TWI907948B - Hydrogenated block copolymers, hydrogenated block copolymer compositions, and molded articles - Google Patents

Abstract

This invention provides a hydrogenated block copolymer exhibiting excellent low elasticity and wear resistance. The hydrogenated block copolymer (A) of this 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 conjugated diene monomer unit, and the content of the hydrogenated copolymer block (b) is 65-95% by mass. <Condition (2)>: The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 40-75% by mass. <Condition (3)>: The ratio g = P/P0 of the peak intensity P detected by thermal decomposition gas chromatography-mass spectrometry and calculated according to (Equation I) is 0.75 or higher. P0 = k × RS (Equation I) (In (Equation I), RS is the content (mass %) of vinyl aromatic monomer units in block (b) relative to the entire hydrogenated block copolymer (A). k represents the proportionality constant when approximating RS (mass %) with the peak intensity P.)

Description

Hydrogenated block copolymers, hydrogenated block copolymer compositions, and molded articles

This invention relates to a hydrogenated block copolymer, a hydrogenated block copolymer composition, and a molded article.

Hydrogenates of block copolymers containing conjugated diene compounds and vinyl aromatic compounds possess the same elasticity at room temperature as vulcanized natural or synthetic rubber, even without vulcanization, and exhibit the same processability as thermoplastic resins at high temperatures. Therefore, they are widely used in plastic modifiers, adhesives, automotive parts, and medical devices. Furthermore, due to their excellent weather resistance and heat resistance, these block copolymer hydrogenates are particularly widely used in practical applications as materials for automotive parts and medical devices.

However, hydrogenated block copolymers containing conjugated diene compounds and vinyl aromatic compounds, such as hydrogenated styrene elastomers (hereinafter sometimes referred to as "TPS materials"), exhibit poor abrasion resistance, thus limiting their applications. To address this issue, the industry has proposed a resin composition of a random copolymer styrene elastomer and polypropylene resin, comprising 40% by mass or more but less than 95% by mass of vinyl aromatic monomers, and a molded article of the resin composition, revealing that the molded article exhibits excellent abrasion resistance (see, for example, Patent 1).

Furthermore, in recent years, autonomous driving and mobility services have garnered attention as innovative directions in the automotive industry. This trend will also change the performance requirements for automotive interior materials. For example, it is predicted that with the advancement of autonomous driving, the meaning of the car as a living space will be further enhanced. Therefore, in order to continuously construct spaces where passengers can live more comfortably and to create a high-end feel, materials with low rebound are needed. Moreover, from the perspective of mobility services, with the penetration of car sharing, the industry is constantly pursuing the longevity and cleanliness of vehicles. Therefore, the frequency of cleaning automotive interior materials has increased, requiring higher wear resistance in the resin compositions of automotive interior materials. As mentioned above, due to the penetration of autonomous driving or mobility services, in recent years, the polymers of resin composition materials have needed to have superior wear resistance and good tactile feel compared to previous products.

In view of the requirements described above, the industry has proposed a hydrogenated block copolymer that exhibits a tanδ (loss tangent) peak within a specific temperature range, and resin compositions using this hydrogenated block copolymer show excellent energy absorption and low elasticity (see, for example, Patent 2). [Prior Art Documents] [Patent Documents]

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

[Problem to be solved by the invention] However, the previously proposed hydrogenated block copolymers have the following problems: there is room for improvement in terms of good tactile feel, i.e., low elasticity and abrasion resistance.

Therefore, the purpose of this invention is to provide a hydrogenated block copolymer that exhibits excellent low elasticity and wear resistance. [Technical means to solve the problem]

The inventors have made repeated efforts to solve the problems of the prior art, and have discovered that a hydrogenated block copolymer can be provided, thus completing the present invention. This hydrogenated block copolymer has a specific structure, and by specifying the content of the hydrogenated copolymer block (b) containing vinyl aromatic monomers and conjugated diene monomers, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b), and a prescribed random parameter g, it exhibits excellent low elasticity and wear resistance. That is, the present invention is as follows.

[1] A hydrogenated block copolymer (A) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, and comprising at least one polymer block (a) in which the vinyl aromatic monomer unit is the main component, and satisfying 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 conjugated diene monomer unit, and the content of the hydrogenated copolymer block (b) in the above-mentioned 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 unit in the above-mentioned hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less. <Condition (3)>: The ratio g = P/P0 of the peak intensity P detected by the thermal decomposition gas chromatography mass spectrometry analysis device and the P0 calculated according to the following (Equation I) is 0.75 or higher. P0 = k × RS (Equation I) (In Equation I, RS is the content (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A). k represents the proportionality constant when the content RS (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A) is approximated with the peak intensity P, which is obtained by analyzing the homogeneous polymerization hydrogenated block copolymer (A) using a thermal decomposition gas chromatography mass spectrometry analysis device) [2] As described in [1] above, the ratio g = P/P0 of the above peak intensity P and P0 obtained by using the above (Equation 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 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: a hydrogenated block copolymer (A) as described in any one of [1] to [4] above: 1% by mass and 50% by mass, at least one olefinic resin (B): 5% by mass and 90% by mass, at least one thermoplastic resin (C): 1% by mass and 50% by mass, and at least one softener (D): 5% by mass and 90% by mass. [6] A hydrogenated block copolymer composition as described in [5] above, wherein the olefinic resin (B) comprises at least one polypropylene resin. [7] A molded body, which is a molded body of the hydrogenated block copolymer composition as described in [5] above. [8] The molded body described in [5] above is a foamed body. [Effects of the Invention]

According to the present invention, hydrogenated block copolymers exhibiting excellent low elasticity and wear resistance can be obtained.

The following describes in detail the forms used to implement the present invention (hereinafter referred to as "the embodiments"). Furthermore, the embodiments described below are examples used to illustrate the present invention and are not intended to limit the present invention to the following objectives. The present invention can be implemented with various variations within the scope of its objectives.

[Hydrogenated Block Copolymer] The hydrogenated block copolymer of this embodiment (hereinafter, sometimes referred to as hydrogenated block copolymer (A)) is a hydrogenated block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and containing at least one polymer block (a) with a vinyl aromatic monomer unit 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 conjugated diene monomer unit, and the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) of this embodiment is 65% by mass or more and 95% by mass or less. <Condition (2)>: The content of the vinyl aromatic monomer unit in the above-mentioned hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less. <Condition (3)>: The ratio g = P/P0 of the peak intensity P detected by a thermal decomposition gas chromatography-mass spectrometry analysis apparatus and P0 calculated according to the following (Equation I) is 0.75 or more. P0 = k × RS … (Equation I) (RS is the content (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A). k represents the proportionality constant when approximating the content RS of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A) with the peak intensity P, which is obtained by analyzing the hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization) using a thermal decomposition gas chromatography-mass spectrometry analysis device.)

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

(Vinyl Aromatic Monomer Unit) The hydrogenated block copolymer (A) of this embodiment comprises vinyl aromatic monomer units. Examples of vinyl aromatic compounds forming the vinyl aromatic monomer units include, but are not limited to, monomer units derived from styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Styrene is particularly preferred from the viewpoint of balancing cost and the mechanical strength of the resin composition comprising the hydrogenated block copolymer. Only one of these monomer units may be used, or two or more may be used in combination.

(Conjugated Diene Monomer Unit) The hydrogenated block copolymer (A) of this embodiment comprises a conjugated diene monomer unit. The conjugated diene monomer unit is derived from a diene hydrocarbon having one 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. Especially from the viewpoint of a good balance between processability and mechanical strength, 1,3-butadiene and isoprene are preferred. One or more of these monomers may be used alone.

(Amount of vinyl bonds in all conjugated diene monomer units) The hydrogenated block copolymer (A) of this embodiment does not have a particular limitation on the amount of vinyl bonds in all conjugated diene monomer units, but it is preferably 5% by mass or more. More preferably 15% by mass or more, and even more preferably 20% by mass or more. If the amount of vinyl bonds in all conjugated diene monomer units of the hydrogenated block copolymer (A) is 5% by mass or more, then during the hydrogenation step, precipitation from solution caused by crystallization of the hydrogenated conjugated diene blocks can be suppressed. Furthermore, if the vinyl bond content is 5% by mass or more, the crystallization of the hydrogenated conjugated diene blocks is suppressed, and good flexibility can be obtained in the hydrogenated block copolymer, its composition, and the molded article of this embodiment. Also, the vinyl bond content in all conjugated diene monomer units of the hydrogenated block copolymer (A) of this embodiment is preferably 60% by mass or less, and more preferably 50% by mass or less. If the vinyl bond content in all conjugated diene monomer units of the hydrogenated block copolymer (A) is 60% by mass or less, good tensile strength can be obtained in the hydrogenated block copolymer, its composition, and the molded article of this embodiment. The amount of vinyl bonds in all conjugated diene monomer units of the hydrogenated block copolymer (A) can be controlled within the above-mentioned value range, for example, by using modifiers such as tertiary amine compounds or ether compounds (vinyl bond content modifiers). Furthermore, the amount of vinyl bonds can be measured by the method described in the following embodiments.

(Content of all vinyl aromatic monomers) The content of all vinyl aromatic monomers in the hydrogenated block copolymer (A) of this 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 even more preferably 60% by mass or more and 80% by mass or less. If the content of all vinyl aromatic monomers is 50% by mass or more, the hydrogenated block copolymer (A) of this embodiment tends to have good oil resistance. If the oil resistance is good, it can be used in automotive materials and other applications requiring more stringent oil resistance. For applications requiring stricter oil resistance, such as automotive interior materials, when molding thinner-walled or more complex/larger molded bodies, and for longer-term use, the hydrogenated block copolymer (A) of this embodiment tends to suppress material deformation or appearance defects. Furthermore, in this specification, "typical molded body" is defined as a simple, small molded body of approximately 150 mm square, with a thickness of about 2 mm and a flat surface. It has been confirmed that, compared to this "typical molded body," thin-walled or complex and large molded bodies tend to exhibit reduced properties in oil resistance, abrasion resistance, damage resistance, appearance, low-temperature characteristics, tactile feel, and shape retention. Furthermore, if the oil resistance is good, there is a tendency to increase the upper limit of the amount of hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of the present embodiment, thereby increasing the degree of freedom in formulation. Generally, the less hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of the present embodiment, the better the oil resistance becomes. However, there is a tendency for the more hydrogenated block copolymer (A) in the composition, the better the abrasion resistance or tactile feel. Therefore, a higher upper limit for the amount in the composition is preferable. Moreover, the content of all vinyl aromatic monomer units in the hydrogenated block copolymer (A) of the present embodiment can be determined using the unhydrogenated block copolymer or the hydrogenated block copolymer after hydrogenation as samples and with a UV spectrophotometer. Furthermore, the content of all vinyl aromatic monomer units in the hydrogenated block copolymer (A) can be controlled within the above-mentioned value range by mainly adjusting the amount of vinyl aromatic compounds added to the polymerization reactor, the reaction temperature, and the reaction time.

Furthermore, in this specification, the term "as the main component" for the polymer block constituting the hydrogenated block copolymer (a) means that the specified proportion of the block polymer is 85% by mass or more, preferably 90% by mass or more, and even more preferably 95% by mass or more. Furthermore, the content of vinyl aromatic monomer units in the aforementioned hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less (as described in <condition (2)>), thus the aforementioned polymer block (a) and the hydrogenated polymer block (b) can be clearly distinguished.

(Polymer block (a) with vinyl aromatic monomers as the main component) The hydrogenated block copolymer (A) of this embodiment contains at least one polymer block (a) with vinyl aromatic monomers as the main component. Therefore, it tends to prevent particle adhesion. Furthermore, the content of the above-mentioned polymer block (a) in the hydrogenated block copolymer (A) of this embodiment is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. If the content of the polymer block (a) with vinyl aromatic monomers as the main component is 5% by mass or more, the particle adhesion resistance of the hydrogenated block copolymer (A) becomes good, and it tends to exhibit good tensile properties in the hydrogenated block copolymer, its composition, and the molded article of this embodiment.

When the particles of the hydrogenated block copolymer (A) of this embodiment exhibit good anti-blocking properties, they tend to be less prone to sticking even under conditions such as longer transport times, higher loads, and harsher temperature environments (e.g., regions with high external temperatures or drastic temperature differences). This facilitates particle measurement or admixture during composite molding. Furthermore, it can reduce the amount of anti-stick agent required, thereby preventing equipment contamination, reducing environmental impact, and suppressing unexpected degradation of physical properties, such as decreased transparency and mechanical strength.

The content of the polymer block (a) in the hydrogenated block copolymer (A) of this embodiment can be determined by using nuclear magnetic resonance (NMR) as a sample, either the unhydrogenated block copolymer or the hydrogenated block copolymer (Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), hereinafter referred to as "NMR method"). Specifically, it can be determined by the method described in the following embodiments. Furthermore, the content of the polymer block (a) in the hydrogenated block copolymer (A) can be controlled within the above-mentioned value range by mainly adjusting the amount of 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 this embodiment contains at least one hydrogenated copolymer block (b) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, 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.

The hydrogenated block copolymer (A) of this embodiment contains 65% by mass or more and 95% by mass or less, preferably 70% by mass or more and 90% by mass or less, and more preferably 75% by mass or more and 85% by mass or less. If the content of the hydrogenated block copolymer (A) of this embodiment contains 65% by mass or more and 95% by mass or less, the hydrogenated block copolymer (A) of this embodiment tends to exhibit good wear resistance. Furthermore, if the abrasion resistance is 70% or more and 90% or less, it exhibits even higher abrasion resistance. If the abrasion resistance is 75% or more and 85% or less, it can be used in the following situations: applications where abrasion resistance requirements are even more stringent, such as applications in automotive interior materials where excellent abrasion resistance is required in thinner molded bodies, or applications in automotive interior materials where abrasion resistance is required due to higher loads or coarser weave fabrics, such as fine white cloth No. 3, which has a coarser weave than cotton fabric, i.e., coarse twill cotton fabric, etc., and where maintaining appearance for a long time is required. Furthermore, if the wear resistance is good, the lower limit of the amount of hydrogenated block copolymer (A) in the hydrogenated block copolymer composition using this embodiment can be reduced, tending to increase the degree of freedom in formulation. Generally, the more hydrogenated block copolymer (A) is formulated in the following hydrogenated block copolymer composition, the better the wear resistance becomes. However, since the less hydrogenated block copolymer (A) is formulated, the better the oil resistance or material cost becomes, the lower limit of the formulation amount is preferred to be lower. If the content of hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) of this embodiment is 65% by mass or more and 95% by mass or less, it exhibits excellent low elasticity and thus tends to exhibit a good tactile feel. Furthermore, if it is 70% by mass or more and 90% by mass or less, the low elasticity is improved, making it suitable for applications with more stringent tactile requirements. If it is 75% by mass or more and 85% by mass or less, it can be appropriately used for applications with even more stringent tactile requirements, such as automotive interior materials.

<Condition (2)> The content of vinyl aromatic monomer units in the hydrogenated block copolymer (a) of the present embodiment in the above-mentioned hydrogenated copolymer block (b) (100% by mass) is 40% by mass or more and 75% by mass or less.

The content of vinyl aromatic monomer units 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 vinyl aromatic monomer units in the hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less, the hydrogenated block copolymer (a) of this embodiment tends to exhibit good wear resistance. Furthermore, if the abrasion resistance is 45% or more and 70% or less, it exhibits even higher abrasion resistance. If the abrasion resistance is 55% or more and 65% or less, it tends to be used in the following situations: applications where the abrasion resistance requirements are even more stringent, such as in automotive interior materials, applications where excellent abrasion resistance is required in molded bodies with thinner walls, or in automotive interior materials applications where higher load-bearing capacity or coarser fabrics are required during vehicle use, such as coarser twill cotton fabrics with a coarser weave than fine white cotton No. 3, etc., where abrasion resistance is required to maintain appearance for a long time. If the content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less, it exhibits excellent low elasticity and thus tends to provide a good tactile feel. Furthermore, if it is 45% by mass or more and 70% by mass or less, the low elasticity is improved, making it suitable for applications with more stringent tactile requirements. If it is 55% by mass or more and 65% by mass or less, it can be used in applications with even more stringent tactile requirements, such as automotive interior materials.

Furthermore, the content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) can be determined using nuclear magnetic resonance (NMR) or similar methods. Also, the content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) can be controlled within the aforementioned range by adjusting the amount, feeding rate, and reaction temperature of the vinyl aromatic compounds and conjugated diene compounds added to the polymerization reactor.

(Weight average molecular weight of hydrogenated block copolymer (A)) From the viewpoint of extrusion molding properties and obtaining good mechanical strength during the particle manufacturing of the hydrogenated block copolymer of this embodiment, 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 even more preferably 100,000 or more and 400,000 or less. If the weight-average molecular weight (Mw) is above 10,000, the hydrogenated block copolymer composition using this embodiment tends to exhibit good mechanical strength. Furthermore, if the weight-average molecular weight (Mw) is below 500,000, during the particle manufacturing (extrusion molding) of the hydrogenated block copolymer, the hydrogenated block copolymer (A) tends to melt easily, the filament is more stable, and the extrusion molding properties are improved. Moreover, the weight-average molecular weight of the hydrogenated block copolymer (A) of this embodiment can be determined using gel permeation chromatography (GPC) and obtained using a calibration curve derived from the determination of commercially available standard polystyrene (using the peak molecular weight of standard polystyrene).

(Molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (A) in this embodiment) The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (A) is preferably 10 or less, more preferably 1 to 8, and even more 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 determined using gel osmosis chromatography (GPC). The molecular weight of the peak in the chromatogram is determined using a calibration curve derived from the determination of commercially available standard polystyrene (using the peak molecular weight of standard polystyrene). The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (A) is determined based on the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn).

(Hydrolysis rate of double bonds in the conjugated diene monomer unit in the hydrogenated block copolymer (A)) In the hydrogenated block copolymer composition using the present embodiment, from the viewpoint of obtaining good weather resistance and low-temperature characteristics, the hydrogenation rate of double bonds in the conjugated diene monomer unit 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, and further preferably 92 mol% or more. The hydrogenation rate of double bonds in the conjugated diene monomer unit in the hydrogenated block copolymer (A) can be controlled within the above-mentioned value range by adjusting the amount of hydrogenation. The hydrogenation rate of the hydrogenated block copolymer (A) can be determined using nuclear magnetic resonance (NMR) devices.

(Hydrolysis rate of aromatic double bonds in the vinyl aromatic monomer units of the hydrogenated block copolymer (A)) Regarding the hydrolysis rate of aromatic double bonds in the vinyl aromatic monomer units of the hydrogenated block copolymer (A) of this embodiment, from the viewpoint of obtaining good weather resistance, it is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 10 mol% or less. The hydrolysis rate of aromatic double bonds in the vinyl aromatic monomer units of the hydrogenated block copolymer (A) can be determined using a nuclear magnetic resonance (NMR) apparatus or the like.

(Crystallization peak of hydrogenated block copolymer (A)) Preferably, in the differential scanning calorimetry (DSC) curve, the hydrogenated block copolymer (A) does not substantially contain hydrogenated compounds that cause crystallization peaks in the range of -25 to 80°C. Here, "there is no substantial crystallization peak caused by the hydrogenated copolymer block (b) in the range of -25 to 80°C" means that in this temperature range, no peak caused by the crystallization of the hydrogenated copolymer block (b) appears, or even if a peak caused by crystallization is confirmed, the heat of the crystallization peak generated by the crystallization does not reach 3 J/g, preferably not 2 J/g, more preferably not 1 J/g, and even more preferably no heat of crystallization peak. As described above, if there is no substantial crystallization peak caused by the hydrogenated copolymer block (b) within the temperature range of -25 to 80°C, good softness can be obtained in the hydrogenated block copolymer (A) of this embodiment, thereby making it more suitable to achieve the softening of the hydrogenated block copolymer composition described below. In order to obtain the hydrogenated block copolymer (A) in which there is no substantial crystallization peak caused by the hydrogenated copolymer block (b) within the temperature range of -25 to 80°C, it is only necessary to carry out a hydrogenation reaction on the copolymer. The copolymer is obtained by using a modifier that specifies the adjustment of the vinyl bond quantity or the copolymerization of the vinyl aromatic compound and the conjugated diene, and by carrying out a polymerization reaction under the following conditions.

(The tanδ (loss tangent) peak in the viscoelasticity test graph of the hydrogenated block copolymer (A) of this embodiment is preferably such that at least one tanδ (loss tangent) peak exists in the viscoelasticity test graph above -25°C and below 45°C. More preferably, it exists above -5°C and below 40°C, even more preferably above 10°C and below 35°C, and even more preferably above 15°C and below 30°C. This tanδ peak is caused by the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A). By exhibiting at least one peak within a temperature range of -25°C to 60°C, the hydrogenated block copolymer (A) of this embodiment exhibits low elasticity, thus tending to provide a good tactile feel. Furthermore, the tanδ of the hydrogenated block copolymer (A) can be measured using a viscoelasticity measuring apparatus (manufactured by TA Instruments Inc., ARES) under conditions of 0.5% strain, 1 Hz frequency, and a heating rate of 3°C/min. Specifically, it can be measured using the method described in the following embodiments.

(Random parameter g of hydrogenated block copolymer (A)) <Condition (3)> The ratio of the peak intensity P detected by thermal decomposition gas chromatography mass spectrometry analysis device to P0 calculated according to the following (Equation I): g = P/P0 is 0.75 or more. P0 = k × RS (Equation I) (In Equation I, RS is the content (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A). k represents the proportionality constant when approximating the content RS (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A) with the peak intensity P, which is obtained by analyzing the homogeneous hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization) using a thermal decomposition gas chromatography-mass spectrometry analysis device.)

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

In the hydrogenated block copolymer (A) of this embodiment, the random parameter g is 0.75 or higher, preferably 0.8 or higher, more preferably 0.85 or higher, and even more preferably 0.9 or higher. If the random parameter g is 0.75 or higher, the hydrogenated block copolymer (A) of this embodiment tends to exhibit good wear resistance. Furthermore, if the value is 0.9 or higher, it exhibits even higher abrasion resistance and can be used in the following situations: applications with stricter abrasion resistance requirements, such as automotive interior materials; applications requiring excellent abrasion resistance in thinner-walled molded parts; or automotive interior materials applications where higher loads or coarser weave fabrics, such as coarser twill cotton fabrics (like No. 3 fine white cotton), are required to maintain appearance for a long time. Also, if the random parameter g is 0.75 or higher, the height of the tanδ peak of the hydrogenated block copolymer (A) in this embodiment is increased, low elasticity is improved, and a good tactile feel is exhibited. Furthermore, if the value is above 0.9, a higher tanδ peak can be obtained, resulting in better low elasticity and a tendency to achieve a better tactile feel.

[Calculation Method of Random Parameter g] The random parameter g can be calculated based on a 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)-(conjugated diene monomer)-(vinyl aromatic monomer) structure in the hydrogenated copolymer block (b), which is assumed to be defined by the following two conditions (i) and (ii).

(Condition (i)) When the retention time of the peaks originating from styrene dimers (attributed by sample determination) detected under the conditions shown in Table 1 below is set to 0 min, the peaks detected are those with relative retention times of 1.83 min, 2.15 min, and 2.45 min (with an allowable error of approximately 0.01 min). (Condition (ii)) Fragmented peaks with 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 of P0 obtained using the following (Equation I): g = P/P0. P0 = k × RS … (Equation I) In the above (Equation I), RS is the content (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the hydrogenated block copolymer (a) as a whole, which can be measured using nuclear magnetic resonance (NMR) or the like. In Equation I above, k is a proportionality constant obtained using a first-order approximation formula, which is the ratio of the content RS (mass %) of the vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer (A) to the peak intensity P. The peak intensity P is the peak intensity measured using a pyrolysis gas chromatography-mass spectrometry (py-GC/MS) apparatus for hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization). Experimentally, the value of k is approximately 0.0056. For example, when the RS of a certain hydrogenated block copolymer is 40% by mass, P0 is 0.0056 × 40 = 0.224 according to Equation I above. When the peak intensity P = 0.112 obtained using py-GC/MS, g = 0.112/0.224 = 0.5 can be calculated.

P0 is an estimated value of the peak intensity P measured by py-GC/MS during the polymerization of the hydrogenated block copolymer (A) using the specific polymerization method described below (homogeneous polymerization). By comparing the above P0 with the actual detected P value in the form of the random parameter g = P/P0, the uniformity of the arrangement of the vinyl aromatic monomers and conjugated diene monomers in the hydrogenated copolymer block (b) can be evaluated.

Since the detection sensitivity of the MS detector used in py-GC/MS determination changes with each adjustment, an external standard is used for sensitivity correction. In this manual, unless otherwise specified, the peak intensity P is defined as the value obtained by dividing the absolute area of the peak by the baseline value X obtained from the determination of the external standard. Preferred external standard is dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol, hereinafter referred to as BHT), which is not easily decomposed under heat or oxygen atmospheres and is easy to handle. The baseline value X is defined as the peak area obtained when 0.010 mg of the external standard is measured under the conditions specified in Table 1 below. Furthermore, in Table 1, the "sample measurement quantity" is the measurement value obtained after preparing the solution, adding it dropwise to the sample cup, and then air-drying it. Therefore, the measurement sample quantity is set to 0.10 mg as a solid.

[Table 1] py-GC/MS test conditions pyrolysis device Frontier Labs manufactures the Multishot Pyrolyzer EGA/PY-3030D. Pyrolysis unit heating conditions 500℃ GC device Agilent Technologies manufactures the 7890A. Use tubing DB-1 (30 m×0.25 mmΦ, film thickness 0.25 μm) Column temperature mode After holding at 40°C for 5 minutes, the temperature is increased to 320°C at a rate of 20°C/min and held at 320°C for 11 minutes. gas flow rate 1 ml/min Sample injection port temperature 320℃ Flow split ratio 1/50 Sample quantification 0.10 mg MS Packaging JEOL RESONANCE manufactures JMS-Q1500GC Interface temperature 320℃ Ionization EI 70 eV Scanning range m/z 10～800 Ion source temperature 240℃

[Homogeneous Polymerization Method] The hydrogenated block copolymer (A) of this embodiment is produced by homogeneous polymerization based on the calculation of the random parameter g in <condition (3)>. In the production of the hydrogenated block copolymer (A) using homogeneous polymerization, it is preferable to use the ReactIR 45P in Situ FTIR spectrophotometer (hereinafter referred to as ReactIR) manufactured by Mettler Toledo. By using the ReactIR, the concentrations of vinyl aromatic compounds and conjugated diene compounds in the polymerization reaction can be quantified in real time. Therefore, the feed rate of vinyl aromatic compounds and conjugated diene compounds can be controlled based on the quantitative results, so as to produce a more uniform random copolymer.

As an example of the manufacturing method of the hydrogenated block copolymer (A) of this embodiment, there is a method in which the reactivity ratio of the vinyl aromatic compound to the conjugated diene compound within a certain time period is immediately determined by measuring ReactIR, and the feed rate of the vinyl aromatic compound and the conjugated diene compound as polymer monomers is immediately controlled in such a way as to achieve the desired reactivity ratio. Based on the specified feed rates S0 of the vinyl aromatic compound and B0 of the conyoderm compound at time t0 to t1, and the changes ΔS and ΔB of the vinyl aromatic compound and conyoderm compound in the reaction system at the specified time t0 to t1, the reactivity ratio (S0 + ΔS)/(B0 + ΔB) of the vinyl aromatic compound and conyoderm compound is calculated in real time. The feed rates of the vinyl aromatic compound and conyoderm compound are then immediately controlled to achieve the desired reactivity ratio. For example, if the reactivity ratio (S0 + ΔS)/(B0 + ΔB) is higher than the desired reactivity ratio, the feed rate of the conyoderm compound can be increased or decreased.

Typically, in the copolymerization of vinyl aromatic compounds and conydate compounds, when polymerizing uniformly at the desired reactivity ratio, the feed rate ratio of the vinyl aromatic compound to the conydate compound must be the same as the desired reactivity ratio at the start of feeding, and the feeding of both the vinyl aromatic compound and the conydate compound must be stopped simultaneously at the end of copolymerization. For example, in the copolymerization of styrene and butadiene, butadiene typically reacts faster than styrene. Therefore, initially, the reactivity ratio (S0 + ΔS)/(B0 + ΔB) tends to be lower than the target value, and gradually approaches the target reactivity ratio. Conversely, immediately after feeding is stopped, the reactivity ratio (S0 + ΔS)/(B0 + ΔB) tends to be higher than the target value. By using ReactIR as described above, the reactivity ratio (S0 + ΔS)/(B0 + ΔB) can be measured in real time, and the feed rate ratio of styrene to butadiene can be controlled in a way that achieves the target reactivity ratio. In this way, the reactivity ratio (S0 + ΔS)/(B0 + ΔB) at the beginning and end of the feed can be controlled as the target reactivity ratio.

Below, three specific hydrogenated block copolymers (a)-I to (a)-III were obtained, and their peak intensities P were determined using a pyrolysis gas chromatography-mass spectrometry (py-GC/MS) analyzer. Furthermore, based on the first-order approximation formula between the content RS (mass %) of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) relative to the total content of the hydrogenated block copolymers ((a)-I to (a)-III) and the peak intensities P, the coefficient k in the above (Equation I) was calculated to be k = 0.05563. The values used to determine k are shown in Table 2 below.

<Hydrogenated Block Copolymer (A)-I> Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirrer and jacket. First, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of styrene was added. Next, 0.053 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 50 parts by mass of butadiene and 30 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR is used to measure the concentrations of butadiene and styrene in the reaction system in real time, and the feed rate is adjusted appropriately to achieve a 1:1 (mass part conversion) polymerization rate for each. Then, methanol is added to stop the polymerization reaction. Regarding the block copolymer obtained by the above method, the styrene content is 50% by mass, and the content of vinyl aromatic monomers in the (b) hydrogenated copolymer blocks relative to the overall hydrogenated block copolymer (a) is 30% by mass. Furthermore, for every 100 parts by mass of the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared in the above manner (based on Ti) is added, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain 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 butadiene (50 parts by mass) and styrene (30 parts by mass) of the above-mentioned hydrogenated block copolymer (A)-I were changed to 40 parts by mass of butadiene and 40 parts by mass of styrene, and polymerization and hydrogenation reactions were carried out to obtain hydrogenated block copolymer (A)-II. In the block copolymer before the hydrogenation reaction, the styrene content was 60% by mass, and the content of vinyl aromatic monomer units RS in the hydrogenated copolymer block (b) of the whole hydrogenated block copolymer (A) was 40% by mass, and the hydrogenation rate of hydrogenated block copolymer (A)-II was 98 moles.

<Hydrogenated Block Copolymer (A)-III> The 50 parts by mass of butadiene and 30 parts by mass of styrene in the above-mentioned hydrogenated block copolymer (A)-I were changed to 30 parts by mass of butadiene and 50 parts by mass of styrene, and a polymerization reaction and a 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% by mass, and the content of vinyl aromatic monomer units RS in the hydrogenated copolymer block (b) of the whole hydrogenated block copolymer (A) was 50% by mass, and the hydrogenation rate of hydrogenated block copolymer (A)-III was 98 moles.

[Table 2] (A)-I (A)-II (A)-III The content of vinyl aromatic monomer units (RS, by mass %) in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer (A). 30 40 50 Crest Intensity P 0.167 0.223 0.278

(Structure of hydrogenated block copolymer (A)) The structure of the hydrogenated block copolymer (A) of this embodiment can be exemplified by having 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) with a vinyl aromatic monomer unit as the main component, b represents a hydrogenated copolymer block (b) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and c represents a hydrogenated polymer block (c) with a conjugated diene monomer unit as the main component. n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X represents the residue of the coupling agent or the residue of the multifunctional initiator.

(Other examples of the structure of hydrogenated block copolymer (A)) The hydrogenated block copolymer (A) of this embodiment can also be a modified block copolymer bonded with atomic groups having specified functional groups. The type of modification, functional groups, etc., can be appropriately set according to the structure of the resin used in the preparation of the composition using the hydrogenated block copolymer (A) of this embodiment. Furthermore, when the hydrogenated block copolymer (A) is set as a modified block copolymer, it can also be a secondary modified block copolymer. In this specification, "secondary modification" is a designation based on the characteristics imparted by the manufacturing method. The initial step of bonding functional groups to the polymer is called primary modification, and the step of reacting other compounds with its functional groups is called secondary modification. For example, a typical manufacturing method involves polymerizing in solution and then reacting other compounds (e.g., maleic acid) with a modifier (e.g., amine) and the polymerization terminus in an extruder to produce a primary modified product, thereby producing a secondary modified product.

[Method for manufacturing hydrogenated block copolymer (A)] The block copolymer (A) of this embodiment, in its pre-hydrogenation state, can be obtained, for example, by using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent to enable the vinyl aromatic compound and the conjugated diene compound to undergo anionic polymerization.

(Chemical solvents) 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) There is no particular limitation on the type of polymerization initiator. Examples include aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds that are known to have anionic polymerization activity for vinyl aromatic compounds and conjugated dienes. As organic alkali metal compounds, aliphatic and aromatic hydrocarbon lithium compounds with 1 to 20 carbon atoms are preferred, but they are not limited to the above. Compounds containing one lithium atom in one molecule, dilithium compounds, trilithium compounds, and tetralithium compounds containing multiple lithium atoms in one molecule can also be used. Specifically, examples include: the reaction products of n-propyl lithium, n-butyl lithium, dibutyl lithium, tributyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, the reaction products of diisopropylbenzene and dibutyl lithium, and the reaction products of divinylbenzene and dibutyl lithium with a small amount of 1,3-butadiene. Furthermore, organoalkali metal compounds disclosed in U.S. Patent No. 5,708,092, British Patent No. 2,241,239, and U.S. Patent No. 5,527,753 can also be used.

(Modifier) When using an organoalkali metal compound as a polymerization initiator to copolymerize a vinyl aromatic compound with a conjugated diene compound, a prescribed modifier is used to adjust the content of vinyl bonds (1,2- or 3,4- bonds) generated by the conjugated diene compound incorporated into the polymer, or the random copolymerization of the vinyl aromatic monomers and the conjugated diene monomers. Examples of such modifiers include, but are not limited to, tertiary amine compounds, ether compounds, and metal alkoxide compounds. A modifier may be used alone or in combination of two or more.

As tertiary amine compounds, examples include compounds represented by the general formula R1R2R3N (where R1, R2, and R3 represent hydrocarbons with 1 to 20 carbon atoms or hydrocarbons having tertiary amine groups), but are not limited to these. 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, trimethylaminoethylpiperidine, N,N,N',N'',N''-pentamethylethylenediamine, N,N'-dioctyl-p-phenylenediamine, etc.

