JP7560271B2 - Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article - Google Patents

Description

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

Conventionally, materials for automobile interiors have been required to have a good balance between abrasion resistance and mechanical strength, and olefin-based resins have been mainly used as such materials.
On the other hand, in order to meet environmental needs such as weight reduction, recyclability, and ease of incineration of automotive parts, and to achieve heat resistance, cold resistance, heat aging resistance, light resistance, and low odor while eliminating a cheap appearance, etc., styrene-based thermoplastic elastomer materials (hereinafter sometimes simply abbreviated as "TPS materials") have been put into practical use in recent years.

Furthermore, with the increasing demand for car sharing and self-driving cars in recent years, there is a demand for TPS materials for automotive interiors that can achieve a good feel (low hardness) and mechanical strength while maintaining a high level of abrasion resistance.
In response to such demands, for example, Patent Document 1 proposes a composition of a random copolymer styrene-based elastomer having a vinyl aromatic hydrocarbon content of 40% by mass or more and less than 95% by mass and a polypropylene resin, and a molded article of the composition, and discloses that the molded article has excellent abrasion resistance.

WO 03/035705

However, the random copolymer styrene-based elastomer described in Patent Document 1 has a problem that it has poor dispersibility in polypropylene resin, and therefore when it is mixed with polypropylene resin, it does not have sufficient processability.In addition, the strands are easily broken during extrusion, so that the extrusion moldability is also insufficient.
Furthermore, in recent years, with the increasing demand for car sharing and self-driving cars, high design quality is required for materials for automotive interiors, and in view of such design quality, there is a demand for the production of molded articles with complex shapes.
Molded articles with complex shapes are mainly produced by injection molding, but in this case, the material for the molded article needs to have a high melt flow rate (hereinafter, MFR). Therefore, there is a demand for resin compositions with a higher MFR while maintaining required performance such as abrasion resistance.

The present invention aims to provide a hydrogenated block copolymer capable of providing a resin composition having excellent abrasion resistance and a high MFR, a resin composition containing the hydrogenated block copolymer, and a molded article.

Means for Solving the Problems of the Prior Art As a result of intensive research conducted by the present inventors in order to solve the problems of the prior art described above, it has been found that a resin composition having improved abrasion resistance and MFR can be provided by using a hydrogenated block copolymer having a specific structure, in which the content of a polymer block mainly composed of a vinyl aromatic compound monomer unit, the weight average molecular weight, the hydrogenation rate, the area in a GPC curve for a specific range of molecular weights, the vinyl bond amount, and the content of a vinyl aromatic compound monomer unit in the specific polymer block are specified, and thus the present invention has been completed.
That is, the present invention is as follows.

[1]
A hydrogenated block copolymer comprising vinyl aromatic compound monomer units and conjugated diene monomer units,
A hydrogenated block copolymer satisfying the following requirements (1) to (7):
(1): (b) Contains at least one hydrogenated copolymer block composed of vinyl aromatic compound monomer units and conjugated diene monomer units.
(2): (a) has a polymer block mainly composed of a vinyl aromatic compound monomer unit, and the content of the polymer block mainly composed of a vinyl aromatic compound monomer unit (a) is 1 mass % or more and 40 mass % or less.
(3): The weight average molecular weight (Mw) is 200,000 or less.
(4): The hydrogenation rate of the double bonds of the conjugated diene monomer units is 20% or more.
(5): In a molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC) measurement, the ratio of the area in the molecular weight range of 10,000 to 150,000 to the area in the molecular weight range of 10,000 to 1,000,000 is more than 50% and 88% or less, and the ratio of the area in the molecular weight range of 200,000 to 1,000,000 to the area in the molecular weight range of 10,000 to 1,000,000 is 10% or more .
(6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more.
(7): The content of vinyl aromatic compound monomer units in the (b) hydrogenated copolymer block is 45% by mass or more and 79% by mass or less;
The hydrogenated block copolymer has a total vinyl aromatic compound monomer unit content of 40% by mass or more and 80% by mass or less.
[2]
The hydrogenated block copolymer according to [1] above, wherein the amount of vinyl bonds in the hydrogenated block copolymer is 30% by mass or more.
[3]
The hydrogenated block copolymer according to [1] or [2] above, wherein the content of the polymer block (a) mainly composed of vinyl aromatic compound monomer units is 1 mass% or more and 20 mass% or less.
[4]
(c) containing 1% by mass or more of a hydrogenated polymer block mainly composed of a conjugated diene monomer unit;
The hydrogenated block copolymer according to any one of [1] to [3] above.
[5]
The hydrogenated block copolymer according to any one of [1] to [4] above, wherein at least one tan δ peak in a viscoelasticity measurement chart is present at a temperature between 0° C. and 30° C.
[6]
The hydrogenated block copolymer (a) according to any one of [1] to [5] above: 1% by mass or more and 95% by mass or less;
At least one type of olefin resin (ii): 5% by mass or more and 99% by mass or less;
A hydrogenated block copolymer composition comprising:
[7]
The hydrogenated block copolymer composition according to [6] above, wherein the olefin resin (b) contains at least one polypropylene resin.
[8]
A molded article of the hydrogenated block copolymer composition according to [6] or [7] above.

