diene monomer react.

In the hydrogenated block copolymer (A) of the present embodiment, the above-mentioned random parameter g is 0.75 or more, preferably 0.8 or more, more preferably 0.85 or more, and further preferably 0.9 or more. If the random parameter g is 0.75 or more, the hydrogenated block copolymer (A) of the present embodiment tends to show good wear resistance. Furthermore, if it is 0.9 or more, it shows higher wear resistance and can be used in the following situations: in applications where the wear resistance is more stringent, such as automotive interior materials, applications where excellent wear resistance is required in thinner-walled molded bodies, or automotive interior materials applications, applications where wear resistance is required by higher loads or coarser mesh fabrics, such as fabrics coarser than cotton fabrics such as fine white cloth No. 3, i.e., coarse twill cotton fabrics, etc., when riding in a car, and it is required to maintain the appearance for a long time. In addition, if the random parameter g is 0.75 or more, the height of the tanδ peak of the hydrogenated block copolymer (A) of the present embodiment is increased, the low resilience is improved, and a good touch is shown. Furthermore, if it is above 0.9, a higher tanδ peak can be obtained, which can lead to better low resilience and a tendency to obtain a better touch.

[Calculation method of random parameter g] The random parameter g can be calculated based on the specific peak intensity obtained by py-GC/MS measurement. The peak intensity P used in the calculation of g is the sum of the three peak intensities of the decomposition product of the (vinyl aromatic monomer)-(covalent diene monomer)-(vinyl aromatic monomer) structure in the hydrogenated copolymer block (b), and the three peaks are defined by the following two conditions (i) and (ii).

(Condition (i)) When the retention time of the peak derived from styrene dimer (attributed by sample measurement) detected when the sample was measured under the conditions shown in Table 1 below was set to 0 min, the peaks detected were at relative retention times of 1.83 min, 2.15 min, and 2.45 min (with an allowable error of about 0.01 min). (Condition (ii)) The fragment peaks had mass values of 252, 264, and 276, respectively.

The relative area value obtained by performing the following device sensitivity correction on the sum of the absolute area values of the three peaks defined by the above method is set as the peak intensity P. The random parameter g can be calculated by the ratio with P0 obtained by the following (Formula I): g = P/P0. P0 = k × RS    …  (Formula I) In the above (Formula I), RS is the content (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (A), which can be measured by a nuclear magnetic resonance device (NMR) or the like. In the above (Formula I), k is a proportional constant obtained by using the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (A) and the peak intensity P, which is the peak intensity when the hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization method) is measured using a pyrolysis gas chromatography mass spectrometry analyzer (py-GC/MS). Experimentally, the value of k is about 0.0056. For example, when the RS of a certain hydrogenated block copolymer is 40 mass %, P0 becomes 0.0056×40=0.224 according to the above (Formula I). When the peak intensity P = 0.112 obtained by py-GC/MS, it can be calculated as g = 0.112/0.224 = 0.5.

P0 is an estimated value of the peak intensity P measured by py-GC/MS when the hydrogenated block copolymer (A) is polymerized by the specific polymerization method (homogeneous polymerization method) described below. By comparing the above P0 with the value of P actually detected in the form of a random parameter g = P/P0, it is possible to evaluate how uniformly the vinyl aromatic monomers and the covalent diene monomers in the hydrogenated copolymer block (b) are arranged.

Since the detection sensitivity of the MS detector in py-GC/MS measurement changes every time it is adjusted, an external standard substance is used for sensitivity correction. In this manual, unless otherwise specified, the value of the peak intensity P is set to the value obtained by dividing the peak absolute area value by the reference value X obtained by the measurement of the external standard substance. As an external standard substance, it is preferred to use dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol, hereinafter referred to as BHT), which is not easily decomposed under heat or oxygen atmosphere and is easy to handle. The reference value X is set to the peak area value obtained when 0.010 mg of the external standard substance is measured under the conditions of the following Table 1. Furthermore, in Table 1, "sample measurement amount" is the measurement value obtained by preparing the solution and dropping it into the sample cup and then air-drying it, so the measured sample amount is set to 0.10 mg of solid.

[Table 1] py-GC/MS measurement conditions Pyrolyzer device Frontier Lab Multishot Pyrolyzer EGA/PY-3030D Pyrolyzer heating conditions 500℃ GC device Agilent Technologies manufactures the 7890A Use the column DB-1 (30 m×0.25 mmΦ, film thickness 0.25 μm) Column temperature mode After keeping at 40℃ for 5 min, increase the temperature to 320℃ at 20℃/min and keep at 320℃ for 11 min Gas flow rate 1 ml/min Sample injection port temperature 320℃ Split Ratio 1/50 Sample measurement 0.10 mg MS device JEOL RESONANCE Co., Ltd. manufactures JMS-Q1500GC Interface temperature 320℃ Ionization EI 70 eV Scanning range m/z 10～800 Ion source temperature 240℃

[Homogeneous Polymerization] The hydrogenated block copolymer (A) of this embodiment is prepared by homogeneous polymerization in the calculation of the random parameter g of <Condition (3)>. In the preparation of the hydrogenated block copolymer (A) by homogeneous polymerization, it is preferred to use an in situ FTIR spectrophotometer ReactIR 45P (hereinafter referred to as ReactIR) manufactured by Mettler Toledo. By using the above-mentioned ReactIR, the concentration of the vinyl aromatic compound and the concentration of the covalent diene compound in the polymerization reaction can be quantified in real time, so the feed rate of the vinyl aromatic compound and the covalent diene compound can be controlled based on the quantitative results, and a uniform random copolymer can be prepared at a higher level.

As an example of a method for producing the hydrogenated block copolymer (A) of the present embodiment, there is the following method: the reactivity ratio of the vinyl aromatic compound and the covalent diene compound within a certain time is immediately determined by the measurement of ReactIR, and the feed rate of the vinyl aromatic compound and the covalent diene compound as polymerization monomers is immediately controlled in such a way as to obtain the desired reactivity ratio. According to the feed amount S0 of the vinyl aromatic compound at the specified time t0-t1, the feed amount B0 of the co-diene compound, the change ΔS of the vinyl aromatic compound in the reaction system at the specified time t0-t1, and the change ΔB of the co-diene compound, the reactivity ratio (S0+ΔS)/(B0+ΔB) of the vinyl aromatic compound and the co-diene compound is immediately obtained, and the feed rate of the vinyl aromatic compound and the co-diene compound is immediately controlled in such a way that the desired reactivity ratio is obtained. For example, when the above reactivity ratio: (S0+ΔS)/(B0+ΔB) is higher than the desired reactivity ratio, the feed rate of the co-diene compound can be increased or the feed rate of the vinyl aromatic compound can be delayed.

Generally, in the copolymerization of a vinyl aromatic compound and a covalent diene compound, when the polymerization is carried out uniformly at a desired reactivity ratio, it is necessary to start feeding with the feed rate ratio of the vinyl aromatic compound and the covalent diene compound being the same as the desired reactivity ratio, and to terminate the feeding of the vinyl aromatic compound and the covalent diene compound at the end of the copolymerization. For example, in the case of copolymerization of styrene and butadiene, generally, the reaction rate of butadiene is faster than the reaction rate of styrene, so immediately after the start of feeding, the reactivity ratio: (S0+ΔS)/(B0+ΔB) tends to become less than the target value, and gradually approaches the target reactivity ratio. Also, immediately after the end of feeding, the reactivity ratio: (S0+ΔS)/(B0+ΔB) tends to be greater than the target value. By using the above-mentioned ReactIR, the reactivity ratio: (S0+ΔS)/(B0+ΔB) is measured in real time, and the feed rate ratio of styrene and butadiene is controlled in such a way as to achieve the target reactivity ratio. Thus, the reactivity ratio: (S0+ΔS)/(B0+ΔB) immediately after the feed starts and at the end of the feed can be controlled to the target reactivity ratio.

Below, three specific hydrogenated block copolymers (A)-I to (A)-III were obtained and measured by thermal decomposition gas chromatography mass spectrometry (py-GC/MS) to obtain peak intensity P. In addition, based on the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer ((A)-I to (A)-III) and the first-order approximation formula of the peak intensity P, the coefficient k of the above (Formula I) was calculated as k=005563. The determined values for k are shown in the following Table 2.

<Hydrogenated block copolymer (A)-I> Batch polymerization was performed using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20 mass%) containing 20 parts by mass of styrene was added. Second, 0.053 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was performed at 65°C for 1 hour. Second, a cyclohexane solution (concentration 20 mass%) containing 50 parts by mass of butadiene and 30 parts by mass of styrene was added, and polymerization was performed at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (converted by mass). Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained by the above method had a styrene content of 50 mass%, and the content RS of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) was 30 mass%. Furthermore, in the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared in the above manner was added based on Ti per 100 mass parts of the block copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (A)-I. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-I was 98 mol %.

<Hydrogenated block copolymer (A)-II> The 50 mass parts of butadiene and 30 mass parts of styrene in the above hydrogenated block copolymer (A)-I were changed to 40 mass parts of butadiene and 40 mass parts of styrene, and polymerization and hydrogenation were carried out to obtain hydrogenated block copolymer (A)-II. The styrene content in the block copolymer before the hydrogenation reaction was 60 mass%, and the content RS of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) as a whole was 40 mass%, and the hydrogenation rate of the hydrogenated block copolymer (A)-II was 98 mol%.

<Hydrogenated block copolymer (A)-III> The 50 mass parts of butadiene and 30 mass parts of styrene in the above hydrogenated block copolymer (A)-I were changed to 30 mass parts of butadiene and 50 mass parts of styrene, and polymerization reaction and hydrogenation reaction were carried out to obtain hydrogenated block copolymer (A)-III. In the block copolymer before the hydrogenation reaction, the styrene content was 70 mass%, and the content RS of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) as a whole was 50 mass%, and the hydrogenation rate of the hydrogenated block copolymer (A)-III was 98 mol%.

[Table 2] (A)-I (A)-II (A)-III The content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (a) as a whole RS (mass %) 30 40 50 Peak intensity P 0.167 0.223 0.278

(Structure of Hydrogenated Block Copolymer (A)) The structure of the hydrogenated block copolymer (A) according to the present embodiment may be, for example, a structure represented by the following general formula. 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, ca-(ba) _n -c, ac-(ba) _n -c, ab-(ca) _n -b, ac-(bc) _n -ac, c-(abc) _n -ac , a-(cb) _n -ca, c-(ac) _n -bcac, [(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 Furthermore, in the above general formulas, a represents a polymer block (a) mainly composed of a vinyl aromatic monomer unit, b represents a hydrogenated copolymer block (b) comprising a vinyl aromatic monomer unit and a covalent diene monomer unit, and c represents a hydrogenated polymer block (c) mainly composed of a covalent diene monomer unit. n is an integer greater than 1, preferably an integer from 1 to 5. m is an integer greater than 2, preferably an integer from 2 to 11. X represents a residual group of a coupling agent or a residual group of a multifunctional initiator.

(Other examples of the structure of the hydrogenated block copolymer (A)) The hydrogenated block copolymer (A) of the present embodiment may also be a modified block copolymer to which an atomic group having a prescribed functional group is bonded. It is sufficient to appropriately set the presence or absence of modification, the type of functional group, etc. according to the structure of the resin to be kneaded when preparing a composition using the hydrogenated block copolymer (A) of the present embodiment. In addition, when the hydrogenated block copolymer (A) is set as a modified block copolymer, it may also be a secondary modified block copolymer. In this specification, "secondary modification" is a name given by a manufacturing method, and the initial step of bonding the functional group to the polymer is called the primary modification, and the step of reacting other compounds with its functional group is called the secondary modification. For example, a typical manufacturing method is to carry out polymerization in a solution, and then react other compounds (such as maleic acid) with a primary modified product formed by a reaction between a modifier (such as an amine) and the polymerization termination terminal in an extruder to produce a secondary modified product.

[Method for producing hydrogenated block copolymer (A)] The block copolymer in the state before hydrogenation of the hydrogenated block copolymer (A) of the present embodiment can be obtained, for example, by the following method: using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent to allow a vinyl aromatic compound and a conjugated diene compound to undergo active anionic polymerization.

(Hydrocarbon solvent) Examples of hydrocarbon solvents include: aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, but are not limited to the above.

(Polymerization initiator) The polymerization initiator is not particularly limited, and examples thereof include: organic alkali metal compounds such as aliphatic alkali metal compounds, aromatic alkali metal compounds, and organic amine alkali metal compounds that are known to have anionic polymerization activity for vinyl aromatic compounds and conjugated dienes. As the organic alkali metal compound, for example, aliphatic and aromatic alkali lithium compounds having 1 to 20 carbon atoms are preferred, but are not limited to the above, and compounds containing one lithium in one molecule, dilithium compounds containing multiple lithium in one molecule, trilithium compounds, and tetralithium compounds can be used. Specifically, examples include: n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, the reaction product of diisopropenylbenzene and sec-butyl lithium, the reaction product of divinylbenzene and sec-butyl lithium and a small amount of 1,3-butadiene, etc. Furthermore, for example, the organoalkali metal compounds disclosed in the specification of U.S. Patent No. 5,708,092, the specification of British Patent No. 2,241,239, and the specification of U.S. Patent No. 5,527,753 can also be applied.

(Adjuster) When an organic alkali metal compound is used as a polymerization initiator to copolymerize a vinyl aromatic compound and a covalent diene compound, a prescribed adjuster is used to adjust the content of the vinyl bond (1,2-bond or 3,4-bond) generated by the covalent diene compound incorporated into the polymer, or the random copolymerization of the vinyl aromatic monomer unit and the covalent diene monomer unit. Such adjusters include, for example, tertiary amine compounds, ether compounds, metal alcoholate compounds, etc., but are not limited to the above. The adjuster may be used alone or in combination of two or more.

As tertiary amine compounds, for example, compounds represented by the general formula R1R2R3N (here, R1, R2, and R3 represent a alkyl group having 1 to 20 carbon atoms or a alkyl group having a tertiary amine group) can be cited, but are not limited to the above. Specifically, examples include: trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperidinium, N,N,N',N'',N''-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, etc.

As ether compounds, for example, linear ether compounds and cyclic ether compounds can be applied, but are not limited to the above. As linear ether compounds, for example, dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and other ethylene glycol dialkyl ether compounds; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and other diethylene glycol dialkyl ether compounds, but are not limited to the above. As cyclic ether compounds, for example, tetrahydrofuran, dioxane, 2,5-dimethyloxycyclopentane, 2,2,5,5-tetramethyloxycyclopentane, 2,2-bis(2-tetrahydrofuranyl)propane, alkyl ethers of furan methanol, etc. can be cited, but are not limited to the above.

Examples of the metal alkoxide compound include sodium tert-pentoxide, sodium tert-butoxide, potassium tert-pentoxide, potassium tert-butoxide, and the like, but the compound is not limited thereto.

(Polymerization method) As a method for polymerizing a vinyl aromatic compound and a copolyene compound using an organic alkali metal compound as a polymerization initiator, a previously known method can be applied. For example, it can be any of batch polymerization, continuous polymerization, or a combination thereof, but it is not limited to the above. In particular, in order to obtain a copolymer with excellent heat resistance, batch polymerization is suitable. The polymerization temperature is preferably 0°C to 180°C, and more preferably 30°C to 150°C. The polymerization time varies depending on the conditions, but is usually within 48 hours, and preferably 0.1 to 10 hours. In addition, as the atmosphere of the polymerization system, an inert gas atmosphere such as nitrogen is preferred. The polymerization pressure is not particularly limited as long as it is set to a pressure range that can maintain the monomer and solvent in the liquid phase within the above temperature range. Furthermore, it is better to pay more attention to avoid the mixing of impurities such as water, oxygen, carbon dioxide, etc. into the polymerization system that may cause the catalyst and active polymer to become inert.