As ether compounds, examples include, for example, isolinear ether compounds and cyclic ether compounds, but are not limited to the above. Examples of linear ether compounds include, for example, dialkyl ethers of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and dialkyl ethers of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether, but are not limited to the above. Examples of cyclic ether compounds include, for example, tetrahydrofuran, dialkylene, 2,5-dimethyloxacyclopentane, 2,2,5,5-tetramethyloxacyclopentane, 2,2-bis(2-tetrahydrofuranyl)propane, and alkyl ethers of furanol, but are not limited to the above.

Examples of metal alkoxides include sodium tripentoxide, sodium tributoxide, potassium tripentoxide, potassium tributoxide, etc., but are not limited to these.

(Polymerization Method) The method for polymerizing vinyl aromatic compounds and conjugated diene compounds using an organoalkali metal compound as a polymerization initiator can employ previously known methods. For example, it can be batch polymerization, continuous polymerization, or any combination thereof, but is not limited to the above. Batch polymerization is particularly suitable for obtaining copolymers with excellent heat resistance. The polymerization temperature is preferably 0°C to 180°C, more preferably 30°C to 150°C. The polymerization time varies depending on the conditions, typically within 48 hours, preferably 0.1 to 10 hours. Furthermore, the atmosphere for the polymerization system is preferably an inert gas atmosphere such as nitrogen. The polymerization pressure is not particularly limited, as long as it is set within the above temperature range to maintain the monomer and solvent in a liquid phase. Furthermore, it is preferable to take extra care to avoid the introduction of impurities into the polymerization system that could inert the catalyst and active polymers, such as water, oxygen, and carbon dioxide.

Alternatively, at the end of the above polymerization step, a necessary amount of a coupling agent with two or more functions can be added to carry out the coupling reaction. Known coupling agents can be used as difunctional coupling agents, and there are no particular limitations. Examples include: alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. Furthermore, as a multifunctional coupling agent with three or more functions, previously known agents can be used without particular limitation. Examples include: polyols with three or more ternary components, epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, and other polyepoxides; halogenated silicon compounds represented by the general formula _{R4 - nSiXn} (where R represents an alkyl group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), such as methyl silicon trichloride, tert-butyl silicon trichloride, silicon tetrachloride, and their bromides; and compounds with the general formula _{R4 -} nSnXn _. (Here, R represents an hydrocarbon with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer from 3 to 4.) The halogenated tin compounds represented are, for example, polyvalent halogen compounds such as methyl tin trichloride, tributyl tin trichloride, and tin tetrachloride. Alternatively, dimethyl carbonate or diethyl carbonate may also be used.

(Modification Step) As described above, the hydrogenated block copolymer (A) of this embodiment can be a modified block copolymer bonded with functional groups. The bonding of functional groups is preferably a step prior to the hydrogenation step described below. As for the aforementioned "functional group", examples include groups containing at least one functional group selected from hydroxyl, carboxyl, carbonyl, thiocarbonyl, acetyl halide, acid anhydride, carboxylic acid, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylic acid ester, acetamino, sulfonic acid, sulfonate, phosphate, phosphate ester, amino, imine, nitrile, pyridinyl, quinolinyl, epoxy, thioepoxy, thio, isocyanate, isothiocyanate, halogenated silica, silanol, alkoxysilyl, halogenated tin, borate, boron-containing group, borate salt, alkoxytin, phenyltin, etc., but are not limited to the above. Preferably, the atomic group has at least one functional group selected from hydroxyl, epoxy, amino, silanol, alkoxysilyl. The aforementioned "atomic group with functional group" can be bonded using a modifier. Examples of modifiers include tetraglycidyl-m-phenylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidyloxyethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyldimethylphenoxysilane, bis(γ-glycidyloxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidineone, 1,3-diethyl-2-imidazolidineone, N,N'-dimethylpropylurea, N-methylpyrrolidone, etc., but are not limited to the above.

Modified block copolymers are not particularly limited and can be obtained, for example, by anionic living polymerization using a polymerization initiator with functional groups or an unsaturated monomer with functional groups, or by forming functional groups at the active end, or by subjecting a modifier containing functional groups to an addition reaction. Alternatively, they can be obtained by reacting an organolithium compound or other organolithium metal compound with the block copolymer (metallization reaction), or by subjecting a modifier with functional groups to an addition reaction with a block polymer containing an organolithium metal. In the latter case, modified hydrogenated block copolymers can also be produced by performing a metallization reaction after obtaining the hydrogenated block copolymer, followed by a reaction of the modifier. The preferred temperature for the modification reaction is 0–150°C, more preferably 20–120°C. The reaction time varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1–10 hours. Depending on the type of modifier used, sometimes during the reaction stage, amine groups may also be converted into organometallic salts. In such cases, these groups can be converted back to amine groups by treatment with compounds containing active hydrogen, such as water or alcohol. Furthermore, in this type of modified block copolymer, a portion of unmodified block copolymer may also be mixed in.

Furthermore, the aforementioned modified block copolymer can also be a secondary modified block copolymer. A secondary modified block copolymer can be obtained by reacting a secondary modifier that is reactive with the functional groups of the modified block copolymer and the modified block copolymer. Examples of secondary modifiers include those having functional groups selected from carboxyl, anhydride, isocyanate, epoxy, silanol, and alkoxysilyl groups, but are not limited to these. Preferably, it has at least two functional groups selected from these functional groups. In the case where the functional group is an anhydride group, it may also have one anhydride group.

As described above, when reacting the secondary modifier with the modified block copolymer, the amount of secondary modifier used is preferably 0.3 to 10 mol, more preferably 0.4 to 5 mol, and even more preferably 0.5 to 4 mol, relative to one equivalent of the functional groups bonded to the modified block copolymer. The method for reacting the modified block copolymer with the secondary modifier can be any known method and is not particularly limited. Examples include the melt-mixing method described below, or methods of dissolving or dispersing the components in a solvent and then reacting them. Furthermore, such secondary modification is preferably performed after the hydrogenation step.

As secondary modifiers, examples include: maleic anhydride, pyromellitic dianhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride, toluene diisocyanate, tetraglycidyl-1,3-diaminomethylcyclohexane, bis-(3-triethoxysilylpropyl)-tetrasulfide, etc., but are not limited to the above.

Furthermore, the hydrogenated block copolymer (A) of this embodiment may be a modified block copolymer obtained by grafting modification with α,β-unsaturated carboxylic acids or their derivatives, such as their anhydrides, esters, amides, and amides. Examples of α,β-unsaturated carboxylic acids or their derivatives include, for example, maleic anhydride, maleic anhydride amide, acrylic acid or its esters, methacrylic acid or its esters, intra-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydrides, but it is not limited to the above. The amount of α,β-unsaturated carboxylic acids or their derivatives added relative to 100 parts by weight of the hydrogenated block copolymer (A) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. The reaction temperature for graft modification is preferably 100–300°C, and more preferably 120–280°C. There are no particular limitations on the method of graft modification; for example, the method described in Japanese Patent Application Publication No. 62-79211 may be used.

(Hydrogenation reaction steps) The hydrogenated block copolymer (A) of this embodiment can be obtained by the following method: using a specified hydrogenation catalyst, the non-hydrogenated unmodified or modified block copolymer as described above is fed into a hydrogenation reaction. There are no particular limitations on what constitutes a hydrogenation catalyst. For example, known catalysts include (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 in which transition metal salts such as organic acids and salts of Ni, Co, Fe, and Cr or acetone salts and reducing agents such as organoaluminum are used; and (3) so-called homogeneous hydrogenation catalysts in which organometallic compounds such as Ti, Ru, Rh, and Zr are used. Furthermore, as a hydrogenation catalyst, for example, the hydrogenation catalysts described in Japanese Patent Publication Nos. 42-8704, 43-6636, 63-4841, 1-37970, 1-53851, and 2-9041 may be used, but are not limited to the above. Suitable hydrogenation catalysts include, for example, titanium diacene compounds, reducing organometallic compounds, or mixtures thereof. As a titanium diacene compound, for example, the compound described in Japanese Patent Application Publication No. 8-109219 may be used, but is not limited to the above. Specifically, examples include compounds such as dicyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride, which have at least one ligand with a (substituted) cyclopentadienyl, indyl, or fumonisinyl skeleton. Reducing organometallic compounds include, but are not limited to, organolithic compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, or organozinc compounds.

The hydrogenation reaction is described below. The reaction temperature is preferably in the range of 0–200°C, more preferably in the range of 30–150°C. The pressure of the hydrogen used in the hydrogenation reaction is preferably 0.1–15 MPa, more preferably 0.2–10 MPa, and further preferably 0.3–5 MPa. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction can be a batch process, a continuous process, or any combination thereof. Preferably, catalyst residues are removed from the solution of the hydrogenated block copolymer obtained after the hydrogenation reaction, and the hydrogenated block copolymer is separated from the solution, as needed. Examples of separation methods include: adding polar solvents such as acetone or alcohol, which are unsuitable solvents for hydrogenated modified copolymers, to the hydrogenated reaction solution to precipitate and recover the polymer; adding the reaction solution to hot water under stirring to remove and recover the solvent by steam stripping; and directly heating the polymer solution to remove the solvent by distillation, etc., but are not limited to the above.

Furthermore, various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, amine stabilizers, and other stabilizers can also be added to the hydrogenated block copolymer (A) of this embodiment.

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

(B) Olefin Resins) The following describes olefin resin (B) constituting the hydrogenated block copolymer composition of this embodiment. Examples of olefin resin (B) include 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, but it is not limited to these. Examples of olefin resin (B) include random copolymers or block copolymers containing combinations of olefins selected from ethylene, propylene, butene, pentene, hexene, and octene. 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 other ethylene and/or propylene-α-olefin copolymers. Furthermore, copolymers with ethylene and/or propylene also include copolymers with other unsaturated monomers. Examples of copolymers of the above with other unsaturated monomers include: 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, and alkyl maleic anhydride; copolymers of ethylene and/or propylene with vinyl acetate and other vinyl esters; and further copolymers of ethylene and/or propylene with non-conjugated dienes such as dicyclopentadiene, 4-ethylidene-2-norphene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene, but not limited to the above. From the viewpoint of economic efficiency, or to improve the compatibility of the hydrogenated block copolymer composition of the present embodiment and obtain higher transparency, the (ethylene) hydrocarbon resin preferably contains at least one polypropylene resin.

Furthermore, olefinic resin (B) can also be modified using specified functional groups. There are no particular limitations on the functional groups; examples include epoxy groups, carboxyl groups, anhydride groups, and hydroxyl groups. There are also no particular limitations on the functional group-containing compounds or modifiers used to modify olefinic resin (B); examples include 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, leuconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, and itaconic anhydride. Apart from this, there are no particular limitations; examples include ionic polymers and chlorinated polyolefins.

From the viewpoint of economic efficiency, or to improve the compatibility of the hydrogenated block copolymer composition of this embodiment and obtain higher transparency, the olefinic resin (B) is preferably a polypropylene homopolymer, a random or block copolymer of ethylene and propylene, or other polypropylene-based resins. In particular, from the viewpoint of transparency and flexibility, a random copolymer of ethylene and propylene is more preferred. The olefinic resin (B) may contain only one type of material or may contain two or more types.

The hydrogenated block copolymer composition of this embodiment contains a hydrogenated block copolymer (A) and at least one olefinic resin (B). The content of 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 even more preferably 5% by mass or more and 40% by mass or less. If the content of hydrogenated block copolymer (A) is 1% by mass or more, the wear resistance of the hydrogenated block copolymer composition tends to increase, and the hardness tends to decrease. On the other hand, if the content of hydrogenated block copolymer (A) is 50% by mass or less, the oil resistance of the hydrogenated block copolymer composition of this embodiment tends to increase. Furthermore, from the viewpoint of the mechanical strength of the hydrogenated block copolymer composition of this embodiment, the content of olefinic resin (ethyl) is 5% by mass or more, and from the viewpoint of the low-temperature characteristics of the hydrogenated block copolymer composition, it is 90% by mass or less. Preferably, it is 7% by mass or more and 85% by mass or less, and more preferably, it is 10% by mass or more and 80% by mass or less.

In addition to the hydrogenated block copolymer (A) and polyolefin resin (B) of this embodiment, the hydrogenated block copolymer composition also contains at least 1% to 50% by mass of at least one thermoplastic resin (C) and at least 5% to 90% by mass of at least one softener (D). Modifiers, additives, etc., may also be formulated.

The aforementioned softener (D) softens the hydrogenated block copolymer composition of this embodiment and imparts fluidity (processability). As a softener, for example, mineral oil or liquid or low molecular weight synthetic softeners can be used, but are not limited to the above; particularly suitable are naphthenic and/or paraffinic processing oils or extender oils. Mineral oil-based softeners are mixtures of aromatic rings, cycloalkane rings, and paraffin chains. Those with paraffin chains comprising more than 50% of the total carbon are called paraffinic; those with cycloalkane rings comprising 30-45% of the total carbon are called cycloalkane; and those with aromatic carbons exceeding 30% are called aromatic. As a synthetic softener, for example, polybutene, low molecular weight polybutadiene, liquid paraffin, etc., can be used, but mineral oil-based softeners are preferred. When high heat resistance and mechanical properties are required for the hydrogenated block copolymer composition of this embodiment, the applied mineral oil-based softener preferably has a kinematic viscosity of 60 cst or higher at 40°C, more preferably 120 cst or higher. One type of softener may be used alone, or two or more may be used in combination.

The aforementioned modifier is intended to improve the surface damage resistance of the hydrogenated block copolymer composition of this embodiment, or to improve adhesion. As a modifier, for example, organopolysiloxanes can be used, but are not limited to the above. It exerts a surface modification effect on the hydrogenated block copolymer composition and functions as an abrasion resistance improving agent. The form of the modifier can be any of low-viscosity liquid to high-viscosity liquid, or solid. From the viewpoint of ensuring good dispersibility in the hydrogenated block copolymer composition of this embodiment, a liquid, i.e., silicone oil, is suitable. Regarding the kinematic viscosity of the modifier, from the viewpoint of suppressing the seepage of the polysiloxane itself, it is preferably 90 cst or higher, and more preferably 1000 cst or higher. Examples of polysiloxanes include, for example, general-purpose silicone oils such as dimethyl polysiloxane and methylphenyl polysiloxane; or various modified silicone oils such as alkyl-modified, polyether-modified, fluorinated, alcohol-modified, amino-modified, and epoxy-modified, but not limited to these. Dimethyl polysiloxane is suitable for its superior effect as a wear resistance improving agent, but there are no particular limitations. One of these modifiers may be used alone, or two or more may be used in combination.

As an additive, there are no particular restrictions as long as it is commonly used in the formulation of fillers, lubricants, release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents, colorants, or thermoplastic resins or rubber-like polymers. Examples of fillers include, for instance, inorganic fillers such as silica, talc, mica, calcium silicate, magnesium aluminum carbonate, 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 are not limited to these. Examples of lubricants include stearic acid, benzyl acid, zinc stearate, calcium stearate, magnesium stearate, and ethyl bis-stearamide, but are not limited to these. Examples of plasticizers include organopolysiloxanes and mineral oils, but are not limited to these. Examples of antioxidants include hindered phenolic antioxidants, but are not limited to these. Examples of heat stabilizers include phosphorus-based, sulfur-based, and amine-based heat stabilizers, but are not limited to these. Examples of light stabilizers include hindered amine-based light stabilizers, but are not limited to these. As ultraviolet absorbers, examples include benzotriazole ultraviolet absorbers, but are not limited to the above. As reinforcing agents, examples include organic fibers, glass fibers, carbon fibers, and metal fibers, but are not limited to the above. As coloring agents, examples include titanium oxide, iron oxide, and carbon black, but are not limited to the above. In addition, examples can be found in "Rubber and Plastic Compounds" (published by Rubber Digest Co., Ltd.).

(C) Thermoplastic Resins Examples of the above-mentioned thermoplastic resins (C) include: block copolymers of conjugated diene compounds and vinyl aromatic compounds and their hydrogenates (but different from the hydrogenated block copolymers (A) of the present embodiment); polymers of the above-mentioned vinyl aromatic compounds; copolymers of the above-mentioned vinyl aromatic compounds with other vinyl monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and methyl acrylate, methacrylate and methyl methacrylate, acrylonitrile, methacrylonitrile, etc.; rubber-modified styrene resins (HIPS); acrylonitrile-butadiene-styrene copolymers (ABS); methacrylate-butadiene-styrene copolymers (MBS), etc., but are not limited to the above.

Furthermore, examples of the above-mentioned (C) thermoplastic resins 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 their hydrolysates; polyethylene-based resins such as ethylene-acrylate ionic polymers 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-based resins such as chlorinated polypropylene; cyclic olefin resins such as ethylene-norphene resins; polybutene-based resins; polyvinyl chloride-based resins; polyvinyl acetate-based resins and their hydrolysates, but are not limited to the above.

Furthermore, examples of (c) thermoplastic resins include: 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 with 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'-dioxanone... Polycarbonate polymers such as diphenyl-2,2'-propane carbonate; thermoplastic polyurethanes such as polyether ether or polyallyl ether; polyoxymethylene resins; polyphenylene ether resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide and poly4,4'-diphenylene sulfide; polyaryl ester resins; polyetherketone polymers or copolymers; polyketide resins; fluorinated resins; polyoxybenzoyl polymers; polyimide resins; 1,2-polybutadiene, trans-polybutadiene and other polybutadiene resins, etc., but not limited to the above.