According to the present invention, a hydrogenated block copolymer is obtained that, when combined with a polyolefin to form a resin composition, provides excellent abrasion resistance and a high MFR.

The following describes in detail the form for carrying out the present invention (hereinafter referred to as the "present embodiment"). Note that the following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content, and the present invention can be carried out in various modifications within the scope of its gist.

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

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

(Conjugated diene monomer units)
The hydrogenated block copolymer (a) of this embodiment contains conjugated diene monomer units.
The conjugated diene monomer unit is a monomer unit derived from a diolefin having a pair of conjugated double bonds, such as, but not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc.
In particular, 1,3-butadiene and isoprene are preferred from the viewpoint of a good balance between moldability and mechanical strength.
These may be used alone or in combination of two or more.

In the hydrogenated block copolymer (a) of this embodiment, the amount of vinyl bonds in the conjugated diene monomer units is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more.
When the vinyl bond content in the conjugated diene monomer unit of the hydrogenated block copolymer (a) is 20% by mass or more, the hydrogenated block copolymer composition of the present embodiment, which combines the hydrogenated block copolymer (a) with the olefin resin (b) described below, tends to have improved hardness and extrusion moldability, and when it is 30% by mass or more, the MFR and abrasion resistance in particular tend to be good. The higher the vinyl bond content, the more the above physical properties improve.
The vinyl bond amount of the hydrogenated block copolymer (a) can be controlled by using a regulator such as a tertiary amine compound or an ether compound described later.

In the hydrogenated block copolymer (a) of the present embodiment, the content of all vinyl aromatic compound monomer units is preferably 40% by mass or more and 80% by mass or less, more preferably 45% by mass or more and 80% by mass or less, even more preferably 47% by mass or more and 78% by mass or less, and even more preferably 50% by mass or more and 75% by mass or less.
When the total content of vinyl aromatic compound monomer units is within the above range, the balance of hardness, extrusion moldability and abrasion resistance tends to be good.
In the present embodiment, the content of all vinyl aromatic compound monomer units in the hydrogenated block copolymer (a) can be measured using an ultraviolet spectrophotometer by using the block copolymer before hydrogenation and the hydrogenated block copolymer after hydrogenation as samples.
The total content of vinyl aromatic compound monomer units in the hydrogenated block copolymer (a) can be controlled within the above-mentioned numerical range mainly by adjusting the amount of vinyl aromatic compound added to the reactor, the reaction temperature and the reaction time.

In this specification, in the composition of the hydrogenated block copolymer, the term "mainly composed of" means that the proportion in a predetermined block polymer or polymer block is 85 mass % or more, preferably 90 mass % or more, and more preferably 95 mass % or more.
In addition, since the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 30% by mass or more and 79% by mass or less, the polymer block (a) and the hydrogenated polymer block (b) can be clearly distinguished from each other.