Furthermore, at the end of the above-mentioned polymerization step, a coupling reaction can be carried out by adding a necessary amount of a coupling agent having two or more functions. As the bifunctional coupling agent, known ones can be used without particular limitation. For example, alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, etc.; dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, etc.; acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, phthalic acid esters, etc. can be cited. As a polyfunctional coupling agent having three or more functions, any known coupling agent can be used without any particular limitation. Examples include: polyhydric alcohols having three or more functions, epoxidized soybean oil, diglycidyl bisphenol A, polyhydric epoxy compounds such as 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane; silicon halides represented by the general formula R _{4 -} nSiX _n (where R represents a alkyl group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), such as methylsilicon trichloride, tert-butylsilicon trichloride, silicon tetrachloride, and bromides thereof; and polyhydric epoxy compounds represented by the general formula R _{4 -} nSnX _n (Here, R represents a carbon number of 1 to 20 alkyl groups, X represents a halogen, and n represents an integer of 3 to 4) a tin halide compound represented by, for example, methyltin trichloride, tert-butyltin trichloride, tin tetrachloride and other polyvalent halogen compounds. In addition, dimethyl carbonate or diethyl carbonate may also be used.

(Modification step) As described above, the hydrogenated block copolymer (A) of the present embodiment may be a modified block copolymer to which an atomic group having a functional group is bonded. The bonding of the atomic group having a functional group is preferably performed as a step before the hydrogenation step described below. Examples of the “atomic group having a functional group” include, but are not limited to, an atomic group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acyl halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoric acid ester group, an amino group, an imino group, a nitrile group, a pyridine group, a quinoline group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silyl halide group, a silanol group, an alkoxysilyl group, a tin halide group, a boric acid group, a boron-containing group, a borate group, an alkoxytin group, a phenyltin group, and the like. It is particularly preferred to be an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amine group, a silanol group, and an alkoxysilyl group. The above-mentioned "atomic group having a functional group" can be bonded using a modifier. Examples of the modifier include tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidyloxyethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyldimethylphenoxysilane, bis(γ-glycidyloxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylurea, N-methylpyrrolidone, etc., but are not limited to the above.

The modified block copolymer is not particularly limited, and can be obtained, for example, by the following method: by anionic living polymerization, using a polymerization initiator having a functional group or an unsaturated monomer having a functional group for polymerization, or forming a functional group at the active end, or allowing a modifier containing a functional group to undergo an addition reaction. As another method, it can be obtained by the following method: reacting an organic alkali metal compound such as an organic lithium compound with a block copolymer (metallization reaction), and allowing a modifier having a functional group to undergo an addition reaction with a block polymer to which an organic alkali metal is added. Among them, in the case of the latter method, the modified hydrogenated block copolymer can also be prepared by performing a metallization reaction after obtaining a hydrogenated block copolymer, and then reacting the modifier. The temperature for the modification reaction is preferably 0 to 150°C, more preferably 20 to 120°C. The time required for the modification reaction varies depending on other conditions, preferably within 24 hours, more preferably 0.1 to 10 hours. Depending on the type of modifier used, sometimes during the stage of reacting the modifier, amine groups and the like are usually converted into organic metal salts, but in this case, they can be converted into amine groups and the like by treating with compounds having active hydrogen such as water or alcohol. Furthermore, in such a modified block copolymer, a portion of unmodified block copolymers may also be mixed in the modified block copolymer.

Furthermore, the modified block copolymer may also be a secondary modified block copolymer. The secondary modified block copolymer may be obtained by reacting a secondary modifier reactive with the functional group of the modified block copolymer with the modified block copolymer. As the secondary modifier, for example, a modifier having a functional group selected from a carboxyl group, an anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group may be cited, but it is not limited to the above, and preferably has at least 2 functional groups selected from these functional groups. Among them, when the functional group is an anhydride group, it may also have one anhydride group.

As described above, when the secondary modifier is reacted with the modified block copolymer, the amount of the secondary modifier used is preferably 0.3 to 10 mol, more preferably 0.4 to 5 mol, and further preferably 0.5 to 4 mol per 1 equivalent of the functional group bonded to the modified block copolymer. Regarding the method of reacting the modified block copolymer with the secondary modifier, a known method can be applied without particular limitation. For example, the following melt kneading method or a method of dissolving or dispersing and mixing each component in a solvent and reacting them can be cited. Furthermore, the secondary modification is preferably performed after the hydrogenation step.

Examples of the secondary modifier include maleic anhydride, pyromellitic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, tolyl diisocyanate, tetraglycidyl-1,3-diaminomethylcyclohexane, bis-(3-triethoxysilylpropyl)-tetrasulfide, but the present invention is not limited thereto.

Furthermore, the hydrogenated block copolymer (A) of the present embodiment can be a modified block copolymer obtained by grafting and modifying α,β-unsaturated carboxylic acid or its derivatives, such as its anhydride, ester, amide, and imide. As α,β-unsaturated carboxylic acid or its derivatives, for example, maleic anhydride, maleic anhydride imide, acrylic acid or its ester, methacrylic acid or its ester, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydride, etc. can be cited, but it is not limited to the above. The addition amount of α,β-unsaturated carboxylic acid or its derivative is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass per 100 parts by mass of the hydrogenated block copolymer (A). The reaction temperature for graft modification is preferably 100 to 300°C, more preferably 120 to 280°C. The graft modification method is not particularly limited, and for example, the method described in Japanese Patent Publication No. 62-79211 can be applied.

(Hydrogenation reaction step) The hydrogenated block copolymer (A) of this embodiment can be obtained by the following method: using a prescribed hydrogenation catalyst, subjecting the non-hydrogenated non-modified or modified block copolymer as described above to a hydrogenation reaction. The hydrogenation catalyst is not particularly limited. For example, known catalysts can be cited, namely (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.; (2) so-called Ziegler-type hydrogenation catalysts using organic acid salts of Ni, Co, Fe, Cr, etc. or transition metal salts such as acetylacetonate and reducing agents such as organic aluminum; (3) so-called organic metal complexes such as organic metal compounds of Ti, Ru, Rh, and Zr, etc. Furthermore, as a hydrogenation catalyst, for example, the hydrogenation catalyst described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041 can also be used, but it is not limited to the above. As a suitable hydrogenation catalyst, a titanocene compound, a reducing organic metal compound, or a mixture thereof can be cited. As a titanocene compound, for example, the compound described in Japanese Patent Publication No. 8-109219 can be used, but it is not limited to the above. Specifically, compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride, can be cited. As reducing organic metal compounds, organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds, or organic zinc compounds can be cited, but are not limited to the above.

The hydrogenation reaction is described. The reaction temperature is usually preferably in the range of 0 to 200°C, more preferably in the range of 30 to 150°C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and further preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof. It is preferred to remove catalyst residues from the solution of the hydrogenated block copolymer obtained through the hydrogenation reaction as needed, and separate the hydrogenated block copolymer from the solution. As separation methods, for example, there are: adding polar solvents such as acetone or alcohol, which are poor solvents for hydrogenated modified copolymers, to the reaction solution after hydrogenation to precipitate the polymer and recover it; putting the reaction solution into hot water while stirring, removing the solvent by steam stripping and recovering it; directly heating the polymer solution to remove the solvent by distillation, etc., but it is not limited to the above.

Furthermore, various stabilizers such as phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers may be added to the hydrogenated block copolymer (A) of the present embodiment.

[Hydrogenated block copolymer composition] The hydrogenated block copolymer composition of the present embodiment contains a hydrogenated block copolymer (A), an olefinic resin (B), a thermoplastic resin (C), and a softener (D). The hydrogenated block copolymer composition of the present embodiment contains the hydrogenated block copolymer (A) of the present embodiment: 1% by mass or more and 50% by mass or less, at least one olefinic resin (B): 5% by mass or more and 90% by mass or less, at least one thermoplastic resin (C): 1% by mass or more and 50% by mass or less, and at least one softener (D): 5% by mass or more and 90% by mass or less.

(Olefinic resin) The olefinic resin (Olefinic resin) constituting the hydrogenated block copolymer composition of the present embodiment is described below. As the olefinic resin (Olefinic resin), for example, homopolymers of α-olefins such as polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 1-octene can be cited, but it is not limited to the above. In addition, random copolymers or block copolymers containing combinations of olefins selected from ethylene, propylene, butene, pentene, hexene, octene, etc. can be cited. Specifically, examples include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-3-methyl-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-1-decene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-4-methyl-1-pentene copolymers, ethylene-propylene-1-butene copolymers, propylene-1-hexene-ethylene copolymers, propylene-1-octene-ethylene copolymers, and the like. In addition, copolymers with ethylene and/or propylene also include copolymers with other unsaturated monomers. As the copolymers of the above-mentioned monomers and other unsaturated monomers, for example, there can be cited: copolymers of ethylene and/or propylene with unsaturated organic acids or their derivatives such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, aryl maleic anhydride, alkyl maleic anhydride, etc.; copolymers of ethylene and/or propylene with vinyl esters such as vinyl acetate; and copolymers of ethylene and/or propylene with non-conjugated dienes such as dicyclopentadiene, 4-ethylidene-2-northene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, etc., but the above are not limited to the above. From the perspective of economy or improving the compatibility of the hydrogenated block copolymer composition of the present embodiment to obtain higher transparency, the (ethylene) hydrocarbon resin preferably contains at least one polypropylene resin.

In addition, the olefinic resin (II) may be modified with a prescribed functional group. The functional group is not particularly limited, and examples thereof include: an epoxy group, a carboxyl group, an anhydride group, a hydroxyl group, etc. The functional group-containing compound or modifier used to modify the olefinic resin (II) is not particularly limited, and examples thereof include the following compounds. For example, unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether; or unsaturated organic acids such as maleic acid, fumaric acid, itaconic acid, linaconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, and itaconic anhydride, etc. may be cited. Other than these, there are no particular limitations, and examples thereof include ionic polymers, chlorinated polyolefins, etc.

From the viewpoint of economy or making the compatibility in the hydrogenated block copolymer composition of the present embodiment better and obtaining higher transparency, the olefinic resin (B) is preferably a polypropylene resin such as a polypropylene homopolymer, a random or block copolymer of ethylene-propylene, etc. In particular, from the viewpoint of transparency and softness, a random copolymer of ethylene-propylene is more preferred. The olefinic resin (B) may include only one single material or may be a combination of two or more.

The hydrogenated block copolymer composition of the present embodiment contains a hydrogenated block copolymer (A) and at least one olefinic resin (B), and the content of the hydrogenated block copolymer (A) is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 45% by mass or less, and further preferably 5% by mass or more and 40% by mass or less. If the content of the hydrogenated block copolymer (A) is 1% by mass or more, the wear resistance of the hydrogenated block copolymer composition tends to be improved and the hardness tends to be reduced. On the other hand, if the content of the hydrogenated block copolymer (A) is 50% by mass or less, the oil resistance of the hydrogenated block copolymer composition of the present embodiment tends to be improved. In addition, from the perspective of the mechanical strength of the hydrogenated block copolymer composition of this embodiment, the content of the olefin resin (B) is 5% by mass or more, and from the perspective of the low-temperature characteristics of the hydrogenated block copolymer composition, it is 90% by mass or less. It is preferably 7% by mass or more and 85% by mass or less, and more preferably 10% by mass or more and 80% by mass or less.

The hydrogenated block copolymer composition of the present embodiment contains, in addition to the hydrogenated block copolymer (A) and the polyolefin resin (B) of the present embodiment, at least one thermoplastic resin (C) in an amount of 1% by mass or more and 50% by mass or less, and at least one softener (D) in an amount of 5% by mass or more and 90% by mass or less. In addition, a modifier, an additive, etc. may also be formulated.

The softener (D) softens the hydrogenated block copolymer composition of the present embodiment and imparts fluidity (molding processability). As the softener, for example, mineral oil or liquid or low molecular weight synthetic softeners can be used, but are not limited to the above, and are particularly suitable for cycloalkane and/or wax processing oils or extender oils. The mineral oil softener is a mixture of aromatic rings, cycloalkane rings and wax chains. The wax chain with carbon number accounting for more than 50% of the total carbon is called a wax chain, the cycloalkane ring with carbon number of 30 to 45% is called a cycloalkane chain, and the aromatic carbon number exceeding 30% is called an aromatic chain. As synthetic softeners, for example, polybutene, low molecular weight polybutadiene, liquid wax, etc. can be used, but the above-mentioned mineral oil-based softeners are more preferred. When the hydrogenated block copolymer composition of the present embodiment requires higher heat resistance and mechanical properties, the mineral oil-based softener used preferably has a kinematic viscosity of 60 cst or more at 40°C, and more preferably 120 cst or more. The softener may be used alone or in combination of two or more.

The above-mentioned modifier is designed to improve the damage resistance of the surface of the hydrogenated block copolymer composition of the present embodiment, or has the function of improving adhesion. As a modifier, for example, organic polysiloxane can be applied, but it is not limited to the above. It exerts the surface modification effect of the hydrogenated block copolymer composition and functions as an auxiliary agent for improving wear resistance. As a form of the modifier, it can be any of a low-viscosity liquid to a high-viscosity liquid or a solid. From the perspective of ensuring good dispersibility in the hydrogenated block copolymer composition of the present embodiment, it is preferably a liquid, that is, silicone oil. Furthermore, regarding the dynamic viscosity of the modifier, from the perspective of inhibiting the exudation of polysiloxane itself, it is preferably 90 cst or more, and more preferably 1000 cst or more. As polysiloxane, for example, general silicone oils such as dimethyl polysiloxane and methylphenyl polysiloxane; or various modified silicone oils such as alkyl modification, polyether modification, fluorine modification, alcohol modification, amino modification, and epoxy modification can be cited, but it is not limited to the above. In terms of the higher effect as an auxiliary agent for improving wear resistance, dimethyl polysiloxane is suitable, but there is no special limitation. These modifiers can be used alone or in combination of two or more.

There are no special restrictions on additives as long as they are fillers, lubricants, release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents, colorants, thermoplastic resins or rubber polymers that are commonly used in the formulation. Examples of fillers include inorganic fillers such as silica, talc, mica, calcium silicate, magnesium aluminate, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, and barium sulfate; and organic fillers such as carbon black, but not limited to the above. Examples of lubricants include stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethyl distearate, etc., but not limited to the above. Examples of plasticizers include organic polysiloxanes, mineral oils, etc., but not limited to the above. As antioxidants, for example, hindered phenol antioxidants can be cited, but not limited to the above. As heat stabilizers, for example, phosphorus-based, sulfur-based and amine-based heat stabilizers can be cited, but not limited to the above. As light stabilizers, for example, hindered amine-based light stabilizers can be cited, but not limited to the above. As ultraviolet absorbers, for example, benzotriazole-based ultraviolet absorbers can be cited, but not limited to the above. As reinforcing agents, for example, organic fibers, glass fibers, carbon fibers, metal whiskers, etc. can be cited, but not limited to the above. As colorants, for example, titanium oxide, iron oxide, carbon black, etc. can be cited, but not limited to the above. In addition, examples include those listed in "Rubber and Plastic Compounding Products" (edited by Rubber Digest Co., Ltd.).

((C) Thermoplastic resin) As the above-mentioned thermoplastic resin (C), for example, block copolymers of covalent diene compounds and vinyl aromatic compounds and hydrogenated products thereof (but different from the hydrogenated block copolymer (A) of the above-mentioned embodiment); polymers of the above-mentioned vinyl aromatic compounds; copolymers of the above-mentioned vinyl aromatic compounds and other vinyl monomers such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and methyl acrylate and other acrylic acid esters, methacrylic acid and methyl methacrylate and other methacrylic acid esters, acrylonitrile, methacrylonitrile, etc.; rubber-modified styrene resin (HIPS); acrylonitrile-butadiene-styrene copolymer (ABS); methacrylate-butadiene-styrene copolymer (MBS), etc., but not limited to the above.