Among the aforementioned thermoplastic resins (propylene), styrene-based resins such as polystyrene and rubber-modified styrene resins are particularly preferred; polyethylene; polyethylene-based 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-based resins such as propylene-ethylene copolymers; polyamide resins; polyester resins; and polycarbonate resins. The number average molecular weight of these thermoplastic resins (propylene) is typically 1000 or more, preferably 50 million to 5 million, and more preferably 10,000 to 1 million.

In the hydrogenated block copolymer composition of this embodiment, from the viewpoint of mechanical strength, the content of thermoplastic resin (propylene) is set to 1% by mass or more, and from the viewpoint of oil resistance, it is set to 50% by mass or less. Preferably, it is 3% by mass or more and 47% by mass or less, more preferably 5% by mass or more and 45% by mass or less. Furthermore, when the total amount of the above-mentioned components (a) and (c) is set to 100 parts by mass, the content of component (c) is preferably 2 to 150 parts by mass, more preferably 2 to 140 parts by mass, and even more preferably 2 to 130 parts by mass.

(D) Softener) Next, the softener (D) constituting the hydrogenated block copolymer composition of this embodiment will be explained. The softener (D) is preferably a rubber softener that softens the hydrogenated block copolymer composition and imparts processability. Examples of softeners (D) include, for example, mineral oils, or liquid or low molecular weight synthetic softeners, but are not limited to the above. Preferably, it is a naphthenic and/or paraffinic processing oil or a bulking oil. Mineral oil-based softeners are mixtures of aromatic rings, cycloalkane rings, and paraffin chains. Those with paraffin chains comprising more than 50% of the total carbon are called paraffin-based softeners, those with cycloalkane rings comprising 30-45% of the total carbon are called cycloalkane-based softeners, and those with aromatic carbons comprising more than 30% are called aromatic-based softeners. Synthetic softeners can be used in the hydrogenated block copolymer compositions of this embodiment without particular limitation; for example, polybutene, low molecular weight polybutadiene, and liquid paraffin can be used. Preferably, the aforementioned mineral oil-based softener for rubber is preferred.

In the hydrogenated block copolymer composition of this embodiment, from the viewpoint of surface feel, the content of softener (D) is set to 5% by mass or more, and from the viewpoint of inhibiting exudation, it is set to 90% by mass or less. Preferably, it is 7% by mass or more and 85% by mass or less, more preferably 10% by mass or more and 80% by mass or less. Furthermore, 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 even more preferably 2 to 100 parts by mass. If the content of softener (D) is below the above-mentioned upper limit, exudation can be inhibited, and the surface feel becomes good.

In the hydrogenated block copolymer composition of this embodiment, in addition to the above-mentioned components (A), (B), (C), and (D), additives may be added as needed. There are no particular restrictions on the type of additives, as long as they are commonly used in the formulation of thermoplastic resins or rubber-like polymers.

The hydrogenated block copolymer composition of this embodiment can be manufactured by previously known methods. Methods for manufacturing the hydrogenated block copolymer composition of this embodiment include, for example, using a Bainbury mixer, single-screw extruder, twin-screw extruder, biaxial kneader, multi-screw extruder, etc., to melt-mix the components (the aforementioned hydrogenated block copolymer (A), polyolefin resin (B), thermoplastic resin (C), softener (D), and other additives); or methods for removing the solvent by heating after dissolving or dispersing the components, etc., but are not limited to the above. From the viewpoint of productivity and excellent mixing properties, melt mixing using an extruder is particularly suitable. Regarding the shape of the hydrogenated block copolymer composition, it can be any shape, such as granules, flakes, ropes, small pieces, etc., but is not limited to the above. Also, it can be directly made into molded products after melt mixing.

(Reinforcing filler and reinforcing filler formulation) A reinforcing filler formulation can be prepared by incorporating at least one reinforcing filler selected from silica-based inorganic fillers, metal oxides, metal hydroxides, metal carbonates and carbon black (hereinafter sometimes referred to as component (C)) into the hydrogenated block copolymer or the above-mentioned hydrogenated block copolymer composition (hereinafter sometimes referred to as component (A)). Relative to 100 parts by weight of the hydrogenated block copolymer or the above-mentioned hydrogenated block copolymer composition (component (A)) of this embodiment, the content of component (C) in the reinforcing filler formulation is preferably 0.5 to 100 parts by weight, more preferably 5 to 100 parts by weight, and even more preferably 20 to 80 parts by weight. When preparing the reinforcing filler formulation using the hydrogenated block copolymer of this embodiment or the hydrogenated block copolymer composition (component (A)), it is preferable to include 0 to 500 parts by weight, more preferably 5 to 300 parts by weight, and even more preferably 10 to 200 parts by weight of a thermoplastic resin and/or rubber polymer (hereinafter sometimes referred to as component (B)) that is different from the hydrogenated block copolymer of this embodiment, the olefinic resin (B), and the thermoplastic resin (C) of the above embodiment.

(Different from components (B) and (C) thermoplastic resins and/or rubber polymers) Examples of the aforementioned thermoplastic resins and/or rubber polymers (component (B)) include: block copolymers of conjugated diene monomers and vinyl aromatic monomers with a vinyl aromatic monomer content exceeding 60% by mass, and their hydroxides (but different from the hydrogenated block copolymers of embodiment (A)); polymers of the aforementioned vinyl aromatic compounds; copolymers of the aforementioned vinyl aromatic compounds with other vinyl compounds (e.g., ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylates such as acrylic acid and methyl acrylate, methacrylates such as methacrylic acid and methyl methacrylate, acrylonitrile, methacrylonitrile, etc.). Polyesters; rubber-modified styrene resins (HIPS); acrylonitrile-butadiene-styrene copolymers (ABS); methacrylate-butadiene-styrene copolymers (MBS); polyethylene; ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers and their hydrolysates, etc., containing ethylene and other copolymerizable monomers with an ethylene content of 50% by mass or more; polyethylene-based resins such as ethylene-acrylate ionic polymers or chlorinated polyethylene; polypropylene; polypropylene-based resins such as propylene-ethylene copolymers, propylene-ethyl acrylate copolymers, or chlorinated polypropylene. Cyclic olefin resins such as ethylene-norphene resins, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins and their hydrolysates, etc., containing propylene and other copolymerizable monomers with a propylene content of 50% by mass 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 content of acrylonitrile monomers of 50% by mass or more, i.e., acrylonitrile resins; nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6, nylon-12 copolymers, etc. Acrylamide resins; polyester resins; thermoplastic polyurethane resins; polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polyurethanes such as polyether sulfide or polyallyl sulfide; 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'-diphenylene sulfide; polyaryl ester resins; polyetherketone polymers or copolymers; polyketide resins; fluorinated resins; polyoxybenzoyl polymers; polyimide resins; polybutadiene resins such as 1,2-polybutadiene and trans-polybutadiene, etc., but not limited to the above. These components (B) may also be groups containing polar groups such as hydroxyl, epoxy, amino, carboxylic acid, and anhydride groups.

The silica-based inorganic filler that can be used as the reinforcing filler (component (C)) is a solid particle with _SiO2 as the main component of the structural unit. Examples include silica, clay, talc, kaolin, mica, wollastonite, montmorillonite, zeolite, glass fiber, and other inorganic fibrous materials, but it is not limited to these. Furthermore, silica-based inorganic fillers that have been hydrophobized on their surface, or mixtures of silica-based inorganic fillers and inorganic fillers other than silica-based fillers, can also be used. Silica and glass fiber are preferred as silica-based inorganic fillers. As for silica, it can be known as dry-process white carbon, wet-process white carbon, synthetic silicate-based white carbon, colloidal silica, etc. The silica-based inorganic filler preferably has an average particle size of 0.01–150 μm. When the silica-based inorganic filler is dispersed in a reinforcing filler formulation, to fully exert its additive effect, the average dispersed particle size is preferably 0.05–1 μm, more preferably 0.05–0.5 μm.

The metal oxide that can be used as the reinforcing filler (component (C)) is a solid particle with the chemical formula MxOy (where M is a metal atom, and x and y are integers from 1 to 6) as the main component of the structural unit. Examples include aluminum oxide, titanium oxide, magnesium oxide, and zinc oxide. Furthermore, a mixture of metal oxide and inorganic fillers other than metal oxides can also be used as a reinforcing filler. Examples of metallic 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, tin oxide hydrate, borax, and other hydrated inorganic metal compounds, but are not limited to the above. Magnesium hydroxide and aluminum hydroxide are particularly preferred. Examples of metallic carbonates used as reinforcing fillers include calcium carbonate and magnesium carbonate, but are not limited to the above. Furthermore, as a reinforcing filler, 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. Carbon black with 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 can be used.

In the reinforcing filler formulation of the hydrogenated block copolymer (A) or hydrogenated block copolymer composition (component (A)) using the present embodiment, a silane coupling agent (hereinafter sometimes referred to as component (D)) may also be formulated. The silane coupling agent (D) is a compound having a group that is affinity or binding to one or both of the hydrogenated block copolymer (A) and the reinforcing filler (C) to make the interaction between the hydrogenated block copolymer (A) of the present embodiment and the reinforcing filler (C) tighter. Preferred silane coupling agents (D) include, for example, those with polysulfide bonds formed by linking two or more syl groups and/or sulfur groups with silanol or alkoxysilane groups, but are not limited to the above. Specifically, examples include: bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide, 3-sylpropyl-trimethoxysilane, 3-triethoxysilylpropyl-N,N-dimethylthioaminomethyltetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, etc. From the perspective of achieving the desired effect, the amount of silane coupling agent (D) relative to the reinforcing filler formulation 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.

The hydrogenated block copolymer (A) of this embodiment, or the reinforcing filler formulation of the above-mentioned hydrogenated block copolymer composition and reinforcing filler, can be vulcanized using a vulcanizing agent, i.e., crosslinked to form a vulcanized composition. Examples of vulcanizing agents include: free radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, and sulfur compounds (sulfur monochloride, sulfur dichloride, disulfide compounds, high-molecular-weight polysulfide compounds, etc.). The amount of vulcanizing agent used is typically 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the hydrogenated block copolymer (A) or the above-mentioned hydrogenated block copolymer composition. As an organic peroxide (hereinafter sometimes referred to as component (E)) used as a sulfiding agent, from the viewpoint of odor or coking stability (the characteristic that it does not crosslink under mixed conditions, but crosslinks rapidly under crosslinking reaction conditions), for example, 2,5-dimethyl-2,5-di-(tert-butylperoxide)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxide)hexyn-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 ester, and ditert-butylperoxide are preferred, but not limited to the above. In addition to the above, other alternatives may include dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxide, tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauryl peroxide, and tert-butylisopropylphenyl peroxide.

Furthermore, during vulcanization, as vulcanization accelerators (hereinafter sometimes referred to as component (F)), sulfinamide, guanidine, thiuram, aldehyde-amine, aldehyde-amine, thiazole, thiourea, and dithiocarbamate compounds may be used in appropriate amounts as needed. Also, as vulcanization aids, zinc oxide and stearic acid may be used in appropriate amounts as needed. Furthermore, when using organic peroxides as the aforementioned vulcanizing agent to crosslink reinforcing filler formulations, the following components may also be used in conjunction with the organic peroxides used as the aforementioned vulcanizing agent: p-quinone dioxime, p,p'-dibenzoquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trihydroxymethylpropane-N,N'-m-phenyldicis-butene diimidimide, and other peroxide crosslinking auxiliaries. Hereinafter, sometimes referred to as component (G); divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate and other multifunctional methacrylate monomers; vinyl butyrate, vinyl stearate and other multifunctional vinyl monomers (hereinafter, sometimes referred to as component (H)). This vulcanization accelerator (F), peroxidation crosslinking aid (G), and multifunctional vinyl monomer (H) are usually used at a ratio of 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the hydrogenated block copolymer (A) or the above-mentioned hydrogenated block copolymer composition (component (A)). As a method for curing reinforcing filler formulations using a vulcanizing agent, previously implemented methods can be applied, such as curing at a temperature of 120–200°C, preferably 140–180°C. The cured reinforcing filler formulation exhibits heat resistance, flexural strength, or oil resistance in the vulcanized state.

To improve the processability of the hydrogenated block copolymer (A) or the reinforcing filler formulation of the hydrogenated block copolymer composition using the present embodiment described above, a softener (hereinafter sometimes referred to as component (I)) may also be formulated. That is, in addition to the softener (D) constituting the hydrogenated block copolymer composition, a softener may be formulated in the required amount. Mineral oil, liquid, or low molecular weight synthetic softener are more suitable. Generally, naphthenic and/or paraffinic processing oils or extender oils used for softening, compatibilizing, and improving the processability of rubber are preferred. Mineral oil-based softeners are mixtures of aromatic rings, cycloalkane rings, and paraffin chains. Those with paraffin chains comprising more than 50% of the total carbon are called paraffin-based softeners, those with cycloalkane rings comprising 30-45% of the total carbon are called cycloalkane-based softeners, and those with aromatic carbons comprising more than 30% are called aromatic-based softeners. Synthetic softeners can be used in the above-mentioned reinforcing filler formulations, such as polybutene, low molecular weight polybutadiene, and liquid paraffin. However, the above-mentioned mineral oil-based softeners are preferred. The amount of softener (component (I)) in the reinforcing filler formulation is preferably 0 to 100 parts by weight relative to 100 parts by weight of the hydrogenated block copolymer (A) or the aforementioned hydrogenated block copolymer composition (component (A)), more preferably 1 to 90 parts by weight, and even more preferably 30 to 90 parts by weight. If the amount of softener exceeds 100 parts by weight, it is easy to seep out, which may cause stickiness on the surface of the composition.

The hydrogenated block copolymer (A) of this embodiment or the reinforcing filler formulation of the above-mentioned hydrogenated block copolymer composition can be suitably used as building materials, wire sheathing materials, or vibration damping materials. Furthermore, its sulfides, utilizing this characteristic, are suitable for tire applications or as materials for vibration-damping rubber, belts, industrial products, footwear, foams, etc.

(Crosslinked Compound) The hydrogenated block copolymer (A) of this embodiment or the above-mentioned hydrogenated block copolymer composition can be crosslinked in the presence of a vulcanizing agent to form a crosslinked compound, namely a crosslinked hydrogenated block copolymer or a crosslinked hydrogenated block copolymer composition. By crosslinking the hydrogenated block copolymer (A) of this embodiment or the above-mentioned hydrogenated block copolymer composition, heat resistance [high-temperature C-Set (compression set)] or flexural resistance can be improved. In the preparation of crosslinks containing the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition of the present embodiment and the reinforcing filler formulation thereof, especially in the case of the mixing ratio of the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)) and the thermoplastic resin and/or rubber polymer (component (B)) different from the above-mentioned olefinic resin (B) or the above-mentioned thermoplastic resin (C) by mass ratio of component (A) to component (B), it is preferably 10/90 to 100/0, more preferably 20/80 to 90/10, and even more preferably 30/70 to 80/20.

When crosslinking the hydrogenated block copolymer (A) or hydrogenated block copolymer composition of this embodiment, the crosslinking method is not particularly limited, but so-called "dynamic crosslinking" is preferred. Dynamic crosslinking is a method that simultaneously disperses and crosslinks various formulations by mixing them in a molten state at 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 carried out using a closed mixer such as a Bamboo mixer or a pressure kneader, or a single-shaft or bi-shaft extruder. The mixing temperature is typically 130–300°C, preferably 150–250°C, and the mixing time is typically 1–30 minutes. As a vulcanizing agent used in dynamic crosslinking, an organic peroxide or phenolic resin crosslinking agent can be appropriately used. The amount used is typically 0.01–15 parts by weight, preferably 0.04–10 parts by weight, relative to 100 parts by weight of the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)). As an organic peroxide used as a vulcanizing agent, component (E) can be used. When using an organic peroxide for crosslinking, component (F) can be used as a vulcanization accelerator. Alternatively, component (G): a peroxide crosslinking auxiliary agent, or component (H): a multifunctional vinyl monomer, can also be used concurrently. The amount of such vulcanization accelerators used is typically 0.01 to 20 parts by weight relative to 100 parts by weight of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)), preferably 0.1 to 15 parts by weight.

In the crosslinks of the hydrogenated block copolymers or combinations of hydrogenated block copolymers (component (A)) using this embodiment, additives such as softeners, heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, fillers, colorants, and lubricants may be formulated as needed, without impairing their purpose. As a softener formulated to control the hardness or flowability of the final product, the aforementioned rubber softener (I) may be used. The softener may be added during the mixing of the components, or it may be pre-included in the hydrogenated block copolymer (A) during its manufacture, thereby preparing oil-extended rubber. The amount of softener added during the preparation of the above-mentioned crosslinks is typically 0 to 200 parts by weight relative to 100 parts by weight of the hydrogenated block copolymer (A) or the hydrogenated block copolymer composition (component (A)), preferably 10 to 150 parts by weight, and even more preferably 20 to 100 parts by weight. Furthermore, as a filler, component (C) as a reinforcing filler can be used. The amount of filler added is typically 0 to 200 parts by weight relative to 100 parts by weight of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)), preferably 10 to 150 parts by weight, and even more preferably 20 to 100 parts by weight. The aforementioned crosslinks are preferably dynamically crosslinked with a gel content (excluding insoluble components such as inorganic fillers) preferably of 5-80% by mass, more preferably of 10-70% by mass, and even more preferably of 20-60% by mass. Regarding the gel content, 1 g of the crosslinks is refluxed for 10 hours using a Soxhlet extractor with boiling xylene. The residue is filtered through an 80-mesh metal sieve, and the ratio (mass %) of the dried mass (g) of the insoluble residue remaining on the sieve to 1 g of the sample is determined. This ratio (mass %) is set as the gel content. The gel content can be controlled by adjusting the type or amount of vulcanizing agent and the vulcanization conditions (temperature, residence time, occupancy, etc.). The aforementioned crosslinks can be used in tire applications or vibration-damping rubber, belts, industrial products, footwear, foams, etc., just like the vulcanized products of the aforementioned reinforcing filler formulations. Furthermore, they can also be used as materials for medical devices or food packaging materials.