(Polymer block (a) mainly composed of vinyl aromatic compound)
The hydrogenated block copolymer (i) of this embodiment contains at least one polymer block (a) mainly composed of vinyl aromatic compound monomer units, from the viewpoint of preventing pellet blocking.
In addition, the hydrogenated block copolymer (a) of the present embodiment has a content of the polymer block (a) of 40% by mass or less, preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.
When the content of the polymer block (a) in the hydrogenated block copolymer (i) of the present embodiment is 40 mass% or less, the hydrogenated block copolymer composition of the present embodiment described later has a good balance between abrasion resistance and hardness.

The content of the polymer block (a) can be measured by a method using a nuclear magnetic resonance (NMR) apparatus (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981) (hereinafter referred to as the "NMR method") using a block copolymer before hydrogenation or a hydrogenated block copolymer after hydrogenation as a sample.
The content of the polymer block (a) in the hydrogenated block copolymer (a) can be controlled within the above-mentioned numerical range mainly by adjusting the amount of the vinyl aromatic compound added to the reactor, the reaction temperature and the reaction time.

(Hydrogenated Copolymer Block (b))
The hydrogenated block copolymer (i) of this embodiment contains a hydrogenated copolymer block (b) composed of a vinyl aromatic compound monomer unit and a conjugated diene monomer unit.
The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is from 30% by mass to 79% by mass, preferably from 40% by mass to 79% by mass, more preferably from 45% by mass to 79% by mass, and even more preferably from 45% by mass to 70% by mass.

When the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 30% by mass or more and 79% by mass or less, the hydrogenated block copolymer composition of the present embodiment described below exhibits good abrasion resistance.Furthermore, when the content is 45% by mass or more and 79% by mass or less, higher abrasion resistance is exhibited, and the composition can be used in applications where stricter abrasion resistance is required.
Furthermore, when the content of the vinyl aromatic compound monomer units in the hydrogenated copolymer block (b) is 79 mass% or less, the extrusion moldability of the hydrogenated block copolymer composition of the present embodiment described later tends to be improved, but the hardness tends to be decreased.
In this embodiment, the content of vinyl aromatic compound monomer units in the hydrogenated copolymer block (b) in the hydrogenated block copolymer (a) can be measured by a nuclear magnetic resonance (NMR) spectrometer or the like.
The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) can be controlled within the above-mentioned numerical range mainly by adjusting the amounts of the vinyl aromatic compound and the conjugated diene added to the reactor and the reaction temperature.

The vinyl bond amount of the conjugated diene portion in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) can be controlled by using a regulator such as a tertiary amine compound or an ether compound described later.
When 1,3-butadiene is used as the conjugated diene, from the viewpoint of obtaining a good balance of abrasion resistance, MFR, and hardness in the hydrogenated block copolymer composition of the present embodiment described later, the 1,2-vinyl bond amount of the conjugated diene portion in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) is preferably 25% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 90% by mass or less.
When isoprene is used as the conjugated diene, or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 3% by mass or more and 75% by mass or less, and more preferably 5% by mass or more and 60% by mass or less.
In this embodiment, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds) is referred to as the amount of vinyl bonds.
The vinyl bond content can be measured by using an infrared spectrophotometer (for example, the Hampton method) to measure the copolymer before hydrogenation as a sample.

(Hydrogenated polymer block (c) mainly composed of conjugated diene monomer units)
The hydrogenated block copolymer (i) of this embodiment preferably contains a hydrogenated polymer block (c) mainly composed of conjugated diene monomer units.
In the hydrogenated block copolymer (a) of the present embodiment, the content of the hydrogenated polymer block (c) is preferably 1 mass% or more, more preferably 2 mass% or more and 20 mass% or less, even more preferably 2 mass% or more and 15 mass% or less, and still more preferably 2 mass% or more and 8 mass% or less, from the viewpoints of the MFR and hardness of the hydrogenated block copolymer (a) and the balance between the MFR, abrasion resistance and hardness of the hydrogenated block copolymer composition of the present embodiment described later.
The content of the hydrogenated polymer block (c) in the hydrogenated block copolymer (a) can be controlled within the above-mentioned numerical range mainly by controlling the amount of conjugated diene added to the reactor and the reaction temperature.