Furthermore, examples of the above-mentioned (c) thermoplastic resin include: polyethylene; ethylene copolymers containing 50% by mass or more of ethylene, such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers and hydrolyzates thereof; polyethylene resins such as ethylene-acrylic acid ionomers or chlorinated polyethylene; polypropylene; propylene copolymers containing 50% by mass or more of propylene, such as propylene-ethylene copolymers, propylene-ethyl acrylate copolymers; or polypropylene resins such as chlorinated polypropylene; cyclic olefin resins such as ethylene-northene resins; polybutene resins; polyvinyl chloride resins; polyvinyl acetate resins and hydrolyzates thereof, but are not limited to the above.

In addition, as (c) thermoplastic resins, for example, there can be cited: polymers of acrylic acid and its esters or amides; polyacrylate resins; polymers of acrylonitrile and/or methacrylonitrile; copolymers containing 50% by mass or more of these acrylonitrile monomers and other copolymerizable monomers, i.e., nitrile resins; polyamide resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, and nylon-6-nylon-12 copolymers; polyester resins; thermoplastic polyurethane resins; poly-4,4'-dioxy The invention also includes polycarbonate polymers such as 2,2'-diphenyl-2,2'-propane carbonate; thermoplastic polysulfones such as polyether sulfones or polyallyl sulfones; polyoxymethylene resins; polyphenylene ether resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide and poly-4,4'-diphenyl sulfide; polyarylate resins; polyetherketone polymers or copolymers; polyketone resins; fluorine resins; polyoxybenzoyl polymers; polyimide resins; polybutadiene resins such as 1,2-polybutadiene and trans-polybutadiene, etc., but is not limited to the above.

Among the above-mentioned thermoplastic resins (C), polystyrene resins such as polystyrene and rubber-modified styrene resins are particularly preferred; polyethylene; polyethylene polymers such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, and ethylene-methacrylate copolymers; polypropylene; polypropylene resins such as propylene-ethylene copolymers; polyamide resins; polyester resins; and polycarbonate resins. The number average molecular weight of the thermoplastic resins (C) is usually 1,000 or more, preferably 5,000 to 5,000,000, and more preferably 10,000 to 1,000,000.

In the hydrogenated block copolymer composition of the present embodiment, the content of the thermoplastic resin (C) is set to 1 mass % or more from the viewpoint of mechanical strength, and is set to 50 mass % or less from the viewpoint of oil resistance. It is preferably 3 mass % or more and 47 mass % or less, and more preferably 5 mass % or more and 45 mass % or less. In addition, when the total amount of the above-mentioned components (A) and (C) is set to 100 mass parts, the content of component (C) is preferably 2 to 150 mass parts, more preferably 2 to 140 mass parts, and further preferably 2 to 130 mass parts.

((D) Softener) Next, the softener (D) constituting the hydrogenated block copolymer composition of the present embodiment is described. The softener (D) is preferably a rubber softener that softens the hydrogenated block copolymer composition and imparts processability. As the softener (D), for example, mineral oil or liquid or low molecular weight synthetic softeners can be cited, but are not limited to the above. Among them, cycloalkane-based and/or wax-based processing oils or extender oils are preferred. Mineral oil-based softeners are mixtures of aromatic rings, cycloalkane rings, and wax chains. The wax chain with carbon numbers accounting for more than 50% of the total carbon is called a wax series, the cycloalkane ring with carbon numbers of 30-45% is called a cycloalkane series, and the aromatic carbon number exceeding 30% is called an aromatic series. Synthetic softeners can be used in the hydrogenated block copolymer composition of the present embodiment without particular limitation, for example, polybutene, low molecular weight polybutadiene, liquid wax, etc. Among them, the above-mentioned mineral oil-based rubber softener is preferred.

In the hydrogenated block copolymer composition of the present embodiment, the content of the softener (D) is set to 5% by mass or more from the viewpoint of surface touch, and is set to 90% by mass or less from the viewpoint of suppressing bleeding. It is preferably 7% by mass or more and 85% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. In addition, when the total amount of components (A) and (B) is set to 100 parts by mass, the content of component (D) is preferably 2 to 150 parts by mass, more preferably 2 to 130 parts by mass, and further preferably 2 to 100 parts by mass. If the content of the softener (D) is below the above upper limit, bleeding can be suppressed and the surface touch becomes good.

In the hydrogenated block copolymer composition of the present embodiment, in addition to the above-mentioned components (A), (B), (C), and (D), additives can be arbitrarily formulated as needed. The type of additive is not particularly limited as long as it is commonly used in the formulation of thermoplastic resins or rubber polymers.

The hydrogenated block copolymer composition of the present embodiment can be produced by a previously known method. The method for producing the hydrogenated block copolymer composition of the present embodiment can be, for example, a method of melt-kneading the components (the above-mentioned hydrogenated block copolymer (A), and polyolefin resin (B), thermoplastic resin (C), softener (D), and other additives) using a mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a bidirectional kneader, or a multi-screw extruder; a method of removing the solvent by heating after dissolving or dispersing and mixing the components, etc., but is not limited to the above. From the viewpoint of productivity and good kneading properties, the melt kneading method using an extruder is particularly suitable. The shape of the hydrogenated block copolymer composition can be any shape such as granules, sheets, ropes, small pieces, etc., but is not limited to the above. In addition, it is also possible to directly produce a molded product after melt kneading.

(Reinforcing filler and reinforcing filler formulation) A reinforcing filler formulation can be prepared by blending at least one reinforcing filler selected from a silica-based inorganic filler, a metal oxide, a metal hydroxide, a metal carbonate, and carbon black (hereinafter, sometimes described as component (C)) into the hydrogenated block copolymer or the above-mentioned hydrogenated block copolymer composition (hereinafter, sometimes described as component (A)) of the present embodiment. Relative to 100 parts by mass of the hydrogenated block copolymer or the above-mentioned hydrogenated block copolymer composition (component (A)) of the present embodiment, the content of component (C) in the reinforcing filler formulation is preferably 0.5 to 100 parts by mass, more preferably 5 to 100 parts by mass, and further preferably 20 to 80 parts by mass. When the reinforcing filler formulation is prepared using the hydrogenated block copolymer of the present embodiment or the hydrogenated block copolymer composition (component (A)), it is preferred that 0 to 500 parts by mass, preferably 5 to 300 parts by mass, and more preferably 10 to 200 parts by mass of a thermoplastic resin and/or a rubbery polymer (hereinafter sometimes referred to as component (B)) different from the hydrogenated block copolymer of the present embodiment and the olefinic resin (B) and the thermoplastic resin (C) is contained relative to 100 parts by mass of component (A).

(Thermoplastic resin and/or rubber polymer different from component (B) and component (C)) As the above-mentioned thermoplastic resin and/or rubber polymer (component (B)), for example, there can be cited: block copolymers of conjugated diene monomers and vinyl aromatic monomers with a vinyl aromatic monomer unit content exceeding 60% by mass and their hydrogenated products (but different from the (A) hydrogenated block copolymer of the present embodiment); polymers of the above-mentioned vinyl aromatic compounds; copolymers of the above-mentioned vinyl aromatic compounds and other vinyl compounds (for example, ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and methyl acrylate and other acrylic acid esters, methacrylic acid and methyl methacrylate and other methacrylic acid esters, acrylonitrile, methacrylonitrile, etc.) Resins; rubber-modified styrene resins (HIPS); acrylonitrile-butadiene-styrene copolymers (ABS); methacrylate-butadiene-styrene copolymers (MBS); polyethylene; copolymers containing ethylene and other copolymerizable monomers such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers and their hydrolyzates, with an ethylene content of 50% or more; polyethylene resins such as ethylene-acrylic acid ionomers or chlorinated polyethylene; polypropylene; polypropylene resins such as propylene-ethylene copolymers, propylene-ethyl acrylate copolymers or chlorinated polypropylene , cyclic olefin resins such as ethylene-northene resins, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins and their hydrolyzates, copolymers containing propylene and other copolymerizable monomers with a propylene content of 50% or more; polymers of acrylic acid and its esters or amides; polyacrylate resins; polymers of acrylonitrile and/or methacrylonitrile; copolymers containing acrylonitrile monomers and other copolymerizable monomers with a propylene monomer content of 50% or more, i.e. nitrile resins; polyacrylic acid such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6, nylon-12 copolymers, etc. Amine resins; polyester resins; thermoplastic polyurethane resins; polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polysulfones such as polyether sulfones or polyallyl sulfones; polyoxymethylene resins; polyphenylene ether resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide and poly-4,4'-diphenyl sulfide; polyarylate resins; polyetherketone polymers or copolymers; polyketone resins; fluorine resins; polyoxybenzoyl polymers; polyimide resins; polybutadiene resins such as 1,2-polybutadiene and trans-polybutadiene, etc., but not limited to the above. The components (B) may also be bonded with an atomic group containing a polar group such as a hydroxyl group, an epoxy group, an amine group, a carboxylic acid group, or an anhydride group.

The silica-based inorganic filler that can be used as the above-mentioned reinforcing filler (component (C)) is a solid particle with a chemical formula _SiO2 as the main component of the structural unit, and examples thereof include: silica, clay, talc, kaolin, mica, wollastonite, montmorillonite, zeolite, glass fiber and other inorganic fiber-like substances, but are not limited to the above. In addition, a silica-based inorganic filler whose surface is hydrophobized or a mixture of a silica-based inorganic filler and an inorganic filler other than silica-based can also be used. As the silica-based inorganic filler, silica and glass fiber are preferred. As silica, what is called dry white carbon, wet white carbon, synthetic silicate white carbon, colloidal silica, etc. can be used. The silica-based inorganic filler preferably has an average particle size of 0.01 to 150 μm. The silica-based inorganic filler is dispersed in the reinforcing filler formulation. In order to fully exert its addition effect, the average dispersed particle size is preferably 0.05 to 1 μm, and more preferably 0.05 to 0.5 μm.

The metal oxide that can be used as the above-mentioned reinforcing filler (component (C)) is a solid particle with a chemical formula of MxOy (M is a metal atom, x and y are integers of 1 to 6 respectively) as the main component of the structural unit, for example: aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, etc. In addition, as a reinforcing filler, a mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used. Examples of metal hydroxides used as reinforcing fillers include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, alkaline magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, hydrates of tin oxide, hydrates of inorganic metal compounds such as borax, etc., but are not limited to the above. Magnesium hydroxide and aluminum hydroxide are particularly preferred. Examples of metal carbonates used as reinforcing fillers include calcium carbonate, magnesium carbonate, etc., but are not limited to the above. In addition, as reinforcing fillers, for example, various grades of carbon black such as FT (Fine Thermal), SRF (Semi-reinforcing Furnace), FEF (Fast Extruding Furnace), HAF (High Abrasion Furnace), ISAF (Intermediate Super Abrasion Furnace), and SAF (Super Abrasion Furnace) can be used, and preferably carbon black having a nitrogen adsorption specific surface area of 50 mg/g or more and a DBP (dibutyl phthalate) oil absorption of 80 mL/100 g or more.

A silane coupling agent (hereinafter sometimes referred to as component (D)) may also be formulated in the reinforcing filler formulation using the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)) of the present embodiment. The silane coupling agent (D) is used to make the interaction between the hydrogenated block copolymer (A) of the present embodiment and the reinforcing filler (C) more intimate, and is a compound having a group having affinity or bonding properties for one or both of the hydrogenated block copolymer (A) and the reinforcing filler (C). As a preferred silane coupling agent (D), for example, there can be cited those having a polysulfide bond formed by linking two or more silyl groups and/or sulfur with a silanol group or an alkoxysilane, but it is not limited to the above. Specifically, there can be cited: bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide, 3-butylpropyl-trimethoxysilane, 3-triethoxysilylpropyl-N,N-dimethylthioaminomethyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, etc. From the perspective of achieving the desired effect, the amount of silane coupling agent (D) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 15% by mass relative to the reinforcing filler formulation.

The reinforcing filler formulation containing the hydrogenated block copolymer (A) of the present embodiment or the above-mentioned hydrogenated block copolymer composition and the reinforcing filler can be vulcanized by a vulcanizing agent, that is, crosslinked 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 compounds, high molecular weight polysulfide compounds, etc.) can be cited. The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer (A) or the above-mentioned hydrogenated block copolymer composition, preferably 0.1 to 15 parts by mass. As the organic peroxide used as the vulcanizing agent (hereinafter, sometimes described as component (E)), from the viewpoint of odor or scorch stability (the property that it does not crosslink under the conditions when the components are mixed, but crosslinks rapidly under the conditions of crosslinking reaction), for example, 2,5-dimethyl-2,5-di-(tert-butylperoxide)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxide)hexyne-3, 1,3-bis(tert-butylperoxide isopropyl)benzene, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 4,4-bis(tert-butylperoxide) valerate n-butyl, di-tert-butyl peroxide are preferred, but are not limited to the above. In addition to the above, for example, diisopropylbenzene peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauryl peroxide, tert-butyl cumyl peroxide, etc. can also be used.

Furthermore, during vulcanization, as a vulcanization accelerator (hereinafter, sometimes described as component (F)), sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, dithiocarbamate-based compounds, etc. can also be used in an amount as needed. Furthermore, as a vulcanization aid, zinc white, stearic acid, etc. can also be used in an amount as needed. When an organic peroxide is used as the above-mentioned vulcanizing agent to crosslink the reinforcing filler formulation, the following components can be used together with the organic peroxide as the above-mentioned vulcanizing agent: a peroxide crosslinking auxiliary agent (in the form of trihydroxymethylpropane-N,N'-m-phenylenedibutylene diimide) such as p-quinone dioxime, p-,p-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trihydroxymethylpropane-N,N'-m-phenylenedibutylene diimide, etc. hereinafter, sometimes described as component (G)); multifunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trihydroxymethylpropane trimethacrylate, and allyl methacrylate; multifunctional vinyl monomers such as vinyl butyrate and vinyl stearate (hereinafter, sometimes described as component (H)), etc. Such vulcanization accelerator (F), peroxide crosslinking aid (G), and multifunctional vinyl monomer (H) are usually used in a ratio of preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the hydrogenated block copolymer (A) or the above-mentioned hydrogenated block copolymer composition (component (A)). As a method of vulcanizing the reinforcing filler formulation using a vulcanizing agent, the previously implemented method can be applied, such as vulcanizing at a temperature of 120 to 200°C, preferably 140 to 180°C. The vulcanized reinforcing filler formulation exhibits heat resistance, flex resistance or oil resistance in the state of a sulfide.

In order to improve the processability of the reinforcing filler formulation using the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition of the present embodiment, a softener (hereinafter, sometimes described as component (I)) may be further formulated. That is, in addition to the softener (D) constituting the hydrogenated block copolymer composition, a softener may be further formulated in a required amount. The softener is preferably a mineral oil or a liquid or low molecular weight synthetic softener. Among them, cycloalkane-based and/or wax-based processing oil or extender oil for softening, compatibilizing, and improving processability of rubber is generally preferred. Mineral oil-based softeners are a mixture of aromatic rings, cycloalkane rings and wax chains. The wax chain with carbon numbers accounting for more than 50% of the total carbon is called a wax series, the cycloalkane ring with carbon numbers of 30-45% is called a cycloalkane series, and the aromatic carbon number exceeding 30% is called an aromatic series. Synthetic softeners can be used in the above-mentioned reinforcing filler formulations, such as polybutene, low molecular weight polybutadiene, liquid wax, etc. However, the above-mentioned mineral oil-based softeners are preferred. The amount of the softener (ingredient (I)) in the reinforcing filler formulation is preferably 0 to 100 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 30 to 90 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer (A) or the above-mentioned hydrogenated block copolymer composition (ingredient (A)). If the amount of the softener exceeds 100 parts by mass, it is easy to ooze out and there is a risk of stickiness on the surface of the composition.