[Molded Article Using Hydrogenated Block Copolymer (A) or Hydrogenated Block Copolymer Composition] The molded article of this embodiment is a molded article of the hydrogenated block copolymer (A) or hydrogenated block copolymer composition of this embodiment, which can be obtained by molding the aforementioned hydrogenated block copolymer (A) or hydrogenated block copolymer composition of this embodiment. 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 agglomeration molding, foam molding, laminated molding, calendering, blow molding, etc. Examples of molded bodies include, but are not limited to, sheets, films, injection molded bodies of various shapes, hollow molded bodies, compressed molded bodies, vacuum molded bodies, extruded molded bodies, foamed molded bodies, non-woven or fibrous molded bodies, and synthetic leather. These molded bodies can be used, for example, in automotive parts, food packaging materials, medical devices, components for home appliances, electronic components, building materials, industrial parts, household goods, toy materials, footwear materials, and fiber materials.

As automotive parts, examples include: side trim strips, gaskets, gear shift knobs, weatherstripping, window frames and their sealing materials, armrests, auxiliary grips, door handles, door handles, console boxes, headrests, instrument panels, bumpers, spoilers, airbag covers, etc., but are not limited to the above. As medical devices, examples include: medical tubes, medical hoses, catheters, blood bags, infusion bags, platelet storage bags, artificial dialysis bags, etc., but are not limited to the above. As building materials, examples include: wall materials, flooring materials, etc., but are not limited to the above. Besides these, there are no particular limitations. Examples include: industrial hoses, food hoses, vacuum cleaner hoses, refrigerator seals, wires and various other coating materials, grip coating materials, soft toys, etc. The above-mentioned molded bodies can also be appropriately processed by foaming, powdering, stretching, bonding, printing, coating, plating, etc. The hydrogenated block copolymer (A) of this embodiment and the above-mentioned hydrogenated block copolymer compositions exhibit excellent flexibility, low rebound elasticity, transparency, and kink resistance, making them extremely useful as materials for hollow molded bodies such as hoses and tubes.

Secondly, the hydrogenated block copolymer (A) and the molded articles of the hydrogenated block copolymer composition using this embodiment will be explained in terms of purpose as divided into [first molded article] to [third molded article].

[First Molded Body] As a first example of a molded body using the hydrogenated block copolymer (A) of this embodiment, an example may be a molded body that substantially contains only the hydrogenated block copolymer (A). "Substantially contains only the hydrogenated block copolymer (A)" means that the polymer constituting the molded body is primarily the hydrogenated block copolymer (A), and does not exclude the inclusion of the various additives described below. Furthermore, the addition of other polymers is not excluded, provided it does not impair the function of the hydrogenated block copolymer (A). The permissible amount of other polymers added also depends on the polymer's structure or application; for example, in the case of resin compositions with polyolefins such as polypropylene, it is approximately 5% by mass or less. If it is a resin composition with other elastomers, although it also depends on the structure of the other elastomers, its addition amount is allowed to be up to 80% by mass. In addition to being suitable for transparent tubes and bags used in medical applications, the first molded body can also be used as an adhesive layer for forming an adhesive film for protective films, 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 a good balance of these properties. Without prejudice to the purpose of this embodiment, the tube may contain other components besides the hydrogenated block copolymer (A) of this embodiment. Other components may include, but are not limited to, hydrogenated copolymers (styrene-based thermoplastic elastomers) with structures different from hydrogenated block copolymer (A), thermal stabilizers, antioxidants, UV absorbers, anti-aging agents, plasticizers, light stabilizers, crystal nucleating agents, impact modifiers, pigments, lubricants, softeners, antistatic agents, dispersants, flame retardants, copper scavenging agents, crosslinking agents, flame retardant accelerants, compatibilizers, and adhesive imparters. Only one of these other components may be used, or two or more may be used in combination.

<Lubricant> To prevent adhesion between tube surfaces or internal parts and to improve the feel and texture, the tubes described above may contain a lubricant. Preferably, the lubricant is a lubricant selected from at least one (preferably at least two) of fatty acid amine-based lubricants, stearate metal salt-based lubricants, and fatty acid monoglyceride-based lubricants. Examples of fatty amide lubricants include: erucic acid amide, benzyl amide, oleyl amide, stearyl amide, N-stearyl lauryl amide, N-stearyl stearyl amide, N-stearyl benzyl amide, N-stearyl erucic acid amide, N-oleyl oleyl amide, N-oleyl benzyl amide, N-lauryl erucic acid amide, ethyl bisoleyl amide, ethyl bisstearyl amide, hexamethylene bisoleyl amide, hexamethylene biserucic acid amide, etc., but are not limited to the above. Among these, erucic acid amide, betaine amide, oleyl amide, stearyl amide, and ethyldistearate amide are preferred, with oleyl amide being more preferred. Examples of metals that can be used as stearic acid metal salt lubricants include, for example, zinc, sodium, calcium, magnesium, and lithium. Among these, zinc stearate is preferred. Examples of fatty acid monoglyceride lubricants include, for example, glyceryl laurate, glyceryl myristate, glyceryl palmitate, glyceryl stearate, glyceryl oleate, and glyceryl betaine, but are not limited to these. Among these, glyceryl stearate is preferred. From the viewpoint of preventing adhesion, the content of lubricant in the aforementioned tube is preferably 0.05% by mass or more. From the viewpoint of preventing 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 viewpoints, the content of lubricant in the aforementioned tube is preferably in the range of 0.05% to 1.0% by mass, and more preferably in the range of 0.05% to 0.7% by mass. One type of fatty amide lubricant, stearate metal salt lubricant, and fatty acid monoglyceride lubricant may be used alone, or two or more may be used in combination. The preferred method is to use erucic acid amine, zinc stearate, and ethyl bis-stearic acid amine in combination, with a preferred mass ratio of erucic acid amine/zinc stearate/ethyl bis-stearic acid amine = 0.20/0.15/0.15.

<Softener> The above-mentioned tubes may contain a softener. Examples of softeners include paraffin oils, naphthenic oils, aromatic oils, solid paraffin wax, liquid paraffin, white mineral oil, and plant-based softeners, but are not limited to these. Among these, paraffin oils, liquid paraffin, and white mineral oil are preferred from the viewpoint of low-temperature characteristics or impermeability. The kinematic viscosity of the softener at 40°C is preferably 500 ^mm² /sec or less. The lower limit of the kinematic viscosity of the softener at 40°C is not particularly limited, but is preferably 10 ^mm² /sec. If the kinematic viscosity of the softener at 40°C is below 500 ^mm² /sec, the flowability and processability of the aforementioned tubes tend to improve further. The kinematic viscosity of the softener can be measured by methods such as testing with a glass capillary viscometer.

<Adhesive Enhancing Agent> The tube may also contain an adhesive enhancing agent. Examples of adhesive enhancing agents include: benzofuran-indene resin, p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, terpene resin, hydrogenated terpene resin, terpene-phenol resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, and aliphatic/alicyclic hydrocarbon resin. 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-based resins, etc., but not limited to the above.

<Method for Manufacturing the Tube> [Method for Manufacturing the Material Constituting the Tube] The material constituting the tube may be, for example, the hydrogenated block copolymer (A) of this embodiment, and other components added as needed, and is prepared by dry admixture of these components; or by mixing using an apparatus for mixing common polymeric substances. There are no particular limitations on the mixing apparatus; examples include: a Bamboo mixer, a Laboplastomill, a single-shaft extruder, a twin-shaft extruder, etc. From the viewpoint of productivity and good mixing properties, it is preferable to manufacture the tube by melt mixing using an extruder. The melting temperature during mixing can be appropriately set, typically in the range of 130–300°C, preferably in the range of 150–250°C.

[Tube Forming Method] There are no particular limitations on the tube forming method. For example, the following method can be used: The hydrogenated block copolymer (A) of this embodiment, and other components added as needed, are appropriately selected, fed into an extruder to melt it, and then passed into a mold to form a tube. The tube is then water-cooled or air-cooled to produce the tube. The extruder can be a single-shaft or multi-shaft extruder. Furthermore, multi-layer tubes can also be formed by extruding multiple layers using multiple extruders. The tube shape is not particularly limited; round or elliptical tubes are commonly used. The tube diameter is not particularly limited; for example, a diameter of 1–50 mm is preferred, more preferably 2–30 mm, and even more preferably 3–20 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 can also be made into a multilayer tube by laminating other polymers to the extent that it does not impede the purpose of this embodiment. The aforementioned other polymers can be used alone or in combination of two or more, and can be used in single layers or in multiple layers with different types of polymers. Furthermore, by multilayering and appropriately selecting two or more different polymers, a tube with varying hardness depending on the location can be obtained, even without seams. The layer containing the aforementioned polymers in the tube with the above-mentioned multilayer structure can be located in any of the innermost, middle, or outermost layers, depending on the desired properties imparted.

From the perspective of maintaining flexibility by suppressing the increase of wall thickness and subsequently improving pressure resistance, pressure-resistant tubes (hose) can be made by winding braided reinforcing threads or spiral reinforcements in the aforementioned tubes. The braided reinforcing threads are located inside or between layers in the thickness direction and can be made of vinylon, polyamide, polyester, aramid fiber, carbon fiber, metal wire, etc. The spiral reinforcements are located on the outer periphery and can be made of metal, plastic, etc.

The aforementioned tube achieves a high level of transparency, flexibility, kink resistance, solvent adhesion, and a good balance of various properties, making it suitable for a wide range of applications, including household appliances, automotive interior and exterior parts, daily necessities, entertainment products, toys, industrial products, food manufacturing equipment, medical applications, and drinking water applications. Among these, the aforementioned tube is particularly suitable for medical applications. For example, it can also be appropriately used as tubing for infusion sets, enteral nutrition devices, extension tubing, drug delivery tubing, blood circulation tubing, feeding tubing, connecting tubing, leaflet-type intravenous needle tubing, and further, suction tubing, drainage tubing, enteral nutrition tubing, gastric tube tubing, drug delivery tubing, peritoneal dialysis tubing, blood tubing, balloon tubing, urethral tubing, etc.

(Adhesive Membrane) The adhesive membrane comprises: a substrate membrane; and an adhesive layer disposed on the substrate membrane, comprising the hydrogenated block copolymer (A) of this embodiment, and exhibiting excellent balance of various properties such as initial adhesion, adhesion hyperactivity, and roll-up properties. An adhesive preamble may also be contained in the adhesive layer of the adhesive membrane. As an adhesive enhancer, there are no particular limitations as long as it is a resin capable of imparting adhesiveness to the adhesive layer. Examples include: hydrogenated terpene resins, rosin-based terpene resins, hydrogenated rosin-based terpene resins, aromatic modified hydrogenated terpene resins, benzofuran resins, phenolic resins, terpene-phenol resins, hydrogenated terpene-phenol resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and other known adhesive enhancers. Hydrogenated terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene-phenol resins, and terpene-phenol resins are particularly preferred. One type of adhesive enhancer may be used alone, or two or more may be used in combination. As an adhesive preform, one such preform can be used, for example, those described in "Rubber and Plastic Formulation Pharmaceuticals" (published by Rubber Digest). By using an adhesive preform, improved adhesion can be achieved. The content of the adhesive preform in the adhesive layer is preferably 0.5–50% by mass, more preferably 5–45% by mass, and even more preferably 10–30% by mass. If the content of the adhesive preform in the adhesive layer is less than 50% by mass, it can effectively prevent excessive adhesion and further reduce the amount of paste residue during peeling. If it is 0.5% by mass or more, it tends to achieve adequate adhesion.

<Substrate Film> There are no particular limitations on the material used for the substrate film; any type of non-polar resin or polar resin can be used. From the perspective of performance or price, polyethylene, homopolymer polypropylene, or block polypropylene are preferred non-polar resins, while polyethylene terephthalate, polybutylene terephthalate, and other polyester resins, polyamide resins, ethylene-vinyl acetate copolymers, and their hydrolysates are preferred polar resins. The thickness of the substrate film is preferably less than 1 mm, more preferably less than 300 μm, and even more preferably 10–200 μm. If the thickness of the substrate film is 10 μm or more, it can adequately protect the substrate. If the thickness of the substrate film is less than 1 mm, it can obtain a good modulus of elasticity for practical use, good surface tracking, and effectively prevent bulging or peeling.

<Adhesive Layer> The adhesive film has an adhesive layer comprising the hydrogenated block copolymer (A) of this embodiment on the aforementioned substrate film. The adhesive layer may also contain other materials as described below.

[Other Materials in the Adhesive Layer] <Hydrogenated Styrene-Based Elastomers> The adhesive layer of the adhesive film may also contain hydrogenated styrene-based elastomers. Examples of representative hydrogenated styrene-based elastomers include: styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene random polymer (SBR), styrene-ethylene-butene-styrene (SEBS) formed by hydrogenating SBS, and styrene-ethylene-propylene-styrene (SEPS). However, these are not limited to the above. In addition, elastomers with structures such as styrene-ethylene-butene (SEB), styrene-ethylene-propylene (SEP), and styrene-isobutene-styrene triblock copolymer (SIBS) may also be used. Furthermore, as the aforementioned hydrogenated styrene-based elastomers, reactive elastomers endowed with various functional groups can also be used. Examples of such functional groups include: hydroxyl, carboxyl, carbonyl, thiocarbonyl, acetyl halide, acid anhydride, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylic acid ester, acetamino, sulfonic acid, sulfonate, phosphoric acid, phosphate ester, amino, imino, nitrile, pyridinyl, quinolinyl, epoxy, thioepoxy, thio, isocyanate, isothiocyanate, halogenated silica, alkoxysilyl, halogenated tin, borate, boron-containing groups, borate salts, alkoxytin, and phenyltin, but are not limited to the above.

<Alkene Resins and Alkene Elastomers> The adhesive layer of an adhesive film may also contain alkene resins and alkene elastomers. Examples of alkene resins and alkene elastomers include: α-olefin polymers or copolymers with 2 to 20 carbon atoms, and copolymers of ethylene with unsaturated carboxylic acids or unsaturated carboxylic acid esters. Specifically, examples include: ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methylpentene copolymers, ethylene-1-octene copolymers, propylene homopolymers, propylene-ethylene copolymers, propylene-ethylene-1-butene copolymers, 1-butene homopolymers, 1-butene-ethylene copolymers, 1-butene-propylene copolymers, 4-methylpentene homopolymers, 4-methylpentene-1-propylene copolymers, 4-methylpentene-1-butene copolymers, 4-methylpentene-1-propylene-1-butene copolymers, propylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers.

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

<Softener> The adhesive layer of the adhesive film may also contain a softener. There are no particular limitations on the type of softener; for example, either mineral oil-based softeners or synthetic resin-based softeners can be used. Examples of mineral oil-based softeners include mixtures of aromatic hydrocarbons, cycloalkane hydrocarbons, and paraffinic hydrocarbons. Furthermore, paraffinic hydrocarbons with more than 50% carbon atoms are called paraffinic oils, cycloalkane hydrocarbons with 30-45% carbon atoms are called cycloalkane oils, and aromatic hydrocarbons with more than 35% carbon atoms are called aromatic oils. As a mineral oil-based softener, paraffin-based oils used as rubber softeners are preferred; as a synthetic resin-based softener, polybutene and low molecular weight polybutadiene are preferred.

<Antioxidants, light stabilizers, etc.> Antioxidants and light stabilizers can also be added to the adhesive layer of adhesive films. Examples of antioxidants include: 2,6-di-tert-butyl-4-methylphenol, octadecyl 3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,4-bis[(octylthio)methyl]-orthocresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, propylene... Hindered phenolic antioxidants such as 2,4-diterpentyl-6-[1-(3,5-diterpentyl-2-hydroxyphenyl)ethyl]phenyl ester and 2-[1-(2-hydroxy-3,5-diterpentylphenyl)] ester of acrylate; sulfur-based antioxidants such as dilauryl thiodipropionate, lauryl stearate thiodipropionate, and pentaerythritol tetra(β-lauryl thiopropionate); and phosphorus-based antioxidants such as tri(nonylphenyl) phosphite and tri(2,4-diterpentylphenyl) phosphite, but not limited to the above. Examples of light stabilizers include, but are not limited to, benzotriazole-based UV absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-tert-butylphenyl)benzotriazole, and 2-(2'-hydroxy-3',5'-ditert-butylphenyl)-5-chlorobenzotriazole, benzophenone-based UV absorbers such as 2-hydroxy-4-methoxybenzophenone, or hindered amine-based light stabilizers.

<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 aforementioned additives include: pigments such as red lead and titanium dioxide; waxes such as solid paraffin 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; and 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 these. In addition to the above, examples of synthetic rubbers can be found in publications such as "Rubber and Plastics Formulation Products" (published by Rubber Digest).