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

(tan δ (loss tangent) in the viscoelasticity measurement chart of hydrogenated block copolymer (a))
In the hydrogenated block copolymer (a) of this embodiment, in a viscoelasticity measurement chart, at least one tan δ (loss tangent) peak is preferably present at a temperature between −25° C. and 40° C., more preferably between −15° C. and 35° C., even more preferably between −10° C. and 30° C., and even more preferably between 0° C. and 30° C.
This tan δ peak is a peak due to the hydrogenated copolymer block (b) in the hydrogenated block copolymer (a). The presence of at least one such peak in the range of −25° C. to 40° C. is important for maintaining the hardness of the hydrogenated block copolymer and the abrasion resistance and good tactile feel in the hydrogenated block copolymer composition of the present embodiment described later.
As described above, the hydrogenated copolymer block (b) is obtained by hydrogenating a copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units.
In order to have at least one peak of tan δ (loss tangent) in the range of -25°C or more and 40°C or less, it is effective to control the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio), and the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio) is preferably 75/25 to 16/84, more preferably 70/30 to 18/82, and even more preferably 60/40 to 25/75.
In order to have at least one peak of tan δ (loss tangent) in the range of 0° C. or more and 30° C. or less, it is effective to control the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio), and the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio) is preferably 65/35 to 16/84, more preferably 60/40 to 25/75, and even more preferably 55/45 to 30/70.
Tan δ can be measured using a viscoelasticity measuring device (ARES, manufactured by TA Instruments Co., Ltd.) under conditions of a strain of 0.5%, a frequency of 1 Hz, and a temperature rise rate of 3° C./min. Specifically, it can be measured by the method described in the Examples below.

(Weight average molecular weight of hydrogenated block copolymer (a))
The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) of this embodiment is 200,000 or less, and from the viewpoint of obtaining a good balance of abrasion resistance, MFR, hardness, and pellet blocking properties in the hydrogenated block copolymer composition of this embodiment described later, it is preferably from 50,000 to 190,000, more preferably from 60,000 to 180,000, and even more preferably from 70,000 to 170,000.
In the present embodiment, the weight average molecular weight of the hydrogenated block copolymer (a) is determined by measuring by gel permeation chromatography (GPC) and using a calibration curve (created using the peak molecular weights of the standard polystyrene) obtained from the measurement of commercially available standard polystyrene.

(Distribution in molecular weight curve of hydrogenated block copolymer (a))
In the GPC curve of the hydrogenated block copolymer (a) of this embodiment, the ratio (%) of the area in the molecular weight range of 10,000 to 150,000 to the area in the molecular weight range of 10,000 to 1,000,000 exceeds 50%.
From the viewpoint of obtaining a good balance between abrasion resistance, MFR, hardness and pellet blocking resistance, the content is more than 50%, preferably 60 to 99%, and more preferably 70 to 95%.
The greater the proportion of the area in the range of molecular weight from 10,000 to 150,000, the higher the MFR and the lower the hardness. Conversely, the smaller the proportion, the higher the abrasion resistance and the lower the pellet blocking tendency.
The proportion of the area of the molecular weight range of 10,000 to 150,000 in the GPC curve of the hydrogenated block copolymer (a) of this embodiment can be controlled to within the above-mentioned numerical range by controlling the amounts of the polymerization initiator and coupling agent, or by mixing two or more types of polymers having appropriate molecular weight distributions.

In addition, in the GPC curve of the hydrogenated block copolymer (a) of this embodiment, the ratio (%) of the area in the molecular weight range of 200,000 to 1,000,000 to the area in the molecular weight range of 10,000 to 1,000,000 is preferably 10% or more, and more preferably 20% or more, from the viewpoint of achieving a balance between abrasion resistance and pellet blocking properties.
The greater the proportion of the area in the range of molecular weight of 200,000 to 1,000,000, the more improved the abrasion resistance and the less prone to pellet blocking.
In particular, in order to improve abrasion resistance and pellet blocking, it is preferable that the proportion of the area in the range where the molecular weight of the hydrogenated block copolymer (a) is 200,000 or more is in the above-mentioned numerical range, it is more preferable that the proportion of the area in the range where the molecular weight is 220,000 or more is in the above-mentioned numerical range, and it is even more preferable that the proportion of the area in the range where the molecular weight is 240,000 or more is in the above-mentioned numerical range.
In order to improve the MFR, it is preferable that the proportion of the area in the range where the molecular weight of the hydrogenated block copolymer (a) is 1,000,000 or less is in the above-mentioned numerical range, more preferably the area in the range where it is 700,000 or less is in the above-mentioned numerical range, even more preferably the area in the range where it is 500,000 or less is in the above-mentioned numerical range, and even more preferably the area in the range where it is 300,000 or less is in the above-mentioned numerical range.
The proportion of the area in the GPC curve of the hydrogenated block copolymer (a) of this embodiment corresponding to a molecular weight of 200,000 to 1,000,000 can be controlled within the above-mentioned numerical range by adjusting the amounts of the polymerization initiator and coupling agent, or by mixing two or more types of polymers having appropriate molecular weight distributions.