The reinforcing filler formulation containing the hydrogenated block copolymer (A) of this embodiment or the above hydrogenated block copolymer composition can be suitably used as a building material, wire sheathing material or vibration damping material, etc. Moreover, its sulfide is suitable for tire use or anti-vibration rubber, belts, industrial products, shoes, foams, etc. by utilizing this characteristic.

(Crosslinked product) The hydrogenated block copolymer (A) of the present embodiment or the above hydrogenated block copolymer composition can be crosslinked in the presence of a vulcanizing agent to form a crosslinked product, i.e., a crosslinked hydrogenated block copolymer or a crosslinked hydrogenated block copolymer composition. By crosslinking the hydrogenated block copolymer (A) of the present embodiment or the above hydrogenated block copolymer composition, heat resistance [high temperature C-Set (compression set, compression permanent set)] or flexural resistance can be improved. In the case of preparing a crosslinked product of the reinforcing filler formulation containing the hydrogenated block copolymer (A) of the present embodiment or the hydrogenated block copolymer composition, in particular, the blending ratio of the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)) and the thermoplastic resin different from the olefinic resin (B) or the thermoplastic resin (C) and/or the rubbery polymer (component (B)) is preferably 10/90 to 100/0, more preferably 20/80 to 90/10, and further preferably 30/70 to 80/20 in terms of the mass ratio of component (A)/component (B).

When the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition of the present embodiment is crosslinked, the crosslinking method is not particularly limited, and it is preferred to perform so-called "dynamic crosslinking". Dynamic crosslinking is a method of simultaneously dispersing and crosslinking various formulations by kneading them in a molten state under the temperature conditions of the vulcanizing agent reaction, and is described in detail in the literature of A. Y. Coran et al. (Rub. Chem. and Technol. vol. 53.141 - (1980)). Dynamic crosslinking is usually performed using a closed mixer such as a Banbury mixer or a pressure kneading machine, or a single-screw or double-screw extruder. The kneading temperature is usually 130 to 300°C, preferably 150 to 250°C, and the kneading time is usually 1 to 30 minutes. As the vulcanizing agent used in the dynamic crosslinking, an organic peroxide or a phenolic resin crosslinking agent can be suitably used, and the amount used is usually 0.01 to 15 parts by mass, preferably 0.04 to 10 parts by mass, relative to 100 parts by mass of the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)). As the organic peroxide used as the vulcanizing agent, the above-mentioned component (E) can be used. When the organic peroxide is used for crosslinking, the above-mentioned component (F) can be used as a vulcanization accelerator, and the above-mentioned component (G): a peroxide crosslinking aid or the above-mentioned component (H): a multifunctional vinyl monomer, etc. can also be used in combination. The amount of such vulcanization accelerators used is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)).

In the crosslinked product of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)) using the present embodiment, additives such as softeners, heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, fillers, colorants, lubricants, etc. may be formulated as needed within the scope that does not impair its purpose. As a softener formulated to control the hardness or fluidity of the final product, the above-mentioned rubber softener (I) can be used. The softener can be added when the components are mixed, or it can be included in the above-mentioned hydrogenated block copolymer in advance when the hydrogenated block copolymer (A) is produced, that is, to prepare an oil-extended rubber. The amount of the softener added when preparing the crosslinked product is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, and more preferably 20 to 100 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)). In addition, as a filler, the above-mentioned component (C) as a reinforcing filler can be used. The amount of the filler added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, and more preferably 20 to 100 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). The crosslinked product is preferably dynamically crosslinked in a manner such that the gel content (excluding insoluble components such as inorganic fillers) is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, and further preferably 20 to 60 mass%. Regarding the gel content, 1 g of the crosslinked product is refluxed for 10 hours using a Soxhlet extractor with boiling xylene, and the residue is filtered using an 80-mesh metal sieve. The dry mass (g) of the insoluble matter remaining on the sieve is measured to determine the ratio (mass %) of the insoluble matter relative to 1 g of the sample, and the ratio (mass %) is set as the gel content. The gel content can be controlled by adjusting the type or amount of the vulcanizing agent, the conditions during vulcanization (temperature, residence time, occupancy, etc.). The crosslinked product can be used for tire applications or anti-vibration rubber, belts, industrial products, shoes, foams, etc. in the same way as the sulfide of the reinforcing filler formulation, and can also be used as a medical device material or food packaging material.

[Molded article using hydrogenated block copolymer (A) or hydrogenated block copolymer composition] The molded article of the present embodiment is a molded article of the hydrogenated block copolymer (A) or hydrogenated block copolymer composition of the present embodiment, which can be obtained by molding the hydrogenated block copolymer (A) of the present embodiment or the hydrogenated block copolymer composition. The molded article can be manufactured, for example, by extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotation molding, powder slurry molding, foam molding, lamination molding, calendering molding, blow molding, etc. Examples of the above-mentioned molded bodies include sheets, films, injection molded bodies of various shapes, hollow molded bodies, pressurized molded bodies, vacuum molded bodies, extruded molded bodies, foamed molded bodies, non-woven fabrics or fiber-shaped molded bodies, synthetic leather, and many other molded bodies, but are not limited to the above. Such molded bodies can be used, for example, for automobile parts, food packaging materials, medical equipment, home appliance components, electronic component components, building materials, industrial parts, household goods, toy materials, shoe materials, fiber materials, etc.

As automotive parts, for example, side trims, gaskets, shift knobs, weather strips, window frames and their sealing materials, armrests, auxiliary grips, door handles, handles, console boxes, headrests, dashboards, bumpers, spoilers, airbag covers, etc. can be cited, but are not limited to the above. As medical equipment, for example, medical tubes, medical hoses, catheters, blood collection bags, infusion bags, platelet storage bags, artificial dialysis bags, etc. can be cited, but are not limited to the above. As building materials, for example, wall materials, floor materials, etc. can be cited, but are not limited to the above. In addition, there is no particular limitation, for example: industrial hoses, food hoses, vacuum cleaner hoses, refrigerator seals, wires and other various covering materials, handle covering materials, soft dolls, etc. The above-mentioned molded body can also be appropriately processed by foaming, powdering, stretching, bonding, printing, painting, coating, etc. The hydrogenated block copolymer (A) of this embodiment and the above-mentioned hydrogenated block copolymer composition show excellent effects of softness, low rebound elasticity, transparency, and kink resistance, so it is very useful as a material for hollow molded bodies such as hoses and tubes.

Next, molded products using the hydrogenated block copolymer (A) and the hydrogenated block copolymer composition according to the present embodiment will be described by being divided into [first molded product] to [third molded product] according to the purpose.

[First molded body] As a first aspect of a molded body using the hydrogenated block copolymer (A) of the present embodiment, a molded body substantially containing only the hydrogenated block copolymer (A) can be exemplified. “Substantially containing only the hydrogenated block copolymer (A)” means that the polymer constituting the molded body is only the hydrogenated block copolymer (A), and does not exclude the inclusion of the various additives described below. Furthermore, it does not exclude the aspect of adding other polymers within the scope that does not impair the function of the hydrogenated block copolymer (A). The allowable amount of other polymers to be added also depends on the structure or use of the polymer. For example, in the case of a resin composition with a polyolefin such as polypropylene, it is generally less than 5% by mass. If it is a resin composition with other elastomers, the amount of addition can be allowed to be less than 80% by mass, although it also depends on the structure of the above-mentioned other elastomers. In addition to being suitable for transparent tubes and bags used in medical purposes, the first molded body can also be used as an adhesive layer constituting an adhesive film for a protective film, but the first molded body is not limited to the above.

(Tube) The tube using the hydrogenated block copolymer (A) of this embodiment has excellent transparency, flexibility, kink resistance, solvent adhesion, and balance of various properties. The tube may further contain other components in addition to the hydrogenated block copolymer (A) of this embodiment within the scope of not impairing the purpose of this embodiment. As other components, for example, hydrogenated copolymers (styrene-based thermoplastic elastomers) having a structure different from that of hydrogenated block copolymer (A), heat stabilizers, antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, light stabilizers, crystallization nucleating agents, impact modifiers, pigments, lubricants, softeners, antistatic agents, dispersants, flame retardants, copper anti-pollution agents, crosslinking agents, flame retardant aids, compatibilizers, and adhesion agents, but are not limited to the above. These other components may be used alone or in combination of two or more.

<Lubricant> The above-mentioned tube may contain a lubricant to prevent the tube surfaces or the inside from sticking to each other and to improve the texture such as the hand feel. As the lubricant, at least one (preferably at least two) lubricants selected from fatty amide lubricants, stearic acid metal salt lubricants, and fatty acid monoglyceride lubricants are preferred. Examples of the fatty amide lubricant include erucic acid amide, behenyl amide, oleyl amide, stearyl amide, N-stearyl lauryl amide, N-stearyl stearyl amide, N-stearyl behenyl amide, N-stearyl erucic acid amide, N-oleyl oleyl amide, N-oleyl behenyl amide, N-lauryl erucic acid amide, ethylene dioleyl amide, ethylene distearyl amide, hexamethylene dioleyl amide, hexamethylene dierucic acid amide, etc., but the present invention is not limited to the above. Among them, erucic acid amide, behenyl amide, oleyl amide, stearyl amide, and ethyl distearate amide are preferred, and oleyl amide is more preferred. As metal species of stearic acid metal salt lubricants, for example, zinc, sodium, calcium, magnesium, lithium, etc. can be cited. Among them, zinc stearate is preferred. As fatty acid monoglyceride lubricants, for example, lauric acid monoglyceride, myristic acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, behenic acid monoglyceride, etc. can be cited, but are not limited to the above. Among them, stearic acid monoglyceride is preferred. From the perspective of preventing sticking, the lubricant content in the tube is preferably 0.05% by mass or more, and from the perspective of avoiding the lubricant from seeping out of the tube and affecting the printability of the tube surface, it is preferably 1.0% by mass or less, and more preferably 0.7% by mass or less. From these perspectives, the lubricant content in the tube is preferably 0.05-1.0% by mass, and more preferably 0.05-0.7% by mass. The fatty amide lubricant, the metal stearate lubricant, and the fatty acid monoglyceride lubricant can be used alone or in combination of two or more. Among them, it is better to use erucic acid amide, zinc stearate, and ethyl distearate together, and the best mass ratio is erucic acid amide/zinc stearate/ethyl distearate = 0.20/0.15/0.15.

<Softener> The tube may contain a softener. Examples of the softener include, but are not limited to, paraffin oil, cycloparaffin oil, aromatic oil, solid paraffin, liquid paraffin, white mineral oil, and plant-based softeners. Among these, paraffin oil, liquid paraffin, and white mineral oil are more preferred from the viewpoint of low temperature characteristics and anti-bleeding properties. The kinematic viscosity of the softener at 40°C is preferably 500 mm ² /sec or less. The lower limit of the kinematic viscosity of the softener at 40°C is not particularly limited, but is preferably 10 mm ² /sec. If the kinematic viscosity of the softener at 40°C is 500 mm ² /sec or less, the fluidity of the tube mentioned above tends to be further improved, and the molding processability tends to be further improved. The kinematic viscosity of the softener can be measured by a test method using a glass capillary viscometer.

<Adhesive agent> The tube may contain an adhesive agent. Examples of adhesive agents include benzofuran-indene resins, p-tert-butylphenol-acetylene resins, phenol-formaldehyde resins, xylene-formaldehyde resins, terpene resins, hydrogenated terpene resins, terpene-phenol resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/alicyclic hydrocarbon resins, Oil resins, aliphatic/aromatic hydrocarbon resins, hydrogenated modified alicyclic hydrocarbon resins, hydrogenated alicyclic hydrocarbon resins, hydrocarbon adhesive resins, polybutene, liquid polybutadiene, cis-1,4-polyisoprene rubber, hydrogenated polyisoprene rubber, liquid polyisoprene rubber, rosin resins, etc., but not limited to the above.

<Method for manufacturing tube> [Method for manufacturing tube-forming material] The tube-forming material can be prepared by, for example, appropriately selecting the hydrogenated block copolymer (A) of the present embodiment and other components added as needed, by a method of dry-mixing the components; by a method of mixing using a device for mixing conventional polymer materials, etc. The mixing device is not particularly limited, and examples thereof include: a Banbury mixer, a Laboplastomill, a single-screw extruder, a double-screw extruder and other kneading devices. From the viewpoint of productivity and good kneading properties, it is preferably manufactured by a melt mixing method using an extruder. The melting temperature during kneading can be appropriately set, and is usually in the range of 130 to 300°C, and preferably in the range of 150 to 250°C.

[Tube forming method] There is no particular limitation on the tube forming method, and for example, the following method can be cited: the hydrogenated block copolymer (A) of the present embodiment and other components added as needed are appropriately selected, put into an extruder to be melted, passed into a mold to be formed into a tube, and water-cooled or air-cooled to form a tube. As an extruder, a single-axis or multi-axis extruder can be used, and a multi-layer tube can also be formed, which is formed by extruding multiple layers using multiple extruders. There is no particular limitation on the shape of the tube, and generally circular, elliptical, etc. tubes are used. There is no particular limitation on the thickness of the tube, and for example, the outer diameter is preferably 1 to 50 mm, more preferably 2 to 30 mm, and further preferably 3 to 20 mm. Furthermore, the thickness of the tube is preferably 0.3 to 30 mm, more preferably 0.4 to 20 mm, and even more preferably 0.5 to 10 mm.

The tube may also be made into a multilayer tube by layering other polymers within the scope that does not hinder the purpose of the present embodiment. The above-mentioned other polymers may be used alone or in combination of two or more, and may be layered in a single layer or multiple layers in which the types of each layer may be different. Furthermore, by multi-layering, by appropriately selecting two or more different polymers, a tube having different hardness depending on the location can be obtained, although it has no seams. The layer containing the above-mentioned polymers in the tube having the above-mentioned multi-layer structure may be located in any of the innermost layer, the middle layer, and the outermost layer, depending on the required performance to be given.

In the above-mentioned tube, from the viewpoint of further suppressing the increase of wall thickness and maintaining flexibility, and then improving pressure resistance, a braided reinforcing wire or a spiral reinforcing body can be wound to make a pressure-resistant tube (hose). The braided reinforcing wire is set inside or between layers in the thickness direction, and can use vinyl, polyamide, polyester, aromatic polyamide fiber, carbon fiber, metal wire, etc. The spiral reinforcing body is set on the periphery and can use metal, plastic, etc.

The above-mentioned tube can achieve excellent transparency, flexibility, kink resistance, solvent adhesion, and a good balance of various characteristics at a high level, and can be used without limiting the purpose. The above-mentioned characteristics can be effectively utilized for a wide range of uses such as home appliances, automotive interior and exterior parts, daily necessities, entertainment products, toys, industrial products, food manufacturing equipment, medical uses, drinking water uses, etc. Among them, the above-mentioned tube can be particularly suitable for medical use. For example, it can also be suitably used as a tube for an infusion set, a tube for a transintestinal nutrition set, an extension tube, a drug administration tube, a blood circuit tube, a nutrition tube, a connecting tube, a bladed intravenous needle tube, and further, a suction catheter, a drainage catheter, a transintestinal nutrition catheter, a gastric tube catheter, a drug administration catheter, a peritoneal dialysis tube, a blood catheter, a balloon catheter, a urethral catheter, etc.