<Saturated Fatty Acid Bisamides> The adhesive layer of an adhesive film may contain saturated fatty acid bisamides that have the effect of inhibiting hyperadhesion. Examples of saturated fatty acid bisamides include, but are not limited to, aliphatic bisamides such as ethyl distearate (EBSA), methylene distearate, and hexamethylene distearate; and aromatic bisamides such as m-phenylenediamine and N,N'-distearate m-phenylenediamine. Only one of these saturated fatty acid bisamides may be used alone, or two or more may be used in combination. Furthermore, styrene-based block phase reinforcing agents with the effect of inhibiting excessive adhesion can be formulated. Examples of styrene-based block phase reinforcing agents, as monomer units, include styrene and styrene compounds such as α-methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene, tributylstyrene, p-ethylstyrene, and divinylbenzene, but are not limited to these. One of these can be used alone, or two or more can be used in combination.

<Method for Manufacturing Resin Material Constituting the Adhesive Layer of the Adhesive Film> The resin material constituting the adhesive layer of the adhesive film of this embodiment can be manufactured by, for example, by dry admixture of the hydrogenated block copolymer (A) of this embodiment and other components added as needed; or by mixing using an apparatus for mixing conventional polymer materials. Examples of mixing apparatus include, but are not limited to, Bamboo mixers, Laboplastomills, single-shaft extruders, and biaxial extruders. From the viewpoint of productivity and good mixing properties, it is preferable to manufacture by melt mixing using an extruder. Furthermore, especially when the adhesive preformer is incorporated into the resin material constituting the adhesive layer, the adhesive preformer tends to be more viscous and sheet-like when using the aforementioned dry admixture method, which may lead to a decrease in processing quality. Therefore, a masterbatch can be prepared by pre-mixing the adhesive preformer into the hydrogenated block copolymer (A) of this embodiment. The melting temperature of the resin material constituting the adhesive layer during mixing can be appropriately set, typically in the range of 130–300°C, preferably in the range of 150–250°C. To achieve lighter weight, softer texture, and improved adhesion, the resin material constituting the adhesive layer can also be foamed. Foaming methods include chemical methods, physical methods, and the use of thermally expandable microspheres, but are not limited to these. Bubbles can be distributed within the material by adding inorganic or organic foaming agents, physical foaming agents, or thermally expandable microspheres. Furthermore, adding hollow fillers (expanded air balloons) can also achieve lightweighting, softening, and improved adhesion.

<Method for Manufacturing an Adhesive Membrane> The adhesive membrane has an adhesive layer comprising the hydrogenated block copolymer (A) of this embodiment on a substrate membrane. The method for manufacturing the adhesive membrane is not particularly limited; examples include methods such as applying a solution or melt of the resin material constituting the adhesive layer onto the substrate membrane, and methods using a membrane extruder. When using a solution or melt of the resin material constituting the adhesive layer, the solution or melt can be prepared after preparing a resin material containing the hydrogenated block copolymer (A) and other components, or it can be mixed after preparing a solution or melt containing the hydrogenated block copolymer (A). When an adhesive film is manufactured by applying a resin material solution, it can be produced, for example, by dissolving the resin material in a solvent capable of dissolving it, applying it to a substrate film using a coating machine, and then heating and drying the solvent, but is not limited to the above. In a method of melting and applying a resin material, for example, an adhesive film can be manufactured by applying molten resin material to a substrate film using a hot melt coating machine, but is not limited to this. In this case, it is preferable to use various substrate films having a glass transition temperature, melting point, or softening point higher than the coating temperature. As a method for manufacturing adhesive films using a membrane extruder, for example, the film can be manufactured by using a melt co-extruder, in which the components of the adhesive layer containing resin material and the components of the thermoplastic resin that can form the substrate film flow in two directions. That is, the fluid for forming the adhesive layer and the fluid for forming the substrate film are combined in the die to form a single fluid and extruded, thus combining the adhesive layer and the resin film layer, but it is not limited to the above. In the case of using a membrane extruder, the resin material for forming the adhesive layer can also be manufactured by pre-dry blending the components for the adhesive layer, thus it is a method with excellent productivity. Furthermore, adhesive films produced during extrusion molding tend to exhibit particularly excellent adhesion and bonding strength. These adhesive films can be temporarily adhered to the surfaces of optical system moldings such as light guide plates or prism sheets, synthetic resin sheets, metal sheets, decorative plywood, coated steel sheets, and various nameplates, serving as protective films to prevent damage or contamination during the processing, handling, and storage of these adhered bodies.

[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 skin materials, sheet molded bodies (sheets, films), drinking water pipes, and drinking water hoses; and packaging materials, such as food packaging materials and clothing packaging materials; adhesive films for protective films, and overmolded bodies with polar resins, but are not limited to the above.

(Overmolded Article) The hydrogenated block copolymer composition of this embodiment tends to exhibit adhesion to polar resins, thus allowing the formation of a multilayered molded article (overmolded article) by overmolding together with the polar resin. The overmolded article, by having a structure comprising a layer containing a polar resin and a layer containing the hydrogenated block copolymer composition of this embodiment stacked on top of that layer, becomes an excellent adhesive.

<Polar Resins> Examples of polar resins include: polyvinyl chloride, ABS, acrylonitrile-styrene copolymer, polyacrylic acid, polymethyl methacrylate and other polyacrylates, polymethacrylic acid, polymethyl methacrylate and other polymethacrylates, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyamide, polyacetal, polycarbonate, polybutylene terephthalate, polyvinylidene fluoride, polyurethane, polyether ether, polyphenylene sulfide, polyarylate, polyamide imide, polyether imide, polyether ketone, polyether ether ketone, polyamide, liquid crystal polymer, polytetrafluoroethylene, phenolic 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 with two or more.

In addition to polar resins, layers containing polar resins may also contain fillers. Examples of fillers in layers containing polar resins include: glass fibers, glass spheres, hollow glass spheres, carbon fibers, cellulose nanofibers, wollastonite, potassium titanium oxide fringes, calcium carbonate fringes, aluminum borate fringes, magnesium sulfate fringes, sepiolite, diaspore, zinc oxide fringes, and other fibrous inorganic fillers; talc; calcium carbonate; and calcium oxide. Zinc carbonate, wollastonite, zeolite, wollastonite, silica, alumina, clay, titanium oxide, magnesium hydroxide, magnesium oxide, sodium silicate, calcium silicate, magnesium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, zinc oxide, potassium titanium oxide, hydrotalcite, barium sulfate, titanium black, and carbon black such as furnace black, thermal black, and acetylene black, etc., but not limited to the above. Fiber-like inorganic fillers can also be used for surface treatment using compounds with affinity or reactive groups for polar resins. One filler may be used alone, or two or more may be used.

<Layer containing hydrogenated block copolymer composition> As a layer constituting the above-mentioned overmolded article containing hydrogenated block copolymer composition, examples include those containing the hydrogenated block copolymer composition of this embodiment and a rubber-like polymer. The rubber-like polymer preferably contains vinyl aromatic monomer units and contains at least one polymer block with vinyl aromatic monomer units as the main component. It is also more preferably that it contains vinyl aromatic monomer units, and the vinyl aromatic monomer units are rubber or elastomers of 60% by mass or less. Examples of rubber-like polymers include, but are not limited to, styrene-butadiene rubber and its hydrogenates (except for the hydrogenated block copolymers of this embodiment), styrene-butadiene block copolymers and their hydrogenates, styrene-butadiene-isoprene block copolymers and their hydrogenates.

In addition to the thermoplastic resin (propylene) mentioned above, the layer containing the hydrogenated block copolymer composition may also contain other thermoplastic resins. Examples of the aforementioned thermoplastic resins (propylene) and other thermoplastic resins include, for example: olefinic polymers such as polypropylene, polyethylene, ethylene-propylene copolymer rubber (EPM), and ethylene-propylene-non-conjugated diene copolymer rubber (EPDM); polyester polymers such as polyester elastomers, 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 homopolymers and polyoxymethylene copolymers; styrene homopolymers, acrylonitrile-styrene... Acrylonitrile resins and styrene-based resins such as acrylonitrile-butadiene-styrene resins; polycarbonate resins; styrene-butadiene copolymer rubbers and styrene-isoprene copolymer rubbers and their hydrogenates or modifications thereof; natural rubbers; synthetic isoprene rubbers and liquid polyisoprene rubbers and their hydrogenates. Or modified compounds; chloroprene rubber; acrylic rubber; butyl rubber; acrylonitrile-butadiene rubber; epichlorohydrin rubber; polysiloxane rubber; fluororubber; chlorosulfonated polyethylene; urethane rubber; polyurethane elastomers; polyamide elastomers; polyester elastomers; soft vinyl chloride resins, etc., but not limited to the above. These thermoplastic resins may be used alone or in combination of two or more.

In addition to the softener (but) mentioned above, the layer comprising the hydrogenated block copolymer composition may also contain other softeners. Examples of the softener (but) and other softeners include, but are not limited to, paraffin oils, naphthenic oils, aromatic oils, solid paraffin, liquid paraffin, white mineral oil, and plant-based softeners. The kinematic viscosity of the softener at 40°C is preferably 500 ^mm² /sec or less. The lower limit of the kinematic viscosity of the softener at 40°C is not particularly limited, but is preferably 10 ^mm² /sec. If the kinematic viscosity of the softener at 40°C is below 500 ^mm² /sec, the flowability and processability of the thermoplastic elastomer composition tend to improve further. The kinematic viscosity of the softener can be measured by methods such as testing with a glass capillary viscometer.

In addition to component (B) mentioned above, the layer containing the hydrogenated block copolymer may further contain other olefinic resins and olefinic elastomers. Examples of components (B) and other olefinic resins and olefinic elastomers include, for example, α-olefin polymers or copolymers having 2 to 20 carbon atoms, copolymers of ethylene with unsaturated carboxylic acids or unsaturated carboxylic acid esters, but are not limited to the above. Examples include: ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methylpentene copolymers, ethylene-1-octene copolymers, propylene homopolymers, propylene-ethylene copolymers, propylene-ethylene-1-butene copolymers, 1-butene homopolymers, 1-butene-ethylene copolymers, 1-butene-propylene copolymers, 4-methylpentene homopolymers, 4-methylpentene-1-propylene copolymers, 4-methylpentene-1-butene copolymers, 4-methylpentene-1-propylene-1-butene copolymers, propylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, etc., but are not limited to the above.

Layers comprising hydrogenated block copolymer compositions may also contain adhesive preambles. Examples of adhesive preambles include: benzofuran-indene resin, p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, terpene resin, hydrogenated terpene resin, terpene-phenol resin, hydrogenated terpene-phenol resin, aromatic modified terpene resin, aromatic modified hydrogenated phenol resin, styrene resin, α-methylstyrene resin, aromatic hydrocarbon resins, and aliphatic hydrocarbons. Resins, aliphatic cyclic hydrocarbon resins, aliphatic/alicyclic 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.

Without prejudice to the purpose of this invention, the layer comprising the hydrogenated block copolymer composition may further include other additives in addition to the aforementioned components. Examples of such other additives include: heat stabilizers, antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, light stabilizers, crystal nucleating agents, impact modifiers, pigments, lubricants, antistatic agents, flame retardants, flame retardant accelerants, and compatibilizers. Only one of these additives may be used, or two or more may be used in combination.

<Method for Manufacturing the Hydrogenated Block Copolymer Composition Constituting the Second Molded Article> The method for manufacturing the hydrogenated block copolymer composition constituting the second molded article is not particularly limited and can be manufactured using previously known methods. For example, melt mixing methods using conventional mixers such as pressure kneaders, Bamboo mixers, closed mixers, Laboplastomills, MIX-LABO, single-screw extruders, twin-screw extruders, bidirectional kneaders, and multi-screw extruders can be used; methods such as removing the solvent by heating after dissolving or dispersing the components can also be used. The shape of the hydrogenated block copolymer composition constituting the second molded article is not particularly limited; examples include granules, flakes, ropes, and small flakes. Furthermore, the molded article can also be directly formed after melt mixing.

<Manufacturing Method of Overmolded Article> If the overmolded article comprises one or more layers of the hydrogenated block copolymer composition of this embodiment and layers of polar resin, the number of layers is not particularly limited. The layer forming method of the overmolded article is not particularly limited, and previously known methods can be used, such as extrusion molding, injection molding (embedding molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder agglomeration molding, foam molding, lamination molding, calendering molding, and blow molding). The layer of the hydrogenated block copolymer composition comprising this embodiment is preferably thermally fused to the layer comprising a polar resin. More specifically, the method for manufacturing the overmolded body preferably includes the following steps: using at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding, to layer the hydrogenated block copolymer composition comprising this embodiment onto the pre-formed layer comprising a polar resin. The method for manufacturing the overmolded body may also include, prior to this step, the following step: using any method, preferably at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding, to layer the polar resin.

Overmolded bodies can be formed into shapes corresponding to various applications such as automotive parts, tools, toys, electrical and electronic equipment parts, medical devices, building materials, piping components, tableware, household and decorative items, industrial parts, various hoses, various housings, various module boxes, various power control unit components, writing instruments, robotic arms, and medical devices. Among these, those with handles and those requiring a strong grip or excellent tactile feedback are preferred. Examples of such molded bodies include, but are not limited to, tools, wires, connectors, portable electronic devices, toothbrushes, electric razors, pens such as ballpoint pens, styluses, and pen styluses, tableware such as forks, knives, and spoons, and components with handles. It is particularly preferred to use power tools that exert a greater load on the human body due to vibration during use. As a component constituting the above-mentioned grip, it is preferably at least one of the following: a tool grip, a wire sheath component, a connector housing, a grip for a portable electronic device, a toothbrush grip, a power razor grip, a cutlery grip, a writing instrument grip, a robotic hand grip, and a grip for an automotive interior component.

[Third Molded Body] The third molded body is a molded body of the hydrogenated block copolymer (A) of this embodiment containing 5 to 99% by mass, or 5 to 80% by mass, or more than 8% by mass and less than 60% by mass, or 10 to 30% by mass, or less than 70% by mass of the total mass of the resin composition, and is a molded body containing 10 to 40% by mass of polyolefin resin as other resin components.

The resin composition constituting the third molding preferably further includes a free radical generating compound, also known as a hardener or hardening initiator. Examples of such free radical generating compounds include, but are not limited to, azides, peroxides, sulfur, and sulfur derivatives. A hardening initiator is particularly preferred as a free radical initiator. The free radical generating compound, also known as a hardening catalyst, generates free radicals at high temperatures or under UV (Ultra Violet) irradiation, or further with the addition of other inducing energies. Using a free radical generating compound, the resin composition can be processed at low temperatures even in the absence of UV or inducing energy, but at activation temperatures, or with the introduction of UV or inducing energy, a high concentration of free radicals will be reliably generated. As a free radical generating compound, any compound capable of generating free radicals can be used if inducing energy such as high temperature or UV irradiation is added. Examples of free radical generating compounds include: 2,5-dimethyl-2,5-di(tert-butyl peroxide)-3-hexyne, ditert-butyl peroxide, tert-butyl isopropylphenyl peroxide, di(tert-butyl isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane, and diisopropylbenzene peroxide, but are not limited to these. Furthermore, typical non-peroxide initiators for free radical generating compounds include: 2,3-dimethyl-2,3-diphenylbutane and 2,3-trimethylsiloxy-2,3-diphenylbutane. Furthermore, 2,2-dimethoxy-1,2-diphenylethane-1-one is a typical example of a UV free radical initiator that is a free radical generating compound. The curing initiator is preferably used in the resin composition at an amount of 0.1–10% by mass, 0.3–7% by mass, or 1–5% by mass, depending on the intended use.

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

Examples of third-order molding materials include: prepregs, metal laminates, CCLs (Copper Clad Laminates), printed wiring boards, multilayer wiring substrates, and electronic devices, but are not limited to the above.

[Other Applications of Hydrogenated Block Copolymers] (Prepregs, Metal Laminates) The hydrogenated block copolymer (A) of this embodiment can be used as a dielectric compound for metal laminates and as a printed circuit board made therefrom. By using the hydrogenated block copolymer (A) of this embodiment, a resin composition with good processability, low solution viscosity, excellent curing properties, high softening temperature, low dielectric loss factor at high frequencies, and low dielectric constant can be obtained. Furthermore, prepregs and metal laminates with excellent adhesion between metal foils and insulating layers can be obtained from the aforementioned resin composition.

The aforementioned prepreg refers to an impregnated fabric obtained by impregnating a base fabric or reinforcing fabric with a resin composition comprising the hydrogenated block copolymer (A) of this embodiment. A metal laminate refers to the substrate of a printed circuit board or circuit board. A metal laminate can be obtained by laminating a metal, such as a copper cladding layer, on one or both sides of a reinforcing material (e.g., fiberglass cloth) impregnated with 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. Layering is achieved by pressing one or more layers of copper and prepreg together under high temperature, high pressure, and vacuum conditions. Printed circuit boards (CCLs) are obtained by etching the copper surface of the CCL to create electronic circuits. The etched CCL is assembled into a multi-layer structure with through-holes that have been plated to establish electrical connections between layers.

In the manufacture of prepregs or metal laminates, solvents may be added to change the solid composition of the resin composition and to adjust its viscosity. Examples of solvents 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 these. Each solvent may be used alone or in combination. Preferred solvents are 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 solvent is preferably adjusted to include 10–50% by mass or 15–40% by mass of solids relative to the total mass of the solution and solids.