(Hydrogenation rate of double bonds of conjugated diene monomer units in hydrogenated block copolymer (a))
The hydrogenation rate of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer (a) of this embodiment is 20% or more, preferably 50% or more, more preferably 85% or more, and even more preferably 92% or more, from the viewpoint of obtaining good hardness and MFR in the hydrogenated block copolymer composition of this embodiment described later.
The hydrogenation rate of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer (a) can be controlled within the above-mentioned numerical range by adjusting the amount of hydrogenation.

(Hydrogenation rate of aromatic double bonds of vinyl aromatic compound units in hydrogenated block copolymer (a))
The hydrogenation rate of the aromatic double bonds of the vinyl aromatic compound units in the hydrogenated block copolymer (a) of the present embodiment is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less.
The hydrogenation rate of the hydrogenated block copolymer (a) can be measured by using a nuclear magnetic resonance (NMR) spectrometer or the like.

(Crystallization peak of hydrogenated block copolymer (a))
The hydrogenated block copolymer (a) of the present embodiment is preferably a hydrogenated product in which a crystallization peak due to the hydrogenated copolymer block (b) is substantially not present in the range of −25 to 80° C. in a differential scanning calorimetry (DSC) chart.
Here, "there is substantially no crystallization peak due to the hydrogenated copolymer block (b) in the range of -25 to 80°C" means that, in this temperature range, no peak due to crystallization of the hydrogenated copolymer block (b) appears, or even if a peak due to crystallization is observed, the crystallization peak heat quantity due to the crystallization is less than 3 J/g, preferably less than 2 J/g, more preferably less than 1 J/g, and even more preferably there is no crystallization peak heat quantity.

As described above, when there is substantially no crystallization peak due to the hydrogenated copolymer block (b) in the range of −25 to 80° C., the hydrogenated block copolymer (a) of this embodiment has good flexibility, and the hydrogenated block copolymer composition of this embodiment, which will be described later, is preferably softened.
In order to obtain the hydrogenated block copolymer (i) in which a crystallization peak due to the hydrogenated copolymer block (b) does not substantially exist in the range of −25 to 80° C., a copolymer obtained by carrying out a polymerization reaction under the conditions described below using a predetermined regulator for adjusting the vinyl bond amount and the copolymerizability between the vinyl aromatic compound and the conjugated diene may be subjected to a hydrogenation reaction.

(Structure of hydrogenated block copolymer (a))
The structure of the hydrogenated block copolymer (a) of this embodiment is not particularly limited, and examples thereof include those having a structure represented by the following general formula.
(b-c) _n , c-(b-c) _n , b-(c-b) _n , (b-c) _m -X, (c-b) _m- X, c-(ba-a) _n , c-(a-b) _n , c-(a-b-a) _n , c-(b-a-b) _n , c-(b-c-a) _n , a-(c-b-c-a) _n , a-c-( b-a) _n , a-c-(a-b) _n , a-c-(b-a) _n -b, [(a-b-c) _n ] _m -X, [a-(b-c) _n ] _m -X, [(a-b) _n -c] _m -X, [(a-b-a) _n -c] _m -X, [(b-a-b) _n -c] _m -X, [(c-b-a) ) _n ] _m -X, [c-(ba-a) _n ] _m -X, [c-(a-ba) _n ] _m -X, [c-(b-a-b) _n ] _m -X
In each of the above general formulas, a represents a polymer block (a) mainly composed of vinyl aromatic compound monomer units, b represents a hydrogenated copolymer block (b) composed of vinyl aromatic compound monomer units and conjugated diene monomer units, and c represents a hydrogenated polymer block (c) mainly composed of conjugated diene monomer units.
n is an integer of 1 or more, and preferably an integer of 1 to 5.
m is an integer of 2 or more, and preferably an integer of 2 to 11.
X represents a residue of a coupling agent or a residue of a multifunctional initiator.