(Adhesive film) The adhesive film comprises: a substrate film; and an adhesive layer, which is disposed on the substrate film and comprises the hydrogenated block copolymer (A) of the present embodiment, and has excellent balance among various properties such as initial adhesion, adhesion enhancement and roll-out properties. The adhesive layer of the adhesive film may also contain an adhesive imparting agent. As the adhesive imparting agent, there is no particular limitation as long as it is a resin that can impart adhesiveness to the adhesive layer. Examples thereof include: hydrogenated terpene resins, rosin-based terpene resins, hydrogenated rosin-based terpene resins, aromatic modified hydrogenated terpene resins, benzofuran-based resins, phenolic resins, terpene-phenolic resins, hydrogenated terpene-phenol resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and other known adhesive imparting resins. Particularly preferred are hydrogenated terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene-phenol resins, and terpene-phenol resins. Adhesives may be used alone or in combination of two or more. As adhesives, for example, those described in "Rubber and Plastic Compounding Chemicals" (Rubber Digest, Inc.) may be used. By using adhesives, it is possible to improve adhesion. The content of the adhesive in the adhesive layer is preferably 0.5 to 50% by mass, more preferably 5 to 45% by mass, and further preferably 10 to 30% by mass. If the content of the adhesive in the adhesive layer is 50% by mass or less, it is effective to prevent hyperadhesion and tends to further reduce the amount of paste residue during peeling. If it is 0.5% by mass or more, there is a tendency to obtain moderate adhesion.

<Base film> The material of the base film is not particularly limited, and any non-polar resin or polar resin can be used. From the perspective of performance or price, polyethylene, homopolypropylene or block polypropylene can be exemplified as a non-polar resin, and polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, ethylene-vinyl acetate copolymers and their hydrolyzates can be exemplified as polar resins. The thickness of the base film is preferably 1 mm or less, more preferably 300 μm or less, and further preferably 10 to 200 μm. If the thickness of the substrate film is 10 μm or more, the adherend can be adequately protected. If the thickness of the substrate film is 1 mm or less, a good elastic modulus can be obtained in practice, good uneven tracking performance can be obtained, and bulging or peeling can be effectively prevented.

<Adhesive layer> The adhesive film has an adhesive layer containing the hydrogenated block copolymer (A) of this embodiment on the above-mentioned base film. The adhesive layer may also contain the following other materials.

[Other materials in the adhesive layer] ＜Hydrogenated styrene elastomer＞ The adhesive layer of the adhesive film may further contain a hydrogenated styrene elastomer. As hydrogenated styrene elastomers, for example, styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene random polymer (SBR), styrene-ethylene-butylene-styrene (SEBS) obtained by saturating SBS by hydrogenation, and styrene-ethylene-propylene-styrene (SEPS) are representative hydrogenated styrene elastomers, but are not limited to the above. In addition, elastomers having structures such as styrene-ethylene-butylene (SEB), styrene-ethylene-propylene (SEP), and styrene-isobutylene-styrene triblock copolymer (SIBS) may be cited. Furthermore, as the above-mentioned hydrogenated styrene-based elastomer, a reactive elastomer to which various functional groups are imparted can also be used. Examples of the above-mentioned functional groups include: hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acyl halide group, acid anhydride group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylate group, amide group, sulfonic acid group, sulfonate group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridine group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silyl halide group, alkoxysilyl group, tin halide group, boric acid group, boron-containing group, borate group, alkoxytin group, phenyltin group, but are not limited to the above.

<Olefinic resin, olefinic elastomer> The adhesive layer of the adhesive film may further contain an olefinic resin or an olefinic elastomer. Examples of the olefinic resin and olefinic elastomer include: a polymer or copolymer of α-olefin having 2 to 20 carbon atoms, and a copolymer of ethylene and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. Specifically, examples include: ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methylpentene copolymer, ethylene-1-octene copolymer, propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, 4-methylpentene homopolymer, 4-methylpentene-1-propylene copolymer, 4-methylpentene-1-butene copolymer, 4-methylpentene-1-propylene-1-butene copolymer, propylene-1-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, etc.

<Acrylic copolymer> The adhesive layer of the adhesive film may further contain an acrylic copolymer. Examples of acrylic copolymers include copolymers of methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, etc., and vinyl acetate, vinyl chloride, styrene, etc., but are not limited to the above.

<Softener> The adhesive layer of the adhesive film may further contain a softener. The softener is not particularly limited, and for example, any of a mineral oil-based softener and a synthetic resin-based softener may be used. As a mineral oil-based softener, for example, a mixture of aromatic hydrocarbons, cycloparaffin hydrocarbons, and wax hydrocarbons may be cited. Furthermore, wax hydrocarbons whose carbon atoms account for 50% or more of all carbon atoms are called wax oils, cycloparaffin hydrocarbons whose carbon atoms account for 30 to 45% are called cycloparaffin oils, and aromatic hydrocarbons whose carbon atoms account for 35% or more are called aromatic oils. As a mineral oil-based softener, wax-based oil for rubber softeners is preferred, and as a synthetic resin-based softener, polybutene, low molecular weight polybutadiene, etc. are preferred.

<Antioxidants, light stabilizers, etc.> Antioxidants, light stabilizers, etc. may be further added to the adhesive layer of the adhesive film. As antioxidants, for example, 2,6-di-tert-butyl-4-methylphenol, 3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionate n-octadecyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,4-bis[(octylthio)methyl]-o-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, acrylic acid Hindered phenol antioxidants such as 2,4-di-tert-pentyl-6-[1-(3,5-di-tert-pentyl-2-hydroxyphenyl)ethyl]phenyl ester and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)]acrylate; sulfur antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate, and pentaerythritol-tetrakis(β-lauryl thiopropionate); phosphorus antioxidants such as tris(nonylphenyl) phosphite and tris(2,4-di-tert-butylphenyl) phosphite, but not limited to the above. Examples of light stabilizers include benzotriazole-based ultraviolet light absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-tert-butylphenyl)benzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, or benzophenone-based ultraviolet light absorbers such as 2-hydroxy-4-methoxybenzophenone, or hindered amine-based light stabilizers, but are not limited to the above.

<Pigments, waxes, thermoplastic resins, natural rubber, synthetic rubber> In addition to the above materials, the adhesive layer of the adhesive film may also contain various additives as needed. Examples of the above-mentioned additives include pigments such as ferrite and titanium dioxide; waxes such as solid wax, microcrystalline wax, and low molecular weight polyethylene wax; polyolefin-based or low molecular weight vinyl aromatic thermoplastic resins such as amorphous polyolefins and ethylene-ethyl acrylate copolymers; natural rubber; synthetic rubbers such as polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, and polypentene rubber, but are not limited to the above. Examples of the above-mentioned synthetic rubbers include those described in "Rubber and Plastic Compounding Products" (edited by Rubber Digest Co., Ltd.) and the like.

<Saturated fatty acid diamide> The adhesive layer of the adhesive film may contain a saturated fatty acid diamide having an effect of inhibiting hyperadhesion. Examples of saturated fatty acid diamides include saturated fatty acid aliphatic diamides such as ethylenebisstearylamide (EBSA), methylenebisstearylamide, and hexamethylenebisstearylamide; and saturated fatty acid aromatic diamides such as meta-xylylenebisstearylamide and N,N'-distearyl meta-xylylene diamide, but are not limited to the above. These saturated fatty acid diamides may be used alone or in combination of two or more. It is also possible to further formulate a styrene-based block phase reinforcing agent that has the effect of inhibiting hyperadhesion. As a styrene-based block phase reinforcing agent, for example, as a monomer unit, there can be exemplified: styrene and α-methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene, tert-butylstyrene, p-ethylstyrene, divinylbenzene and other styrene compounds, but it is not limited to the above. These can be used alone or in combination of two or more.

<Method for producing resin material constituting adhesive layer of adhesive film> The resin material constituting the adhesive layer of the adhesive film of the present embodiment can be produced, for example, by a method of dry-blending the hydrogenated block copolymer (A) of the present embodiment and other components added as needed; or by mixing using a device for mixing conventional polymer materials. As mixing devices, for example, mixing devices such as Banbury mixer, Laboplastomill, single-screw extruder, double-screw extruder, etc. can be cited, but are not limited to the above. From the perspective of productivity and good mixing properties, it is preferably produced by a melt mixing method using an extruder. Moreover, especially when the adhesive agent is mixed in the resin material constituting the adhesive layer, when the above-mentioned dry blending method is used, the adhesive agent has a strong viscosity and is in a flaky form, so there is a risk of poor handling properties. Therefore, a masterbatch can be prepared by pre-mixing the adhesive agent in the hydrogenated block copolymer (A) of the present embodiment. The melting temperature of the resin material constituting the adhesive layer during mixing can be appropriately set, usually in the range of 130 to 300°C, preferably in the range of 150 to 250°C. In order to achieve the effects of weight reduction, flexibility and improved adhesion, the resin material constituting the adhesive layer can also be subjected to a foaming treatment. As foaming methods, there are chemical methods, physical methods, and the use of heat-expandable microspheres, but they are not limited to the above. Bubbles can be distributed inside the material by adding chemical foaming agents such as inorganic foaming agents, organic foaming agents, physical foaming agents, etc., and adding heat-expandable microspheres. In addition, hollow fillers (expanded balloons) can be added to achieve weight reduction, flexibility, and improved adhesion.

<Method for producing adhesive film> The adhesive film has an adhesive layer containing the hydrogenated block copolymer (A) of the present embodiment on a base film. The method for producing the adhesive film is not particularly limited, and examples thereof include a method of applying a solution or melt of a resin material constituting the adhesive layer on a base film, a method of using a film extruder, etc. Here, when a solution or melt of a resin material constituting the adhesive layer is used, a resin material containing the hydrogenated block copolymer (A) and other components may be prepared to form a solution or melt, or a solution or melt to which the hydrogenated block copolymer (A) is added may be prepared and then mixed. In the case of manufacturing an adhesive film by coating a solution of a resin material, for example, it can be manufactured by dissolving in a solvent capable of dissolving the resin material, applying it on a base film using a coating machine, and heating and drying the solvent, but it is not limited to the above. In the method of melting the resin material and coating it, for example, it can be manufactured by using a hot melt coating machine, etc., and coating the molten resin material on a base film, but it is not limited to this. In this case, it is preferable to use various base films having a glass transition temperature, melting point or softening point higher than the coating temperature. As a method of manufacturing an adhesive film using a film extruder, for example, the following method can be used to manufacture the adhesive film: using a melt co-extruder, the components of the adhesive layer including the resin material and the components such as the thermoplastic resin that can constitute the substrate film are made into two flows, that is, the fluid for forming the adhesive layer and the fluid for forming the substrate film are merged in the die nozzle to form a single fluid and extruded, and the adhesive layer and the resin film layer are compounded, but it is not limited to the above. In the case of the method using a film extruder, the resin material for forming the adhesive layer can also be manufactured by pre-drying the components for the adhesive layer, so it is a method with excellent productivity. In addition, when extrusion molding is performed, the adhesive film produced tends to have particularly excellent adhesion and bonding strength. The adhesive film can be temporarily adhered to the surface of optical system moldings such as light guide plates or prism sheets, synthetic resin plates, metal plates, decorative plywood, coated steel plates, various nameplates, etc., and used as a protective film to prevent damage or dirt during processing, transportation, and storage of such adherends.

[Second molded body] The second molded body is a molded body of the hydrogenated block copolymer composition of the present embodiment described above. Examples of the second molded body include: automotive components, such as automotive interior surface materials, sheet-shaped molded bodies (sheets, films), drinking water piping, drinking water pipes; and packaging materials, such as food packaging materials and clothing packaging materials; adhesive films for protective films, and polar resin overmolded molded bodies, but are not limited to the above.

(Coated molded article) The hydrogenated block copolymer composition of the present embodiment has a tendency to show adhesion to polar resins, and thus can be formed into a multi-layered article (coated molded article) formed by coating with a polar resin. The coated molded article has a structure having a layer containing a polar resin and a layer containing the hydrogenated block copolymer composition of the present embodiment laminated on the layer, thereby having excellent adhesion.

<Polar resin> Examples of polar resins include polyvinyl chloride, ABS, acrylonitrile-styrene copolymers, polyacrylic acid, polyacrylates such as polymethyl acrylate, polymethacrylic acid, polymethacrylates such as polymethyl methacrylate, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyamide, polyacetal, polycarbonate, polybutylene terephthalate, polyvinylidene fluoride, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polyamide imide, polyetherimide, polyetherketone, polyetheretherketone, polyimide, liquid crystal polymer, polytetrafluoroethylene, phenol resin, urea resin, melamine resin, unsaturated polyester, epoxy resin, and polyurethane, but are not limited to the above. Polar resins can be used alone or in combination of two or more.

The layer containing the polar resin may contain a filler in addition to the polar resin. Examples of the filler in the layer containing the polar resin include: glass fiber, glass sphere, glass hollow sphere, carbon fiber, cellulose nanofiber, wollastonite, potassium titanium crystal whisker, calcium carbonate crystal whisker, aluminum borate crystal whisker, magnesium sulfate crystal whisker, sepiolite, hard silicate, zinc oxide crystal whisker, etc., fibrous inorganic fillers, talc, calcium carbonate, calcium oxide, Zinc carbonate, wollastonite, zeolite, wollastonite, silica, aluminum oxide, clay, titanium oxide, magnesium hydroxide, magnesium oxide, sodium silicate, calcium silicate, magnesium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, zinc oxide, potassium titanate, hydrotalcite, barium sulfate, titanium black, and carbon black such as furnace black, thermal black, and acetylene black, etc., but not limited to the above. The fibrous inorganic filler can also be surface-treated with a compound having an affinity group or a reactive group for a polar resin. The filler can be used alone or in combination.

<Layer containing hydrogenated block copolymer composition> As the layer containing hydrogenated block copolymer composition constituting the above-mentioned overmolded body, there can be exemplified a layer containing the hydrogenated block copolymer composition of the present embodiment and a rubbery polymer. The rubbery polymer preferably contains vinyl aromatic monomer units and contains at least one polymer block containing vinyl aromatic monomer units as the main component. Furthermore, it is also preferably a rubber or elastomer containing vinyl aromatic monomer units and containing 60% by mass or less of the vinyl aromatic monomer units. Examples of rubbery polymers include styrene butadiene rubber and its hydrogenated products (excluding the hydrogenated block copolymer of the present embodiment), styrene-butadiene block copolymer and its hydrogenated products, styrene-butadiene-isoprene block copolymer and its hydrogenated products, but are not limited to the above.

The layer comprising the hydrogenated block copolymer composition may contain other thermoplastic resins in addition to the above-mentioned thermoplastic resin (C). Examples of the thermoplastic resin (propylene) and other thermoplastic resins include olefin polymers such as polypropylene, polyethylene, ethylene-propylene copolymer rubber (EPM), and ethylene-propylene-non-conjugated diene copolymer rubber (EPDM); polyester polymers such as polyester elastomer, polyethylene terephthalate, and polybutylene terephthalate; polyamide resins such as polyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, and polyamide 6,12; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; polyoxymethylene resins such as polyoxymethylene homopolymer and polyoxymethylene copolymer; styrene homopolymer, acrylonitrile-styrene; styrene resins such as styrene-butadiene-styrene resins; polycarbonate resins; styrene-butadiene copolymer rubbers, styrene-isoprene copolymer rubbers and other styrene elastomers and their hydrogenated products or modified products; natural rubber; synthetic isoprene rubber and liquid polyisoprene rubber and their hydrogenated products or modified products; chloroprene rubber; acrylic rubber; butyl rubber; acrylonitrile-butadiene rubber; epichlorohydrin rubber; polysilicone rubber; fluororubber; chlorosulfonated polyethylene; urethane rubber; polyurethane elastomer; polyamide elastomer; polyester elastomer; soft vinyl chloride resin, etc., but not limited to the above. These thermoplastic resins may be used alone or in combination of two or more.

The layer containing the hydrogenated block copolymer composition may contain other softeners in addition to the above-mentioned softener (D). Examples of the above-mentioned softener (D) and other softeners include, but are not limited to, wax-based oils, cycloparaffin-based oils, aromatic oils, solid wax, liquid wax, white mineral oil, and plant-based softeners. The kinematic viscosity of the softener at 40°C is preferably 500 mm ² /sec or less. The lower limit of the kinematic viscosity of the softener at 40°C is not particularly limited, but is preferably 10 mm ² /sec. If the kinematic viscosity of the softener at 40°C is 500 mm ² /sec or less, the fluidity of the thermoplastic elastomer composition tends to be further improved, and the molding processability tends to be further improved. The kinematic viscosity of the softener can be measured by a test method using a glass capillary viscometer.