In the above-mentioned resin composition, at least one of the following additives may be added: coupling agent, curing accelerator, surfactant, reinforcing agent, viscosity modifier, wetting agent, antioxidant, colorant, etc. The selection of additives is influenced by the intended use and the desired properties, such as dielectric constant, dielectric loss factor, dielectric loss, and/or other desired properties, chosen in a manner that enhances the electrical characteristics of the circuit components or does not substantially cause adverse effects. Curing accelerators are added to increase the reaction rate of the resin composition. Surfactants are added to ensure uniform distribution of inorganic fillers in the resin composition and to prevent the aggregation of inorganic fillers. The reinforcing agent is added to improve the toughness of the resin composition.

The aforementioned resin composition may further include, in an amount of 0.1 to 2% by mass, a bonding accelerator known in the art, such as an N-containing heterocyclic metal bonding accelerator capable of forming a metal foil and composite. This enhances the adhesion between the metal foil and the resin composition layer. The bonding accelerator may also be contained in the resistive metal layer in the form of a solution or dispersion in water or an organic solvent.

The aforementioned resin composition may further include up to 15% by weight of a subsequent promoting polymer, which is selected from the group consisting of poly(aryl ether), carboxyl-functionalized poly(aryl ether), and styrene-ethylene/butene-styrene (SEBS) functionalized with maleic anhydride. Specifically, the curing resin composition preferably contains a copolymer, a curing initiator selected from sulfur curing agents and peroxide curing agents, and a diene rubber as a co-curing additive.

The aforementioned resin composition may further contain soluble polymers such as polyphenylene ether resins, polyolefins, styrene-based polymers, styrene-based block copolymers or hydrogenated styrene-based block copolymers, and high-Tg polycyclic cycloenes. These soluble polymers are used in low amounts to modify the resin composition, improving its film-forming ability, impact resistance, Tg, and processing characteristics.

The amount of any selective additive in the above-mentioned resin composition containing the hydrogenated block copolymer (A) of this embodiment may be set as 0.1 to 25% by mass of the total amount of the resin composition, or more than 0.2% by mass, or more than 0.5% by mass, or less than 10% by mass, or less than 15% by mass, depending on the purpose.

The resin composition comprising the hydrogenated block copolymer (A) of this embodiment is suitable for use in laminates for printed circuit boards, such as copper foil laminates. The laminate can be manufactured by impregnating a substrate or reinforcing material, such as glass fibers, fabrics, or cross-ply laminates, with the resin composition partially or entirely cured to form a prepreg. To manufacture the laminate, one or more layers of copper are deposited on one or more layers of prepreg. Printed circuit boards can be used in a wide range of high-frequency, high-data-speed electrical and electronic applications.

As a method for manufacturing high-frequency CCLs or circuit substrates, the following method can be exemplified. The above-mentioned components are mixed to obtain a resin composition comprising the hydrogenated block copolymer (A) of this embodiment, a curing initiator, and optional components, such as multifunctional co-curing agents like diene polymers, flame retardants, and other optional components. The resin composition is diluted to a suitable viscosity using a solvent such as toluene, xylene, methyl ethyl ketone (MEK), and mixtures thereof to form a glue or varnish. A reinforcing material or substrate, such as fiber, glass felt, wood pulp paper, or fiberglass cloth (optionally treated with a coupling agent), is impregnated in the glue or varnish to the desired thickness. Next, the solvent is removed from the impregnated fiberglass cloth by solvent evaporation to form a prepreg. The prepreg is formed by evaporating the solvent at a temperature below the activation temperature of the curing initiator, or for a time sufficient for solvent evaporation but not reaching the gelation time. The gelation time refers to the time from when the material begins to soften until gelation occurs; gelation is the irreversible change from a self-adhesive liquid to an elastic gel. Prepreg is formed by impregnating a substrate, such as a fiber, with a resin composition, resulting in a semi-cured substrate; or by hot-pressing coated fibers together with a further resin composition; or by hot-pressing without a resin composition. Next, a high-frequency CCL or circuit substrate is formed by building up the prepreg between copper foils and curing it at a temperature of 150–250°C and a pressure of 20 kg/ ^cm² –70 kg/ ^cm².

[Foamed Body] The molded body of this embodiment can also be a foamed body. The foamed body of this embodiment is typically obtained by adding a foaming agent (E) to the hydrogenated block copolymer composition of this embodiment and causing it to foam. Foaming methods can be chemical or physical. Both methods involve adding an inorganic or organic foaming agent, or a physical foaming agent, and then using heating or similar methods to volatilize and/or decompose the foaming agent, causing bubbles to distribute within the hydrogenated block copolymer composition. By making the molded body of the hydrogenated block copolymer composition into a foamed body, it is possible to achieve improvements in lightweighting, flexibility, designability, vibration damping, sound absorption, and thermal insulation properties.

(Foaming Agent (E)) As the above-mentioned foaming agent, inorganic foaming agents, organic foaming agents, or physical foaming agents can be used. Examples of inorganic foaming agents include: sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, sodium borohydride, aluminum acetate, metal powder, etc., but are not limited to the above. Examples of organic foaming agents include: azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N,N'-dinitrospentamethylenetetramine, N,N'-dinitroso-N,N'-dimethylphenylenedimethylamine, benzenesulfonamide, p-toluenesulfonamide, p,p'-oxybisbenzenesulfonamide, p-toluenesulfonamide, etc., but are not limited to the above. Examples of physical blowing agents include: pentane, butane, hexane, etc.; halogenated hydrocarbons such as chloromethane, dichloromethane, etc.; gases such as nitrogen, carbon dioxide, and air; and fluorinated hydrocarbons such as trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorodifluoroethane, and hydrofluorocarbons, but are not limited to the above. Furthermore, these blowing agents can also be used in combination. The amount of blowing agent prepared relative to 100 parts by weight of the hydrogenated block copolymer or hydrogenated block copolymer combination of this embodiment is preferably 0.1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and even more preferably 3 to 20 parts by weight.

(Foaming Aid) In the above-described steps for manufacturing foamed materials, a foaming agent may be used together with the foaming agent. There are no particular limitations on the type of foaming agent used; commonly used foaming agents can be used. Examples include: urea compounds; zinc compounds such as zinc oxide, zinc stearate, zinc benzenesulfonate, zinc toluenesulfonate, zinc trifluoromethanesulfonate, and zinc carbonate; lead compounds such as lead dioxide and tribasic lead. When using both a foaming agent and a foaming aid, the mixing amount is preferably 0.1 to 1000 parts by weight of the foaming aid, more preferably 0.5 to 500 parts by weight, and even more preferably 1 to 200 parts by weight, relative to 100 parts by weight of the foaming agent.

(Foaming Nucleating Agent) A foaming nucleating agent may be used in the above-described foam manufacturing steps. There are no particular limitations on the type of foaming nucleating agent used; any commonly used foaming nucleating agent may be used. Examples include: titanium oxide, talc, kaolin, clay, calcium silicate, silicon dioxide, sodium citrate, calcium carbonate, diatomaceous earth, calcined iron oxide, zeolite, bentonite, glass, limestone, calcium sulfate, alumina, titanium oxide, magnesium carbonate, sodium carbonate, ferric carbonate, and polytetrafluoroethylene powder. Regarding the amount of foaming nucleating agent, relative to 100 parts by weight of the hydrogenated block copolymer or hydrogenated block copolymer composition of this embodiment, it is preferred that the amount of foaming nucleating agent be set to 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, and even more preferably 0.1 to 10 parts by weight.

(Examples of Application of Foamed Materials) The foamed material of this embodiment can be applied to injection-molded, hollow-molded, compressed-molded, vacuum-molded, and extruded products of various shapes, such as sheets, films, or other materials. Furthermore, the foamed material of this embodiment can be widely used in automotive interior materials (dashboards, door panels, seat back panels, steering wheels, etc.), household appliances, tools, furniture (buffers, etc.), and residential building materials—components requiring cushioning. When using the foamed material of this embodiment in automotive interior materials, from a low health hazard perspective, the foaming agent used is preferably sodium bicarbonate, nitrogen, carbon dioxide, air, or other gases.

(Injection Molding Foaming Method) The foam body of this embodiment can be manufactured by injection molding foaming. There are no particular limitations on the injection molding foaming method; examples include short-shot method, full-shot method, and core-pulling method. By using the above methods, a cushioned foam layer and a surface layer with design features or higher hardness compared to the foam layer, such as wrinkles, can be formed in the same steps, thus reducing the number of molding steps. Furthermore, when using the core-pulling method in injection molding foaming, a counter pressure device can be used to eliminate swirl marks on the surface of the molded body.

(Hydrogenated block copolymer composition suitable for foam molding) In the molding of foam, the content of hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of this embodiment is preferably 1% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 49% by mass or less, and even more preferably 20% by mass or more and 48% by mass or less. If the content of hydrogenated block copolymer (A) in the hydrogenated block copolymer composition is within the above range, there is a tendency for finer bubbles and increased bubble independence (increased foaming property) during foam molding. Therefore, it is expected to improve thermal insulation or long-term bubble stability, or improve the molding appearance during core pulling (suppressing shrinkage marks, pits, vortex marks, etc.). Furthermore, the MFR (Melt Flow Rate) of the hydrogenated block copolymer (A) in this embodiment, measured according to JIS K7210 at a temperature of 230°C and a load of 2.16 kg, is 10 or higher. In the hydrogenated block copolymer (A) of the hydrogenated copolymer composition used in foam molding, the aforementioned MFR is preferably 15 or higher, more preferably 30 or higher, and even more preferably 50 or higher. A higher MFR results in better processability, and can be expected to improve the molding appearance of the foam (suppressing shrinkage marks, pits, and swirl marks) or increase the foaming ratio. The preferred range of the foaming ratio depends on the application, but is generally preferably 1.5 times or higher, and more preferably 1.75 times or higher. Due to the higher magnification, it is possible to achieve improvements in lightweighting, flexibility, design, vibration damping, sound absorption, and heat insulation.

The content of olefinic resin (ethyl) 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 even more preferably 12% by mass or more and 40% by mass or less. If the content of olefinic resin (ethyl) is within the above range, there is a tendency for a good balance between foamability and softness.

The thermoplastic resin (propylene) content in the hydrogenated block copolymer composition used in foam molding is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less. If the thermoplastic resin (propylene) content is within the above range, there is a tendency for a good balance between foamability and softness.

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

The present invention will be described in detail below with specific embodiments and comparative examples, but the present invention is not limited by the following embodiments and comparative examples. The methods for measuring and evaluating the physical properties applied in the embodiments and comparative examples will be explained below.

[Specific method for the structure of copolymers] ((1) Content of all vinyl aromatic monomer units (styrene) in hydrogenated block copolymer (A) Using hydrogenated block copolymer, the content of all vinyl aromatic monomer units (styrene) in hydrogenated block copolymer (A) was determined using a UV spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).

((2-1) Content of polymer blocks (polystyrene blocks) with vinyl aromatic monomers as the main component in hydrogenated block copolymer (A)) Using hydrogenated block copolymer, the content of polymer blocks (a) with vinyl aromatic monomers as the main component in hydrogenated block copolymer (A) was determined using nuclear magnetic resonance (NMR) apparatus (Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Hereinafter referred to as "NMR method").

((2-2) Content of hydrogenated copolymer block (b) in hydrogenated block copolymer (A)) By calculating (100 - Content of hydrogenated copolymer block (a) in hydrogenated block copolymer (A), the content of hydrogenated copolymer block (b) in hydrogenated block copolymer (A) can be determined.

((3) Vinyl bond content in hydrogenated block copolymer (A)) Hydrogenated block copolymers were used, and the vinyl bond content was determined using nuclear magnetic resonance (NMR). The vinyl bond content in the conjugated diene monomer units in hydrogenated block copolymer (A) was determined by the following ratio, which is the ratio of the total area of the peaks of 1,2-bonds and 3,4-bonds associated with the conjugated diene monomer units obtained in the NMR determination to the total area of all peaks (the ratio of 1,2-bonds, 3,4-bonds, and 1,4-bonds).

((4) Weight-average molecular weight and molecular weight distribution of hydrogenated block copolymer (A)) Hydrogenated block copolymers were used, and the molecular weight was determined using GPC [Apparatus: HLC-82209PC (manufactured by Tosoh Corporation), column: TSK Geguard column SuperHZ-L (4.6 mm × 20 cm) × 3]. Tetrahydrofuran was used as the solvent. The determination was performed at a temperature of 35°C. The weight-average molecular weight was determined by using a calibration curve (made using the peak molecular weight of standard polystyrene) obtained from the determination of commercially available standard polystyrene, and the molecular weight of the peaks in the chromatogram was obtained. Furthermore, when there are multiple peaks in the chromatogram, the average molecular weight (Mw) obtained by calculating the molecular weight of each peak and the composition ratio of each peak (determined by the area ratio of each peak in the chromatogram) was set as the weight-average molecular weight. Regarding the molecular weight distribution (Mw/Mn), the number average molecular weight (Mn) was also determined using GPC and calculated based on the Mw/Mn ratio.

((5) Hydrogenation rate of double bonds in conjugated diene monomer units of hydrogenated block copolymer (A)) Hydrogenated block copolymer was used, and the hydrogenation rate of double bonds in conjugated diene monomer units of hydrogenated block copolymer (A) was determined using a nuclear magnetic resonance apparatus (manufactured by JEOL RESONANCE, ECS400).

((6-1) The content RS of vinyl aromatic monomers in the hydrogenated copolymer block (b) relative to the total content of vinyl aromatic monomers in the hydrogenated block copolymer (A) and the content of vinyl aromatic monomers in the hydrogenated copolymer block (b)) Based on the difference between the content of all vinyl aromatic monomers in the hydrogenated block copolymer (A) measured in (1) above and the content of polymer blocks (a) in the hydrogenated block copolymer (A) with vinyl aromatic monomers as the main component measured in (2-1) above, the content RS of vinyl aromatic monomers in the hydrogenated copolymer block (b) relative to the total content of vinyl aromatic monomers in the polymer is calculated. Based on the ratio of the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (A) measured in (2-2) above, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) is calculated.

((6-2) Content of congypsum diene monomer units in hydrogenated copolymer block (b) relative to the total content of hydrogenated copolymer (A)) is obtained by subtracting the content of vinyl aromatic monomer units in hydrogenated copolymer block (b) relative to the total content of hydrogenated copolymer (A) from the content of hydrogenated copolymer block (b) in hydrogenated copolymer (A).

[Method for Determining the Physical Properties of Hydrogenated Block Copolymers] ((7) Tanδ Peak Temperature) A "compression-molded sheet of hydrogenated block copolymer" manufactured as described below was cut into dimensions of 12.5 mm in width and 40 mm in length and set as a test sample. Next, the test sample was set to a torsion geometry of the device ARES (manufactured by TA Instruments Co., Ltd., trade name), and the tanδ peak temperature from -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 set as the value obtained from the peak detected by the automatic measurement using the RSI Orchestrator (manufactured by TA Instruments Co., Ltd., trade name).

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

(9) Hardness) A test sample of "hydrogenated block copolymer compression molding sheet" manufactured as described below was prepared. The instantaneous values were measured using a type A hardness tester according to JIS K6253. The instantaneous hardness value was measured when the probe of the hardness tester was lowered onto the test sample. The hardness (JIS-A, instantaneous) is recorded in Tables 4 and 5 below.

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

[Evaluation Method for the Properties of Molded Articles Using Hydrogenated Block Copolymers] ((11) Abrasion Resistance) Using a vibration-type friction tester (manufactured by TESTER SANGYO Co., Ltd., AB-301 type), the surface (leather-textured surface) of the injection-molded sheet produced by the [production of injection-molded sheet] below is rubbed with a friction cloth of fine white cotton No. 3 and a load of 500 g. The abrasion resistance is evaluated according to the following criteria based on the amount of volume reduction after friction. <Evaluation Criteria> 5: After 50,000 friction cycles, the volume reduction is less than 0.01 ml. 4: After 50,000 friction cycles, the volume reduction is 0.01 ml or more but less than 0.05 ml. 3: After 50,000 friction cycles, the volume reduction is 0.05 ml or more but less than 0.10 ml. 2: After 50,000 friction cycles, the volume reduction is 0.10 ml or more but less than 0.15 ml. 1: After 50,000 friction cycles, the volume reduction exceeds 0.15 ml.

A score of 3 or higher is considered acceptable for abrasion resistance. A higher score indicates better durability and greater flexibility in applications involving thinner-walled or more complex molded bodies, especially under heavier loads or with coarser fabrics. Good abrasion resistance allows for applications requiring stringent abrasion resistance, such as automotive materials. For example, in automotive interior materials, it performs comparably to simpler, smaller molded bodies when molded with thinner walls or more complex/larger shapes, and its appearance can be expected to remain consistent over longer periods of use. Furthermore, even assuming wear and tear during travel due to higher loads or coarser fabrics (e.g., coarse twill cotton fabric with a coarser weave than fine white cotton No. 3), the material's appearance can be expected to be maintained for a long time. Also, if abrasion resistance is good, there is a tendency to lower the lower limit of the amount of hydrogenated block copolymer (A) in the hydrogenated block copolymer composition of this embodiment, increasing the degree of freedom in formulation. Generally, a higher amount of hydrogenated block copolymer (A) in a hydrogenated block copolymer composition tends to result in better abrasion resistance, while a lower amount of hydrogenated block copolymer (A) tends to result in better oil resistance or material cost; therefore, a lower lower limit for the formulation amount is preferable.