The layer containing the hydrogenated block copolymer composition may further contain other olefinic resins and olefinic elastomers in addition to the above-mentioned component (B). As the above-mentioned component (B) and other olefinic resins and olefinic elastomers, for example, α-olefin polymers or copolymers having 2 to 20 carbon atoms, copolymers of ethylene and unsaturated carboxylic acids or unsaturated carboxylic acid esters can be cited, but are not limited to the above. For example, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methylpentene copolymer, ethylene-1-octene copolymer, propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, 4-methylpentene homopolymer, 4-methylpentene-1-propylene copolymer, 4-methylpentene-1-butene copolymer, 4-methylpentene-1-propylene-1-butene copolymer, propylene-1-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, etc., but not limited to the above.

The layer containing the hydrogenated block copolymer composition may also contain an adhesive agent. Examples of adhesive agents include benzofuran-indene resins, tert-butylphenol-acetylene resins, phenol-formaldehyde resins, xylene-formaldehyde resins, terpene resins, hydrogenated terpene resins, terpene-phenol resins, hydrogenated terpene-phenol resins, aromatic modified terpene resins, aromatic modified hydrogenated phenol resins, styrene resins, α-methylstyrene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins. Resins, aliphatic cyclic hydrocarbon resins, aliphatic/aliphatic petroleum resins, aliphatic/aromatic hydrocarbon resins, hydrogenated modified alicyclic hydrocarbon resins, hydrogenated alicyclic hydrocarbon resins, hydrocarbon adhesive resins, polybutene, liquid polybutadiene, cis-1,4-polyisoprene rubber, hydrogenated polyisoprene rubber, liquid polyisoprene rubber, rosin-based resins, etc., but not limited to the above.

In the scope that does not impair the purpose of the present invention, the layer containing the hydrogenated block copolymer composition may further contain other additives in addition to the above-mentioned components. As other additives, for example: heat stabilizers, antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, light stabilizers, crystallization nucleating agents, impact modifiers, pigments, lubricants, antistatic agents, flame retardants, flame retardant aids, and compatibilizers, etc. These additives can be used alone or in combination of two or more.

<Method for producing the hydrogenated block copolymer composition constituting the above-mentioned second molded body> The method for producing the hydrogenated block copolymer composition constituting the second molded body is not particularly limited, and it can be produced by a previously known method. For example, a melt kneading method using a common mixer such as a pressure kneader, a Banbury mixer, a closed mixer, a Laboplastomill, a MIX-LABO, a single-screw extruder, a twin-screw extruder, a bidirectional kneader, a multi-screw extruder, etc. can be used; a method of removing the solvent by heating after dissolving or dispersing and mixing the components, etc. The shape of the hydrogenated block copolymer composition constituting the above-mentioned second molded body is not particularly limited, and examples thereof include: granular, sheet, rope, small flake, etc. In addition, a molded product can be directly produced after melt kneading.

<Manufacturing method of overmolded body> If the overmolded body includes one or more layers including the hydrogenated block copolymer composition of the present embodiment and a layer including a polar resin, the number of layers is not particularly limited. The layer formation method of the overmolded body is not particularly limited, and a previously known method can be used, such as extrusion molding, injection molding (insert molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotation molding, powder solidification molding, foaming molding, lamination molding, calendering molding, and blow molding. The layer containing the hydrogenated block copolymer composition of the present embodiment is preferably heat-fused to the layer containing the polar resin. More specifically, the method for manufacturing the overmolded body is preferably in a form including the following steps: using at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding to form the layer containing the hydrogenated block copolymer composition of the present embodiment on the formed layer containing the polar resin. The method for manufacturing the overmolded body may also include the following steps before the step: forming the layer containing the polar resin by any method, preferably at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding.

The overmolded body can be formed into shapes corresponding to various uses such as automobile parts, tools, toys, electrical and electronic equipment parts, medical instruments, building materials, piping components, tableware, daily life, decorative items, industrial parts, various hoses, various housings, various module boxes, various power control unit parts, writing tools, robot hands, and medical instruments. Among them, those with handles and those that require grip or good touch when touched by people are preferred. Examples of such a molded body include: tools, wires, connectors, portable electronic devices, toothbrushes, electric razors, pens such as ballpoint pens, touch pens, and styluses, tableware such as forks, knives, and spoons, and components with a grip portion, but are not limited to the above. It is particularly preferred that the load imposed on the human body by the vibration during use is relatively large for an electric tool. As a component constituting the above-mentioned grip portion, it is preferred that the component constitutes at least one selected from a tool grip, a wire sheathing component, a connector housing, a grip of a portable electronic device, a toothbrush grip, an electric razor grip, a tableware grip, a writing tool grip, a robot grip, and a grip portion of an automobile interior component.

[Third molded body] The third molded body is a molded body of the resin composition containing 5 to 99 mass%, or 5 to 80 mass%, or more than 8 mass% and less than 60 mass%, or 10 to 30 mass%, or less than 70 mass% of the total mass of the resin composition, and is a molded body containing 10 to 40 mass% of a polyolefin resin as other resin components.

The resin composition constituting the third molded body preferably further includes a free radical generating compound also called a curing agent or a curing initiator. Examples of such free radical generating compounds include, but are not limited to, nitrogen anodes, peroxides, sulfur, and sulfur derivatives. The curing initiator is particularly preferred as a free radical initiator. The free radical generating compound also called a curing catalyst generates free radicals at high temperature, or under UV (Ultra Violet) irradiation, and further under other induction energy addition. By using the free radical generating compound, the resin composition can be processed at low temperature even in the absence of UV or induction energy, but at the activation temperature, or under the introduction of UV or induction energy, a high concentration of free radicals will be generated reliably. As the free radical generating compound, any compound capable of generating free radicals at high temperature or by adding induction energy such as UV irradiation can be used. As the free radical generating compound, for example, organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxide)-3-hexyne, di-tert-butyl peroxide, tert-butyl peroxide isopropylbenzene, di(tert-butylperoxide isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, and diisopropylbenzene peroxide can be cited, but are not limited to the above. In addition, as a typical non-peroxidation initiator as a free radical generating compound, for example, compounds such as 2,3-dimethyl-2,3-diphenylbutane and 2,3-trimethylsilanyloxy-2,3-diphenylbutane can be cited. In addition, as a typical UV free radical initiator as a free radical generating compound, 2,2-dimethoxy-1,2-diphenylethane-1-one can be cited. The hardening initiator is preferably used in the resin composition in an amount of 0.1 to 10 mass % or 0.3 to 7 mass % or 1 to 5 mass % depending on the purpose.

The resin composition constituting the third molded body may also contain multifunctional co-hardening additives, diene rubbers, halogenated or non-halogenated flame retardants, inorganic or organic fillers or fibers, monoethylene compounds, or antioxidants, colorants or stabilizers, adhesion promoters, reinforcing agents, film-forming additives and other additives known in the art. In addition, other additives may be further included in an amount ranging from 0.1 to 50% by weight of the resin composition. The resin composition further preferably contains at least inorganic and/or organic fillers. Inorganic fillers can be used to suppress the thermal expansion coefficient and improve the toughness of the laminated sheet. Organic fillers can be used to reduce the dielectric constant of laminated sheets.

Examples of the third molded body include, but are not limited to, prepregs, metal laminates, CCLs (Copper Clad Laminates), printed wiring boards, multilayer wiring boards, and electronic devices.

[Other uses of hydrogenated block copolymers] (Prepreg, metal laminate) The hydrogenated block copolymer (A) of this embodiment can be used for dielectric compounds for metal laminates and printed circuit boards made using the same. By using the hydrogenated block copolymer (A) of this embodiment, a resin composition with good processability, low solution viscosity, excellent curability, high softening point temperature, low dielectric dissipation factor at high frequency, and low dielectric constant characteristics can be obtained, and further, a prepreg and a metal laminate with excellent adhesion between metal foil and insulating layer can be obtained from the above resin composition.

The above-mentioned prepreg refers to a fabric obtained by impregnating a base fabric or a reinforcing fabric with a resin composition containing the hydrogenated block copolymer (A) of the present embodiment. Metal laminate refers to a base material of a printed circuit board or a circuit substrate. The metal laminate can be obtained by laminating a metal, such as a copper cladding layer, on one or both sides of a reinforcing material (such as fiberglass cloth) impregnated in a resin composition. Specifically, a copper foil laminate (CCL) can be obtained, for example, by laminating one or more layers of prepreg on one or more layers of copper foil. Lamination is achieved by pressing one or more sets of copper and prepreg stacks together under high temperature, high pressure and vacuum conditions. Printed circuit boards can be made by etching the copper surface of CCL to make electronic circuits. The etched CCL is assembled into a multi-layer structure with through-holes and plated treatments to establish electrical connections between layers.

When manufacturing prepregs or metal laminates, a solvent may be added to change the solid content of the resin composition and to adjust the viscosity of the resin composition. Examples of the solvent include ketones such as methyl ethyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; amides such as dimethylformamide; aromatic hydrocarbons such as benzene, toluene, and xylene; and chlorinated hydrocarbons such as trichloroethylene, but are not limited to the above. Each solvent may be used alone or in combination. The preferred solvent is selected from the group consisting of methanol, ethanol, ethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, γ-butyrolactone (GBL) and diisobutyl ketone (DIBK). The amount of solvent used depends on the solubility of the components, the amount of filler, the application method and other factors. The amount of solvent used is preferably adjusted in a manner that the solid component contains 10 to 50% by mass, or 15 to 40% by mass, relative to the total mass of the solution and the solid component.

The following additives may be further added to the above resin composition: at least one of a coupling agent, a hardening accelerator, a surfactant, a strengthening agent, a viscosity modifier, a wetting agent, an antioxidant, a coloring agent, etc. The selection of additives is influenced by the application and the desired properties selected in a manner that enhances the electrical properties of the circuit component or does not substantially cause adverse effects, such as dielectric constant, dielectric dissipation factor, dielectric loss and/or other desired properties. The hardening accelerator is added to increase the reaction rate of the resin composition. The surfactant is added to uniformly distribute the inorganic filler in the resin composition and prevent the agglomeration of the inorganic filler. Strengthening agents are added to improve the toughness of resin compositions.

The resin composition can further contain a known adhesion promoter in the art, such as a metal adhesion promoter containing N-doped rings that can form a metal foil and a composite, in an amount of 0.1-2 mass % of the total resin composition. This can enhance the adhesion between the metal foil and the resin composition layer. The adhesion promoter can also be contained in the resistor metal layer in the form of a solution or dispersion of water or an organic solvent.

The resin composition may further include 15% by weight or less of a bonding-promoting polymer selected from the group consisting of poly(arylene ether), carboxyl-functionalized poly(arylene ether), and styrene-ethylene/butylene-styrene (SEBS) functionalized with maleic anhydride. Specifically, the curable resin composition preferably contains a copolymer, a curing initiator selected from a sulfur curing agent and a peroxide curing agent, and a diene rubber as a co-curing additive.

The resin composition may further contain soluble polymers such as polyphenylene ether resin, polyolefin, styrene polymer, styrene block copolymer or hydrogenated styrene block copolymer, high Tg polycycloolefin, etc. These soluble polymers are used in low amounts to modify the resin composition to improve its film forming ability, impact resistance, Tg, and processing characteristics.

The amount of the optional additive in the above-mentioned resin composition including the hydrogenated block copolymer (A) of the present embodiment can be set to a range of 0.1 to 25 mass %, or more than 0.2 mass %, or more than 0.5 mass %, or less than 10 mass %, or less than 15 mass % of the total amount of the resin composition, depending on the purpose.

The above-mentioned resin composition containing the hydrogenated block copolymer (A) of the present embodiment is suitable for use in laminates for printed circuit boards, such as copper foil laminates. The above-mentioned laminate can be manufactured by impregnating the resin composition into a substrate or a reinforcing material such as glass fiber, woven fabric, cross-ply laminate, etc., and then partially or completely hardening the resin composition to form a prepreg. In order to make the laminate, one or more layers of copper are laminated on one or more layers of prepreg. Printed circuit boards can be used for a large number of high-frequency and high-data-speed electrical and electronic applications.

As a method for manufacturing a high-frequency CCL or a circuit substrate, for example, the following method can be cited. The above-mentioned components are mixed to obtain a resin composition, which includes the hydrogenated block copolymer (A) of the present embodiment, a curing initiator, and arbitrarily selected components, such as a multifunctional co-curing agent such as a diene polymer, a flame retardant, and other arbitrarily selected components. The above-mentioned resin composition is diluted to a suitable viscosity using a solvent such as toluene, xylene, methyl ethyl ketone (MEK), and a mixture thereof to form a glue or varnish. A reinforcing material or substrate, such as fiber, glass felt, wood pulp paper, fiberglass cloth (optionally treated with a coupling agent) is impregnated in the glue or varnish to a desired thickness. Next, the solvent is removed from the impregnated fiberglass cloth by evaporation of the solvent to form a prepreg. The prepreg is formed by evaporating the solvent at a temperature that does not reach the activation temperature of the curing initiator, or evaporating the solvent for a time sufficient for the solvent to evaporate but not reaching the gelation time. The gelation time refers to the time from the beginning of softening of the material to the gelation, which is an irreversible change from a viscous liquid to an elastic gel. Prepreg is formed by impregnating a substrate such as a fiber with a resin composition, semi-hardening the obtained impregnated substrate, or hot pressing the coated fiber with a further resin composition, or hot pressing without a resin composition. Next, the prepreg volume is layered between copper foils and hardened at a temperature of 150-250°C and a pressure of 20 kg/ ^cm2-70 kg/ ^cm2 to form a high-frequency CCL or circuit substrate.

[Foam] The molded body of the present embodiment may also be a foam. The foam of the present embodiment can be generally obtained by adding a foaming agent (e) to the hydrogenated block copolymer composition of the present embodiment and foaming the foam. The foaming method includes a chemical method or a physical method. In both cases, a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, or a physical foaming agent is added, and then the foaming agent is volatilized and/or decomposed by heating, etc., so that bubbles are distributed inside the hydrogenated block copolymer composition. By making the molded body of the hydrogenated block copolymer composition into a foam, it is possible to achieve weight reduction, improved flexibility, improved design, improved vibration damping, improved sound absorption characteristics, improved heat insulation characteristics, etc.

(Foaming agent (E)) As the above-mentioned foaming agent, an inorganic foaming agent, an organic foaming agent, or a physical foaming agent can be used. As the inorganic foaming agent, for example, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, sodium borohydride, aluminum acetate, metal powder, etc. can be cited, but it is not limited to the above. Examples of organic foaming agents include: azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N,N'-dinitrosopentamethylenetetramine, N,N'-dinitroso-N,N'-dimethylterephthalamide, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, p-,p-oxybisbenzenesulfonylhydrazine, p-toluenesulfonylamide urea, etc., but are not limited to the above. As physical foaming agents, for example, hydrocarbons such as pentane, butane, and hexane; halogenated hydrocarbons such as methyl chloride and dichloromethane; gases such as nitrogen, carbon dioxide, and air; fluorinated hydrocarbons such as trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, chlorodifluoroethane, and hydrofluorocarbon, etc., but are not limited to the above. In addition, these foaming agents can also be used in combination. The amount of the foaming agent is preferably 0.1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and further preferably 3 to 20 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition of the present embodiment.

(Foaming aid) In the above-mentioned step of preparing the foamed body, a foaming agent may be used together with the foaming aid. The foaming aid is not particularly limited, and those commonly used as foaming aids can be used. For example, urea compounds; zinc compounds such as zinc oxide, zinc stearate, zinc benzenesulfinate, zinc toluenesulfonate, zinc trifluoromethanesulfonate, zinc carbonate; lead compounds such as lead dioxide and tribasic lead, etc. can be cited. When a foaming agent and a foaming aid are used together, the amount of the foaming aid relative to 100 parts by mass of the foaming agent is preferably 0.1 to 1000 parts by mass, more preferably 0.5 to 500 parts by mass, and even more preferably 1 to 200 parts by mass.

(Foaming nucleating agent) In the above-mentioned step of preparing the foamed body, a foaming nucleating agent may be used. As the foaming nucleating agent, there is no particular limitation, and those commonly used as foaming nucleating agents can be used. For example, titanium oxide, talc, kaolin, clay, calcium silicate, silicon dioxide, sodium citrate, calcium carbonate, diatomaceous earth, calcined porphyry, zeolite, bentonite, glass, limestone, calcium sulfate, aluminum oxide, titanium oxide, magnesium carbonate, sodium carbonate, iron carbonate, polytetrafluoroethylene powder can be cited. Regarding the amount of the foaming nucleating agent, relative to 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment, it is preferred to set the foaming nucleating agent to 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, and even more preferably 0.1 to 10 parts by mass.

(Examples of Use of Foam) The foam of this embodiment can be applied to injection molded products, hollow molded products, compressed air molded products, vacuum molded products, extruded molded products, etc. in the form of sheets or films or other various shapes. In addition, the foam of this embodiment can be widely used in automotive interior materials (dashboards, door panels, seat back panels, steering wheels, etc.), home appliances, tools, furniture (cushion parts, etc.), residential building materials, and other components that require cushioning properties. When the foam of this embodiment is used for automotive interior materials, the foaming agent used is preferably sodium bicarbonate or gases such as nitrogen, carbon dioxide, and air from the perspective of low health hazards.

(Injection molding foaming method) The foam body of the present embodiment can be produced by injection molding foaming. There is no particular limitation on the method of injection molding foaming, and examples thereof include: short shot method, full shot method, core pulling method, etc. By using the above method, a foam layer with cushioning properties and a surface layer with a design such as a pleated surface or a hardness compared to the foam layer can be formed in the same step, so it is more effective in reducing the molding steps. In addition, as a method of injection molding foaming, when applying the core pulling method, a counter pressure device can also be used for the purpose of eliminating swirl marks on the surface of the molded body.

(Hydrogenated block copolymer composition suitable for foam molding) The content of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of the present embodiment in foam molding is preferably 1 mass % or more and 50 mass % or less, more preferably 10 mass % or more and 49 mass % or less, and further preferably 20 mass % or more and 48 mass % or less. If the content of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition is within the above range, the bubbles tend to be fine and the independence of the bubbles increases (the foaming property increases) during foam molding, so it can be expected that the heat insulation property is improved or the bubble stability is improved for a long time, or the molding appearance is improved during core-pulling molding (suppression of shrinkage marks, pits, vortex marks, etc.). In addition, the MFR (Melt Flow Rate) of the hydrogenated block copolymer (A) of the present embodiment measured at a temperature of 230°C and a load of 2.16 kg according to JIS K7210 is 10 or more, and in the hydrogenated block copolymer (A) in the hydrogenated copolymer composition used in foam molding, the MFR is preferably 15 or more, more preferably 30 or more, and further preferably 50 or more. If the MFR is higher, good processability can be obtained, and it can be expected to improve the molding appearance during foam molding (suppress shrinkage marks, pits, vortex marks), or increase the foaming ratio. The preferred range of the foaming ratio depends on the application, but it is usually preferably 1.5 times or more, and more preferably 1.75 times or more. Due to the high ratio, it is possible to achieve lightness, improved flexibility, improved design, improved vibration reduction, improved sound absorption, and improved heat insulation properties.

The content of the olefinic resin (II) in the hydrogenated block copolymer composition used in foam molding is preferably 5% by mass or more and 50% by mass or less, more preferably 8% by mass or more and 45% by mass or less, and further preferably 12% by mass or more and 40% by mass or less. If the content of the olefinic resin (II) is within the above range, the balance between foamability and softness tends to be good.

The content of the thermoplastic resin (C) in the hydrogenated block copolymer composition used in foam molding is preferably 1 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 40 mass % or less, and further preferably 10 mass % or more and 30 mass % or less. If the content of the thermoplastic resin (C) is within the above range, the balance between foamability and softness tends to be good.

The content of the softener (D) in the hydrogenated block copolymer composition used in foam molding is preferably 5 mass % or more and 90 mass % or less, more preferably 10 mass % or more and 70 mass % or less, and further preferably 20 mass % or more and 36 mass % or less. If the content of the softener (D) is within the above range, the balance between foamability and softness tends to be good. [Example]

The present invention is described in detail below by taking specific embodiments and comparative examples as examples, but the present invention is not limited to the following embodiments and comparative examples. The following describes the measurement method and evaluation method of the physical properties used in the embodiments and comparative examples.

[Specification method of copolymer structure] ((1) Content of all vinyl aromatic monomer units (styrene) in hydrogenated block copolymer (A)) Using the hydrogenated block copolymer, the content of all vinyl aromatic monomer units (styrene) in the hydrogenated block copolymer (A) was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).

((2-1) Content of polymer block (polystyrene block) (a) mainly composed of vinyl aromatic monomer units in hydrogenated block copolymer (A)) Using hydrogenated block copolymers, the content of polymer block (a) mainly composed of vinyl aromatic monomer units in hydrogenated block copolymers (A) was measured using a nuclear magnetic resonance device (NMR) (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). hereinafter referred to as "NMR method").

((2-2) The content of hydrogenated copolymer block (b) in hydrogenated block copolymer (A)) The content of hydrogenated copolymer block (b) in hydrogenated block copolymer (A) is obtained by calculating (100-the content of hydrogenated copolymer block (a) in hydrogenated block copolymer (A)).

((3) Vinyl bond content in hydrogenated block copolymer (A)) The hydrogenated block copolymer was used and the vinyl bond content was measured using a nuclear magnetic resonance device (NMR). The vinyl bond content in the conjugated diene monomer unit in the hydrogenated block copolymer (A) was obtained by the ratio of the total area of the peaks of 1,2-bond and 3,4-bond related to the conjugated diene monomer unit in the peaks obtained in the NMR measurement to the total area of all peaks (ratio of 1,2-bond, 3,4-bond, and 1,4-bond).

((4) Weight average molecular weight and molecular weight distribution of hydrogenated block copolymer (A)) The hydrogenated block copolymer was measured by GPC [apparatus: HLC-82209PC (manufactured by Tosoh Corporation), column: TSK Geguard colum SuperHZ-L (4.6 mm×20 cm)×3]. The solvent used was tetrahydrofuran. The measurement was performed at a temperature of 35°C. The weight average molecular weight was obtained by using a calibration curve obtained by measuring commercially available standard polystyrene (prepared using the peak molecular weight of 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 calculated from the molecular weight of each peak and the composition ratio of each peak (calculated from the area ratio of each peak in the chromatogram) is set as the weight average molecular weight (Mw). Regarding the molecular weight distribution (Mw/Mn), the number average molecular weight (Mn) is measured by GPC in the same way and calculated from the ratio of Mw/Mn.

((5) Hydrogenation rate of double bonds of conjugated diene monomer units in hydrogenated block copolymer (A)) The hydrogenated block copolymer was used and a nuclear magnetic resonance device (manufactured by JEOL RESONANCE, measurement ECS400) was used to measure the hydrogenation rate of double bonds of conjugated diene monomer units in the hydrogenated block copolymer (A).

((6-1) Content RS of vinyl aromatic monomer units in hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (A), content of vinyl aromatic monomer units in hydrogenated copolymer block (b)) The content RS of vinyl aromatic monomer units in hydrogenated copolymer block (b) relative to the entire polymer is calculated based on the difference between the content of all vinyl aromatic monomer units in hydrogenated block copolymer (A) measured in (1) above and the content of polymer block (a) mainly composed of vinyl aromatic monomer units in hydrogenated block copolymer (A) measured in (2-1) above, and the content of vinyl aromatic monomer units in hydrogenated copolymer block (b) is calculated based on the ratio to the content of hydrogenated copolymer block (b) in hydrogenated block copolymer (A) measured in (2-2) above.

((6-2) Content of the covalent diene monomer unit in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (A)) Calculated by subtracting the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (A) from the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A).

[Method for measuring physical properties of hydrogenated block copolymers] ((7) tanδ peak temperature) The "hydrogenated block copolymer pressure-molded sheet" produced as described below was cut into a size of 12.5 mm in width and 40 mm in length to serve as a sample for measurement. Next, the sample for measurement was set to the torsion geometry of the device ARES (trade name, manufactured by TA Instruments Co., Ltd.) and the tanδ peak temperature of -20 to 60°C was determined under the conditions of 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. The tanδ peak temperature was determined based on the peak detected by automatic measurement using RSI Orchestrator (trade name, manufactured by TA Instruments Co., Ltd.).

((8) Tanδ peak height) The tanδ value at the tanδ peak temperature of -20 to 60℃ obtained in (7) above is set as the tanδ peak height of -20 to 60℃.

((9) Hardness) A sample for measurement of a "pressure-molded sheet of a hydrogenated block copolymer" was prepared as described below. The instantaneous value was measured using a type A hardness tester in accordance with JIS K6253. The instantaneous hardness value when the probe of the hardness tester was lowered onto the measurement sample was measured. In Tables 4 and 5 below, it is recorded as hardness (JIS-A, instantaneous).

((10) Melt flow rate (MFR, unit: g/10 min)) A sample for measurement of a "pressure-molded sheet of a hydrogenated block copolymer" was prepared as described below. MFR was measured at a temperature of 230°C and a load of 2.16 kg in accordance with JIS K7210.

[Evaluation method of properties of molded articles using hydrogenated block copolymers] ((11) Wear resistance) Using a Gakushin friction tester (AB-301 model, manufactured by Tester Sangyo Co., Ltd.), the surface (grained surface) of the injection molded sheet produced by the following [Production of injection molded sheets] was rubbed with a friction cloth made of fine white cloth No. 3 cotton and a load of 500 g. The wear resistance was evaluated based on the volume reduction after friction according to the following criteria. <Evaluation criteria> 5: After 50,000 frictions, the volume reduction is less than 0.01 ml 4: After 50,000 frictions, the volume reduction is 0.01 ml or more and less than 0.05 ml 3: After 50,000 frictions, the volume reduction is 0.05 ml or more and less than 0.10 ml 2: After 50,000 frictions, the volume reduction is 0.10 ml or more and less than 0.15 ml 1: After 50,000 frictions, the volume reduction exceeds 0.15 ml

The score that can be judged as qualified for wear resistance is 3 points or more, and the higher the score, the better it is evaluated from the perspective of improved durability and increased freedom of blending when using the above-mentioned thinner wall/complex molded bodies, with higher loads or coarser mesh fabrics. If the wear resistance is good, it can be used in automotive materials and other applications that require more stringent wear resistance. For example, in automotive interior materials, when thinner wall molding or more complex/large molded bodies are formed, it is not inferior to simple shapes and small ordinary molded bodies, and it can be expected that the appearance of the material can be maintained even when used for a longer period of time. Furthermore, even when the material is worn by a higher load or a coarser mesh (e.g., a coarser mesh than cotton fabric such as fine white cloth No. 3, i.e., a denim cotton fabric) during riding, it can be expected that the material appearance can be maintained for a long time. In addition, if the wear resistance is good, the lower limit of the amount of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of the present embodiment is reduced, and the degree of freedom in the blending tends to be improved. Generally, the more the amount of the hydrogenated block copolymer (A) in the hydrogenated block copolymer composition is, the better the wear resistance tends to be, but the less the amount of the hydrogenated block copolymer (A) is, the better the oil resistance or material cost tends to be, so the lower limit of the blending amount is preferably lower.

((12) Low resilience: Dunlop rebound modulus) A sample for measurement of a "hydrogenated block copolymer pressure-molded sheet" manufactured in the following manner was prepared. The rebound modulus was measured at 23°C using a Dunlop rebound modulus tester in accordance with BS903. From the perspective of touch, if the rebound modulus is 20% or less, it is good in practice, and the lower the value, the more excellent the evaluation tends to be.

(Calculation of random parameter g of hydrogenated block copolymer) The hydrogenated block copolymer (A) was subjected to py-GC/MS measurement under the conditions of Table 3 below, and the peak intensity P was calculated. In addition, P0 was calculated using P0=0.005563×RS based on the content RS of the vinyl aromatic monomer unit in the copolymer block (b) relative to the entire hydrogenated block copolymer (A), and g was calculated based on g=P/P0. Here, the above "0.005563" represents the proportional constant (k) when the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole is first approximated with the peak intensity P, which is obtained when the hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization method) is analyzed using a thermal decomposition gas chromatography mass spectrometer.

[Table 3] Pyrolyzer device Frontier Lab Multishot Pyrolyzer EGA/PY-3030D Pyrolyzer heating conditions 500℃ GC device Agilent Technologies manufactures the 7890A Use the column DB-1 (30 m×0.25 mmΦ, film thickness 0.25 μm) Column temperature mode After keeping at 40℃ for 5 min, increase the temperature to 320℃ at 20℃/min and keep at 320℃ for 11 min Gas flow rate 1 ml/min Sample injection port temperature 320℃ Split Ratio 1/50 Sample measurement 0.10 mg MS device JEOL RESONANCE Co., Ltd. manufactures JMS-Q1500GC Interface temperature 320℃ Ionization EI 70 eV Scanning range m/z 10～800 Ion source temperature 240℃

[Production of Hydrogenated Block Copolymer] (Preparation of Hydrogenated Catalyst) The hydrogenated catalyst used in the production of hydrogenated block copolymers in the following examples and comparative examples was prepared by the following method. A reaction vessel equipped with a stirring device was replaced with nitrogen in advance, and 1 liter of dried and purified cyclohexane was added thereto. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While stirring the mixture thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for about 3 days. Thus, a hydrogenated catalyst was obtained.

(Hydrogenated block copolymer) Hydrogenated block copolymers (A)-1 to (A)-10, (A)-A to (A)-E constituting the hydrogenated block copolymer composition were prepared as follows.

[Example 1] (Hydrogenated block copolymer (A)-1) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 13 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.047 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of vinyl bond adjuster N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium (n-BuLi), and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 30 parts by mass of butadiene and 44 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, while using ReactIR to quantify the concentrations of butadiene and styrene in the reaction system in real time, the feed rate is appropriately adjusted in such a way that the polymerization rate of each reaches 1:1 (mass fraction conversion). In ReactIR, butadiene monomer is tracked at a wavelength of 1589 cm ^-1 , and styrene monomer is always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio is higher than the required reactivity ratio by more than 10%, the feed rate of butadiene is increased. When the reactivity ratio is lower than the required reactivity ratio by more than 10%, the feed rate of butadiene is reduced to adjust to the required reaction ratio until the reaction is completed. Finally, a cyclohexane solution containing 13 parts by mass of styrene (concentration 20 mass%) is added, and polymerization is carried out at 65°C for 1 hour. Thereafter, methanol is added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 70% by mass, a vinyl aromatic monomer unit content RS of the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) of 44% by mass, a vinyl bond content of 21% by mass, and a weight average molecular weight of 160,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared by the above method was added based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-1. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-1 was 98 mol%. Other physical properties are shown in Table 4.

[Example 2] (Hydrogenated block copolymer (A)-2) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 12 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.048 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 12 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 69% by mass, a vinyl aromatic monomer unit content RS of 45% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 20% by mass, and a weight average molecular weight of 160,000. Furthermore, the hydrogenation catalyst prepared by the above method was added to the obtained block copolymer at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-2. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-2 was 98 mol%. Other physical properties are shown in Table 4.

[Example 3] (Hydrogenated block copolymer (A)-3) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.048 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 66% by mass, a vinyl aromatic monomer unit content RS of 50% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 21% by mass, and a weight average molecular weight of 161,000. Furthermore, a hydrogenation catalyst prepared by the above method is added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-3. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-3 was 98 mol%. Other physical properties are shown in Table 4.