((12) Low elasticity: Dunlop rebound modulus) Samples for testing "compression-molded sheets of hydrogenated block copolymers" were prepared as follows. The rebound modulus was measured at 23°C using a Dunlop rebound elasticity tester according to BS903. From a tactile perspective, a rebound modulus of 20% or less is considered good in practice, and the lower the value, the better the evaluation.

(Calculation of the random parameter g of the hydrogenated block copolymer) The hydrogenated block copolymer (A) was subjected to py-GC/MS determination under the conditions shown in Table 3 below, and the peak intensity P was calculated. Furthermore, based on the content RS of vinyl aromatic monomer units in the copolymer block (b) relative to the whole hydrogenated block copolymer (A), P0 was calculated using P0 = 0.005563 × RS, and g was calculated using g = P/P0. Here, "0.005563" represents the proportionality constant (k) that approximates the content RS (mass %) of the vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the overall hydrogenated block copolymer (A) with the peak intensity P, which is obtained by analyzing the hydrogenated block copolymer (A) polymerized by the following specific polymerization method (homogeneous polymerization) using a thermal decomposition gas chromatography-mass spectrometry analysis apparatus.

[Table 3] pyrolysis device Frontier Labs manufactures the Multishot Pyrolyzer EGA/PY-3030D. Pyrolysis unit heating conditions 500℃ GC device Agilent Technologies manufactures the 7890A. Use tubing DB-1 (30 m×0.25 mmΦ, film thickness 0.25 μm) Column temperature mode After holding at 40°C for 5 minutes, the temperature is increased to 320°C at a rate of 20°C/min and held at 320°C for 11 minutes. gas flow rate 1 ml/min Sample injection port temperature 320℃ Flow split ratio 1/50 Sample quantification 0.10 mg MS Packaging JEOL RESONANCE manufactures JMS-Q1500GC Interface temperature 320℃ Ionization EI 70 eV Scanning range m/z 10～800 Ion source temperature 240℃

[Preparation of Hydrogenated Block Copolymers] (Preparation of Hydrogenation Catalyst) The hydrogenation catalyst used in the preparation of hydrogenated block copolymers in the following embodiments and comparative examples was prepared by the following method. First, a reaction vessel equipped with a stirring device was purged with nitrogen, and 1 liter of dried and purified cyclohexane was added. Next, 100 mmol of bis(n-5-cyclopentadienyl)titanium dichloride was added. While stirring thoroughly, a hexane solution containing 200 mmol of trimethylaluminum was added, and the reaction was carried out at room temperature for approximately 3 days. The hydrogenation catalyst was thus obtained.

(Hydrogenated block copolymers) Hydrogenated block copolymers (A)-1 to (A)-10 and (A)-A to (A)-E constituting hydrogenated block copolymer compositions are prepared in the following manner.

[Example 1] (Hydrogenated Block Copolymer (A)-1) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 13 parts by mass of styrene was added. Next, 0.047 parts by mass of n-butyllithium and 0.9 mol of vinyl bond modifier N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 30 parts by mass of butadiene and 44 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased. When the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased, thereby adjusting to the desired reaction ratio until the reaction was completed. Finally, a cyclohexane solution containing 13 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 65°C for 1 hour. Afterwards, methanol was added to stop the polymerization reaction, obtaining a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 70% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 44% by mass, the vinyl bond content is 21% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-1. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-1 was 98 mol%. Other properties are shown in Table 4.

[Example 2] (Hydrogenated Block Copolymer (A)-2) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 12 parts by mass of styrene was added. Next, 0.048 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. Finally, a cyclohexane solution containing 12 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 65°C for 1 hour. Subsequently, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 69% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 45% by mass, the vinyl bond content is 20% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-2. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-2 was 98 mol%. Other properties are shown in Table 4.

[Example 3] (Hydrogenated Block Copolymer (A)-3) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.048 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 66% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 50% by mass, the vinyl bond content is 21% by mass, and the weight average molecular weight is 161,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-3. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-3 was 98 mol%. Other properties are shown in Table 4.

[Example 4] (Hydrogenated Block Copolymer (A)-4) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 7 parts by mass of styrene was added. Next, 0.049 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 35 parts by mass of butadiene and 51 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. Finally, a cyclohexane solution containing 7 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 65°C for 1 hour. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 65% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 51% by mass, the vinyl bond content is 21% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-4. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-4 was 98 mol%. Other properties are shown in Table 4.

[Example 5] (Hydrogenated Block Copolymer (A)-5) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.050 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 39 parts by mass of butadiene and 45 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 61% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 45% by mass, the vinyl bond content is 24% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-5. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-5 was 98 mol%. Other properties are shown in Table 4.

[Example 6] (Hydrogenated Block Copolymer (A)-6) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.050 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 38 parts by mass of butadiene and 46 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 62% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 46% by mass, the vinyl bond content is 22% by mass, and the weight average molecular weight is 159,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-6. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-6 was 98 mol%. Other properties are shown in Table 4.

[Example 7] (Hydrogenated Block Copolymer (A)-7) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.047 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 30 parts by mass of butadiene and 54 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 70% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 54% by mass, the vinyl bond content is 17% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-7. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-7 was 98 mol%. Other properties are shown in Table 4.

[Example 8] (Hydrogenated Block Copolymer (A)-8) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.047 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 29 parts by mass of butadiene and 55 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 71% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 55% by mass, the vinyl bond content is 17% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-8. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-8 was 98 mol%. Other properties are shown in Table 4.

[Example 9] (Hydrogenated Block Copolymer (A)-9) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.048 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added, and polymerization was carried out at 60°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 66% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 50% by mass, the vinyl bond content is 24% by mass, and the weight average molecular weight is 161,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-9. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-9 was 98 mol%. Other properties are shown in Table 4.

[Example 10] (Hydrogenated Block Copolymer (A)-10) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.048 parts by mass of n-butyllithium and 0.5 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 66% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 50% by mass, the vinyl bond content is 17% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-10. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-10 was 98 mol%. Other properties are shown in Table 4.

[Comparative Example 1] (Hydrogenated Block Copolymer (A)-A) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 18 parts by mass of styrene was added. Next, 0.045 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 22 parts by mass of butadiene and 42 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. Finally, a cyclohexane solution containing 18 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 65°C for 1 hour. Subsequently, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 78% by mass, and the content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 42% by mass, the vinyl bond content is 21% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-A. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-A was 98 mol%. Other properties are shown in Table 5.

[Comparative Example 2] (Hydrogenated Block Copolymer (A)-B) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 2 parts by mass of styrene was added. Next, 0.050 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 39 parts by mass of butadiene and 57 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired level, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired level, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. Finally, a cyclohexane solution containing 2 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 65°C for 1 hour. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 61% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 57% by mass, the vinyl bond content is 20% by mass, and the weight average molecular weight is 159,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-B. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-B was 98 mol%. Other properties are shown in Table 5.

[Comparative Example 3] (Hydrogenated Block Copolymer (A)-C) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.054 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 51 parts by mass of butadiene and 33 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 49% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 33% by mass, the vinyl bond content is 30% by mass, and the weight average molecular weight is 160,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-C. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-C was 98 mol%. Other properties are shown in Table 5.

[Comparative Example 4] (Hydrogenated Block Copolymer (A)-D) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.044 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of butadiene and 64 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was used to quantitatively measure the concentrations of butadiene and styrene in the reaction system in real time, while the feed rates were adjusted appropriately to achieve a 1:1 (mass conversion) polymerization rate between the two. In ReactIR, butadiene monomers were tracked at a wavelength of 1589 ^cm⁻¹ , and styrene monomers were continuously tracked at a wavelength of 775 ^cm⁻¹. When the reactivity ratio was more than 10% higher than the desired ratio, the butadiene feed rate was increased; when the reactivity ratio was more than 10% lower than the desired ratio, the butadiene feed rate was decreased. This adjustment was used to achieve the desired reaction ratio until the reaction was complete. 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. Afterward, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content is 80% by mass, the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) of the hydrogenated block copolymer (A) is 64% by mass, the vinyl bond content is 14% by mass, and the weight average molecular weight is 161,000. Furthermore, in the obtained block copolymer, 100 ppm of hydrogenation catalyst prepared in the above manner (based on Ti) is added per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Secondly, relative to 100 parts by weight of the block copolymer, 0.3 parts by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to obtain hydrogenated block copolymer (A)-D. The hydrogenation rate of the obtained hydrogenated block copolymer (A)-D was 98 mol%. Other properties are shown in Table 5.

[Comparative Example 5] (Hydrogenated Block Copolymer (A)-E) Batch polymerization was carried out using a tank reactor (10 L volume) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added. Next, 0.048 parts by mass of n-butyllithium and 0.9 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added relative to 100 parts by mass of all monomers, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (concentration 20% by mass) containing 34 parts by mass of butadiene and 50 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. At this point, ReactIR was not used; butadiene was fed at a constant rate of 34:50. Finally, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added, and polymerization was carried out at 65°C for 1 hour. Subsequently, methanol was added to stop the polymerization reaction, yielding a block copolymer. Regarding the block copolymer obtained by the above method, the styrene content was 66% by mass, and the content of vinyl aromatic monomers in the hydrogenated copolymer block (b) relative to the overall hydrogenated block copolymer (A) 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 a hydrogenation catalyst prepared as described above (based on Ti) was added per 100 parts by weight 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 weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer per 100 parts by weight of the block copolymer to obtain 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 Compression Molded Sheets] Using 4-inch rollers, the hydrogenated block copolymers (A)-1 to (A)-10 and (A)-A to (A)-E prepared in the above manner were individually extruded at 160°C. Subsequently, hydraulic pressure was applied to compress the sheets at 200°C and 100 kg/ ^cm² to produce 2 mm thick compression molded sheets.

[Preparation of Injection Molded Sheets] Using hydrogenated block copolymers (A)-1 to (A)-10 and (A)-A to (A)-E, injection molding was performed at 220°C to produce injection molded sheets with a thickness of 2 mm, and physical property testing sheets were obtained.

The values of the following items were measured 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. (Structural Analysis Values) Content (mass %) of all vinyl aromatic monomer units (styrene) in the hydrogenated block copolymer (A) Content (mass %) of polymer blocks (polystyrene blocks) (a) with vinyl aromatic monomer units as the main component in the hydrogenated block copolymer (A) Content (mass %) of hydrogenated copolymer blocks (b) containing both vinyl aromatic monomer units and conjugated diene monomer units in the hydrogenated block copolymer (A) Content (mass %) of vinyl aromatic monomer units in hydrogenated copolymer blocks (b) relative to the total hydrogenated block copolymer (A) Content (mass %) of conjugated diene in hydrogenated copolymer blocks (b) relative to the total hydrogenated block copolymer (A) Vinyl bond content (mass %) in hydrogenated block copolymer (A) Molecular weight distribution of hydrogenated block copolymer (A) Weight average molecular weight (ten thousand) of hydrogenated block copolymer (A) Hydrogenation rate of double bonds in conjugated diene monomer units of hydrogenated block copolymer (A) (Moles %) (Physical Properties) • Melt flow rate (MFR: 230℃, 2.16 kg) • Tanδ peak temperature (℃) of -20～60℃ in the viscoelasticity test graph • Hardness (JIS-A instantaneous)

Furthermore, polymer blocks (a) to (b) represent the following polymer blocks, respectively: Polymer block (a): A polymer block with a vinyl aromatic monomer as the main component. Copolymer block (b): A hydrogenated copolymer block containing a vinyl aromatic compound monomer and a conjugated diene monomer.

[Table 4] Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 Implementation Example 5 Implementation Example 6 Implementation Example 7 Implementation Example 8 Implementation Example 9 Implementation Example 10 Hydrogenated block copolymers (A)-1 (A)-2 (A)-3 (A)-4 (A)-5 (A)-6 (A)-7 (A)-8 (A)-9 (A)-10 Vinyl bond balance modifier (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 (°C) 80 80 80 80 80 80 80 80 60 80 Effective use of react_IR ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Content (by mass) of all vinyl aromatic monomers 70 69 66 65 61 62 70 71 66 66 Content (mass %) of polymer block (a) 26 twenty four 16 14 16 16 16 16 16 16 Content (mass %) of hydrogenated copolymer block (b) 74 76 84 86 84 84 84 84 84 84 Content (mass %) of vinyl aromatic monomer units in hydrogenated copolymer block (b) 59 59 59 59 53 55 64 66 59 59 The content of vinyl aromatic monomer units (RS, by mass %) in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer (A). 44 45 50 51 45 46 54 55 50 50 The content (mass %) of congypsum diene monomer units in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer (a). 30 31 34 35 39 38 30 29 34 34 Vinyl bond content (mass %) in hydrogenated block copolymer (A) 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 (in 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 in conjugated diene monomer units (moles %) 98 98 98 98 98 98 98 98 98 98 Crest 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 Random 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 tanδ peak temperature (°C) from -20 to 60°C 19 19 19 19 11 15 30 33 18 19 tanδ peak height at -20～60℃ 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 elasticity: Dumbledore rebound elasticity modulus (%) 3.1 2.5 1.0 0.90 15 1.2 1.6 10 2.0 2.0

[Table 5] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Hydrogenated block copolymers (A)-A (A)-B (A)-C (A)-D (A)-E Vinyl bond balance modifier (mol/n-BuLi 1 mol) 0.9 0.9 0.9 0.9 0.9 Polymerization temperature (°C) 80 80 80 80 80 Effective use of react_IR ○ ○ ○ ○ × Content (by mass) of all vinyl aromatic monomers 78 61 49 80 66 Content (mass %) of polymer block (a) 36 4 16 16 16 Content (mass %) of hydrogenated copolymer block (b) 64 96 84 84 84 Content (mass %) of vinyl aromatic monomer units in hydrogenated copolymer block (b) 65 59 39 76 59 The content of vinyl aromatic monomer units (RS, by mass %) in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer (A). 42 57 33 64 50 The content (mass %) of congypsum diene monomer units in the hydrogenated copolymer block (b) relative to the total hydrogenated block copolymer (a). twenty two 39 51 20 34 Vinyl bond content (mass %) in hydrogenated block copolymer (A) twenty one 20 30 14 25 Molecular weight distribution 1.06 1.06 1.06 1.06 1.06 Weight-average molecular weight (in ten thousand) 16.0 15.9 16.0 16.1 16.0 Hydrogenation rate of double bonds in conjugated diene monomer units (moles %) 98 98 98 98 98 Crest Intensity P 0.229 0.302 0.179 0.337 0.199 P0 0.231 0.315 0.182 0.355 0.276 Random 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 tanδ peak temperature (°C) from -20 to 60°C 18 19 -20 46 18 tanδ peak height at -20～60℃ 1.2 2.5 2.2 2.2 1.5 Abrasion resistance: rating 1 1 1 1 1 Low elasticity: Dumbledore rebound elasticity modulus (%) 10 0.50 70 45 6.0

It can be seen that the hydrogenated block copolymers of Examples 1-10 exhibit excellent abrasion resistance and low elasticity. [Industrial Applicability]

The hydrogenated block copolymer of this invention has industrial applicability in the fields of automotive parts (automotive interior materials, automotive packaging materials), medical equipment materials, food packaging containers and other containers, household appliances, industrial parts, toys and other fields.

Claims (8)

A hydrogenated block copolymer (A) comprises a vinyl aromatic monomer unit and a conjugated diene monomer unit, and contains at least one polymer block (a) with the vinyl aromatic monomer unit as the main component, and satisfies the following <conditions (1)> to <conditions (3)>: <condition (1)>: Contains at least one hydrogenated copolymer block (b) comprising a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the content of the hydrogenated copolymer block (b) in the above-mentioned 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 unit in the above-mentioned hydrogenated copolymer block (b) is 40% by mass or more and 75% by mass or less; <condition (3)>: The ratio g = P/P0, obtained by analyzing the peak intensity P detected by thermal decomposition gas chromatography-mass spectrometry according to the following formula (I), is 0.75 or higher; P0 = k × RS (Formula I) (where RS is the content (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A); k represents the proportionality constant when approximating the content RS (mass %) of vinyl aromatic monomer units in the hydrogenated copolymer block (b) relative to the whole hydrogenated block copolymer (A) with the peak intensity P, which is obtained by analyzing the homogeneous hydrogenated block copolymer (A) using thermal decomposition gas chromatography-mass spectrometry). For example, in the hydrogenated block copolymer of claim 1, the ratio g = P/P0 of the above-mentioned peak intensity P to P0 obtained by using the above (Formula I) is 0.9 or more. As in claim 1, the hydrogenated block copolymer contains vinyl aromatic monomers in block (b) of the aforementioned hydrogenated copolymer at a content of 55% by mass or more and 65% by mass or less. For example, in the hydrogenated block copolymer of claim 1, the content of hydrogenated copolymer block (b) in the hydrogenated block copolymer (a) is more than 75% by mass and less than 85% by mass. A hydrogenated block copolymer composition comprising: a hydrogenated block copolymer (A) of any one of claims 1 to 4: 1% by mass or more and 50% by mass; at least one olefinic resin (B): 5% by mass or more and 90% by mass; at least one thermoplastic resin (C): 1% by mass or more and 50% by mass; and at least one softener (D): 5% by mass or more and 90% by mass. The hydrogenated block copolymer composition of claim 5, wherein the olefinic resin (B) comprises at least one polypropylene resin. A molded article, which is a molded article of the hydrogenated block copolymer composition as claimed in claim 5. The molded body in Request 7 is a foamed body.