[Example 4] (Hydrogenated block copolymer (A)-4) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 7 parts by mass of styrene (concentration 20 mass%) was added. Next, 0.049 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 35 parts by mass of butadiene and 51 parts by mass of styrene was added (concentration 20 mass%), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 7 parts by mass of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 65% by mass, a vinyl aromatic monomer unit content RS of the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) of 51% by mass, a vinyl bond content of 21% by mass, and a weight average molecular weight of 160,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared by the above method was added based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-4. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-4 was 98 mol%. Other physical properties are shown in Table 4.

[Example 5] (Hydrogenated block copolymer (A)-5) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.050 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 39 parts by mass of butadiene and 45 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 61% by mass, a vinyl aromatic monomer unit content RS of 45% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 24% by mass, and a weight average molecular weight of 160,000. Furthermore, a hydrogenation catalyst prepared by the above method is added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-5. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-5 was 98 mol%. Other physical properties are shown in Table 4.

[Example 6] (Hydrogenated block copolymer (A)-6) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.050 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 38 parts by mass of butadiene and 46 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 62% by mass, a vinyl aromatic monomer unit content RS of the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) of 46% by mass, a vinyl bond content of 22% by mass, and a weight average molecular weight of 159,000. Furthermore, the hydrogenation catalyst prepared by the above method was added to the obtained block copolymer at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-6. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-6 was 98 mol%. Other physical properties are shown in Table 4.

[Example 7] (Hydrogenated block copolymer (A)-7) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.047 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 30 parts by mass of butadiene and 54 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 70% by mass, a vinyl aromatic monomer unit content RS of 54% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 17% by mass, and a weight average molecular weight of 160,000. Furthermore, a hydrogenation catalyst prepared by the above method was added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-7. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-7 was 98 mol%. Other physical properties are shown in Table 4.

[Example 8] (Hydrogenated block copolymer (A)-8) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.047 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 29 parts by mass of butadiene and 55 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 71% by mass, a vinyl aromatic monomer unit content RS of 55% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 17% by mass, and a weight average molecular weight of 160,000. Furthermore, a hydrogenation catalyst prepared by the above method was added to the obtained block copolymer at a Ti standard of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-8. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-8 was 98 mol%. Other physical properties are shown in Table 4.

[Example 9] (Hydrogenated block copolymer (A)-9) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.048 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 60°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 66% by mass, a vinyl aromatic monomer unit content RS of the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) of 50% by mass, a vinyl bond content of 24% by mass, and a weight average molecular weight of 161,000. Furthermore, a hydrogenation catalyst prepared by the above method is added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-9. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-9 was 98 mol%. Other physical properties are shown in Table 4.

[Example 10] (Hydrogenated block copolymer (A)-10) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.048 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.5 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 66% by mass, a vinyl aromatic monomer unit content RS of 50% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 17% by mass, and a weight average molecular weight of 160,000. Furthermore, a hydrogenation catalyst prepared by the above method was added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-10. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-10 was 98 mol%. Other physical properties are shown in Table 4.

[Comparative Example 1] (Hydrogenated block copolymer (A)-A) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 18 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.045 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 22 parts by mass of butadiene and 42 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 18 parts by mass of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 78% by mass, a vinyl aromatic monomer unit content RS of the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) of 42% by mass, a vinyl bond content of 21% by mass, and a weight average molecular weight of 160,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared by the above method was added based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-A. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-A was 98 mol%. Other physical properties are shown in Table 5.

[Comparative Example 2] (Hydrogenated block copolymer (A)-B) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 2 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.050 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 39 parts by mass of butadiene and 57 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 2 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 61% by mass, a vinyl aromatic monomer unit content RS of 57% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 20% by mass, and a weight average molecular weight of 159,000. Furthermore, a hydrogenation catalyst prepared by the above method is added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-B. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-B was 98 mol%. Other physical properties are shown in Table 5.

[Comparative Example 3] (Hydrogenated block copolymer (A)-C) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.054 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 51 parts by mass of butadiene and 33 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 49% by mass, a vinyl aromatic monomer unit content RS of the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a) of 33% by mass, a vinyl bond content of 30% by mass, and a weight average molecular weight of 160,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared by the above method was added based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-C. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-C was 98 mol%. Other physical properties are shown in Table 5.

[Comparative Example 4] (Hydrogenated block copolymer (A)-D) Batch polymerization was carried out using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.044 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution containing 20 parts by mass of butadiene and 64 parts by mass of styrene was added (concentration 20% by mass), and polymerization was carried out at 80°C for 2 hours. At this time, the concentrations of butadiene and styrene in the reaction system were quantitatively measured in real time by using ReactIR, and the feed rate was appropriately adjusted so that the polymerization rate of each reached 1:1 (mass fraction conversion). In ReactIR, the butadiene monomer was tracked at a wavelength of 1589 cm ^-1 , and the styrene monomer was always tracked at a wavelength of 775 cm ^-1 . When the reactivity ratio was higher than the required reactivity ratio by more than 10%, the feed rate of butadiene was increased, and when the reactivity ratio was lower than the required reactivity ratio by more than 10%, the feed rate of butadiene was reduced, thereby adjusting to the required reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 8 mass parts of styrene (concentration 20 mass%) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. The block copolymer obtained by the above method has a styrene content of 80% by mass, a vinyl aromatic monomer unit content RS of 64% by mass in the hydrogenated copolymer block (b) relative to the entire hydrogenated block copolymer (a), a vinyl bond content of 14% by mass, and a weight average molecular weight of 161,000. Furthermore, a hydrogenation catalyst prepared by the above method is added to the obtained block copolymer at a Ti base of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer to obtain a hydrogenated block copolymer (A)-D. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-D was 98 mol%. Other physical properties are shown in Table 5.

[Comparative Example 5] (Hydrogenated block copolymer (A)-E) Batch polymerization was performed using a tank reactor (content volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20 mass%) containing 8 parts by mass of styrene was added. Next, 0.048 parts by mass of n-butyl lithium was added relative to 100 parts by mass of all monomers, and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added relative to 1 mol of n-butyl lithium, and polymerization was performed at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20 mass%) containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added, and polymerization was performed at 80°C for 2 hours. At this time, ReactIR was not used, and the feed rate was set to butadiene:styrene = 34:50 at a constant rate. Finally, a cyclohexane solution containing 8 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 65°C for 1 hour. Thereafter, methanol was added to stop the polymerization reaction and obtain a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content was 66% by mass, the content RS of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole was 50% by mass, the vinyl bond content was 25% by mass, and the weight average molecular weight was 160,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared in the above manner was added based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to obtain a hydrogenated block copolymer (A)-E. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-E was 98 mol%. Other physical properties are shown in Table 5.

[Preparation of pressure-molded sheets] The hydrogenated block copolymers (A)-1 to (A)-10 and (A)-A to (A)-E prepared in the above manner were individually rolled out at 160°C using a 4-inch roller, and then press-molded by hydraulic pressure at 200°C and 100 kg/ ^cm2 to produce 2 mm thick pressure-molded sheets.

[Preparation of injection molded sheets] Hydrogenated block copolymers (A)-1 to (A)-10 and (A)-A to (A)-E were used for injection molding at 220°C to prepare 2 mm thick injection molded sheets and obtain physical property measurement sheets.

For the hydrogenated block copolymers (A)-1 to 10 and (A)-A to E of [Examples 1 to 10] and [Comparative Examples 1 to 5] above, the values of the following items were measured. (Structural analysis value) Content of all vinyl aromatic monomer units (styrene) in hydrogenated block copolymer (A) (mass %) Content of polymer block (polystyrene block) (a) mainly composed of vinyl aromatic monomer units in hydrogenated block copolymer (A) (mass %) Content of hydrogenated copolymer block (b) containing vinyl aromatic monomer units and covalent diene monomer units in hydrogenated block copolymer (A) (mass %) Content of vinyl aromatic monomer units in hydrogenated copolymer block (b) (mass %) Content of vinyl aromatic monomer units in hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A) (mass %) Content of covalent diene in hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A) (mass %) Vinyl bond content in hydrogenated block copolymer (A) (mass %) Molecular weight distribution of hydrogenated block copolymer (A) Weight average molecular weight of hydrogenated block copolymer (A) (10,000) Hydrogenation rate of double bonds of conjugated diene monomer units in hydrogenated block copolymer (A) (mol %) (Physical properties) ・ Melt flow rate (MFR: 230℃, 2.16 kg) ・ Tanδ peak temperature at -20～60℃ in viscoelasticity measurement chart (℃) ・ Hardness (JIS-A instantaneous)

Furthermore, polymer blocks (a) to (b) represent the following polymer blocks respectively. Polymer block (a): A polymer block mainly composed of vinyl aromatic monomer units Copolymer block (b): A hydrogenated copolymer block containing vinyl aromatic compound monomer units and covalent diene monomer units

[Table 4] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Hydrogenated block copolymer (A) -1 (A)-2 (A)-3 (A) -4 (A) -5 (A)-6 (A)-7 (A)-8 (A)-9 (A) -10 Vinyl bond adjuster (mol/n-BuLi 1 mol) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.5 Polymerization temperature (℃) 80 80 80 80 80 80 80 80 60 80 Effective use of react_IR ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Content of all vinyl aromatic monomer units (mass %) 70 69 66 65 61 62 70 71 66 66 Content of polymer block (a) (mass %) 26 twenty four 16 14 16 16 16 16 16 16 Content of hydrogenated copolymer block (b) (mass %) 74 76 84 86 84 84 84 84 84 84 Content of vinyl aromatic monomer units in hydrogenated copolymer block (b) (mass %) 59 59 59 59 53 55 64 66 59 59 The content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (a) as a whole RS (mass %) 44 45 50 51 45 46 54 55 50 50 Content of the conjugated diene monomer unit in the hydrogenated copolymer block (b) relative to the total content of the hydrogenated block copolymer (a) (mass %) 30 31 34 35 39 38 30 29 34 34 Vinyl bond content in hydrogenated block copolymer (A) (mass %) twenty one 20 twenty one twenty one twenty four twenty two 17 17 twenty four 17 Molecular weight distribution 1.05 1.06 1.08 1.06 1.08 1.07 1.05 1.06 1.06 1.06 Weight average molecular weight (ten thousand) 16.0 16.0 16.1 16.0 16.0 15.9 16.0 16.0 16.1 16.0 Hydrogenation rate of double bonds of conjugated diene monomer units (molar %) 98 98 98 98 98 98 98 98 98 98 Peak intensity P 0.231 0.242 0.262 0.274 0.243 0.239 0.272 0.284 0.240 0.237 P0 0.243 0.249 0.276 0.282 0.248 0.257 0.299 0.308 0.276 0.276 Randomness parameter g(＝P/P0) 0.95 0.97 0.95 0.97 0.98 0.93 0.91 0.92 0.87 0.86 MFR (230℃, 2.16 kg) 2.9 3.9 10.1 11.3 8.3 8.3 10.7 11.8 9.5 9.5 Hardness (JIS-A, instantaneous) 87 86 74 72 70 71 90 92 74 74 -20～60℃ tanδ peak temperature (℃) 19 19 19 19 11 15 30 33 18 19 -20～60℃ tanδ peak height 1.7 1.8 2.2 2.3 2.2 2.2 2.2 2.2 2.0 2.0 Abrasion resistance: Rating 3 5 5 3 3 5 5 3 4 4 Low rebound: Denlop rebound elastic modulus (%) 3.1 2.5 1.0 0.90 15 1.2 1.6 10 2.0 2.0

[Table 5] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Hydrogenated block copolymer (A) (A)-B (A)-C (A)-D (A)-E Vinyl bond adjuster (mol/n-BuLi 1 mol) 0.9 0.9 0.9 0.9 0.9 Polymerization temperature (℃) 80 80 80 80 80 Effective use of react_IR ○ ○ ○ ○ × Content of all vinyl aromatic monomer units (mass %) 78 61 49 80 66 Content of polymer block (a) (mass %) 36 4 16 16 16 Content of hydrogenated copolymer block (b) (mass %) 64 96 84 84 84 Content of vinyl aromatic monomer units in hydrogenated copolymer block (b) (mass %) 65 59 39 76 59 The content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (a) as a whole RS (mass %) 42 57 33 64 50 Content of the conjugated diene monomer unit in the hydrogenated copolymer block (b) relative to the total content of the hydrogenated block copolymer (a) (mass %) twenty two 39 51 20 34 Vinyl bond content in hydrogenated block copolymer (A) (mass %) twenty one 20 30 14 25 Molecular weight distribution 1.06 1.06 1.06 1.06 1.06 Weight average molecular weight (ten thousand) 16.0 15.9 16.0 16.1 16.0 Hydrogenation rate of double bonds of conjugated diene monomer units (molar %) 98 98 98 98 98 Peak intensity P 0.229 0.302 0.179 0.337 0.199 P0 0.231 0.315 0.182 0.355 0.276 Randomness parameter g(＝P/P0) 0.99 0.96 0.98 0.95 0.72 MFR (230℃, 2.16 kg) 2.4 13.7 4.6 14.7 12.5 Hardness (JIS-A, instantaneous) 95 65 55 95＜ 74 -20～60℃ tanδ peak temperature (℃) 18 19 -20 46 18 -20～60℃ tanδ peak height 1.2 2.5 2.2 2.2 1.5 Abrasion resistance: Rating 1 1 1 1 1 Low rebound: Denlop rebound elastic modulus (%) 10 0.50 70 45 6.0

It can be seen that the hydrogenated block copolymers of Examples 1 to 10 have excellent wear resistance and low resilience. [Industrial Applicability]

The hydrogenated block copolymer of the present invention has industrial applicability in the fields of automobile parts (automobile interior materials, automobile packaging materials), medical device materials, various containers such as food packaging containers, home appliances, industrial parts, toys, etc.

Claims (8)

A hydrogenated block copolymer (A) comprising vinyl aromatic monomer units and covalent diene monomer units, and containing at least one polymer block (a) mainly composed of vinyl aromatic monomer units, and satisfying the following <Condition (1)> to <Condition (3)>, <Condition (1)>: containing at least one hydrogenated copolymer block (b) comprising vinyl aromatic monomer units and covalent diene monomer units, and the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) is 65% by mass or more and 95% by mass or less; <Condition (2)>: the content of the vinyl aromatic monomer units in the hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less; <Condition (3)>: The ratio of the peak intensity P detected by a thermal decomposition gas phase chromatography mass spectrometry analyzer to P0 obtained according to the following (Formula I) is g=P/P0 or more, which is 0.75; P0=k×RS (Formula I) (In (Formula I), RS is the content (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole; k represents the proportional constant when the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (A) as a whole is first approximated to the peak intensity P, and the peak intensity P is obtained when the homogeneously polymerized hydrogenated block copolymer (A) is analyzed by a thermal decomposition gas phase chromatography mass spectrometry analyzer). The hydrogenated block copolymer of claim 1, wherein the ratio of the peak intensity P to P0 obtained by the above (Formula I) g = P/P0 is greater than 0.9. The hydrogenated block copolymer of claim 1, wherein the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 55 mass % or more and 65 mass % or less. The hydrogenated block copolymer of claim 1, wherein the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (a) is 75 mass % or more and 85 mass % or less. A hydrogenated block copolymer composition, comprising: a hydrogenated block copolymer (A) as in any one of claims 1 to 4: 1% by mass or more and 50% by mass or less, at least one olefinic resin (B): 5% by mass or more and 90% by mass or less, at least one thermoplastic resin (C): 1% by mass or more and 50% by mass or less, and at least one softener (D): 5% by mass or more and 90% by mass or less. The hydrogenated block copolymer composition of claim 5, wherein the olefinic resin (B) comprises at least one polypropylene resin. A shaped body, which is a shaped body of the hydrogenated block copolymer composition of claim 5. The formed body as claimed in claim 5 is a foamed body.