(Another example of the structure of hydrogenated block copolymer (a))
The hydrogenated block copolymer (a) of this embodiment may be a modified block copolymer in which an atomic group having a predetermined functional group is bonded.
The modified block copolymer may also be a secondary modified block copolymer.

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

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

(Polymerization initiator)
The polymerization initiator is not particularly limited, but examples of the polymerization initiator that can be used include organic alkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds, which are generally known to have anionic polymerization activity for vinyl aromatic compounds and conjugated dienes.
The organic alkali metal compound is not limited to the following, but for example, an aliphatic or aromatic hydrocarbon lithium compound having 1 to 20 carbon atoms is preferable, and a compound containing one lithium atom in one molecule, a dilithium compound containing multiple lithium atoms in one molecule, a trilithium compound, or a tetralithium compound can be used.
Specific examples of such lithium lithium include n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, a reaction product of diisopropenylbenzene with sec-butyl lithium, and a reaction product of divinylbenzene with sec-butyl lithium and a small amount of 1,3-butadiene.
Furthermore, for example, the organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent No. 2,241,239, and US Pat. No. 5,527,753 can also be used.

(Adjusting agent)
For example, when an organic alkali metal compound is used as a polymerization initiator to copolymerize a vinyl aromatic compound with a conjugated diene, the content of vinyl bonds (1,2 bonds or 3,4 bonds) resulting from the conjugated diene incorporated in the polymer and the random copolymerizability of the vinyl aromatic compound with the conjugated diene can be adjusted by using a specific regulator.
Such regulators include, but are not limited to, tertiary amine compounds, ether compounds, metal alcoholate compounds, and the like.
The regulator may be used alone or in combination of two or more kinds.

The tertiary amine compound is not limited to the following, but for example, a compound represented by the general formula R1R2R3N (wherein R1, R2, and R3 each represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group) can be used.
Specific examples include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N",N"-pentamethylethylenetriamine, and N,N'-dioctyl-p-phenylenediamine.

The ether compound is not limited to the following, but for example, a linear ether compound and a cyclic ether compound can be used.
Examples of linear ether compounds include, but are not limited to, dialkyl ether compounds 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 ether compounds of diethylene glycol, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Examples of the cyclic ether compound include, but are not limited to, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers of furfuryl alcohol.

Metal alcoholate compounds include, but are not limited to, sodium t-pentoxide, sodium t-butoxide, potassium t-pentoxide, potassium t-butoxide, etc.

(Polymerization method)
Furthermore, for example, as a method for polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be applied.
Although not limited thereto, for example, any of batch polymerization, continuous polymerization, and a combination of these may be used, with batch polymerization being particularly suitable for obtaining a copolymer having 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, but is usually within 48 hours, preferably 0.1 to 10 hours.
The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
The polymerization pressure is not particularly limited as long as it is set within a pressure range that allows the monomer and the solvent to be maintained in a liquid phase within the above-mentioned temperature range.
Furthermore, it is preferable to take care not to introduce impurities such as water, oxygen, carbon dioxide gas, etc., which may inactivate the catalyst and the living polymer, into the polymerization system.

At the end of the polymerization step, a required amount of a bifunctional or higher functional coupling agent may be added to carry out a coupling reaction.
The bifunctional coupling agent may be any known one and is not particularly limited. For example, 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 phthalic acid esters can be mentioned.
As the polyfunctional coupling agent having three or more functionalities, conventionally known ones can be used, and there is no particular limitation. For example, polyhydric polyalcohols having three or more functionalities, epoxidized soybean oil, diglycidyl bisphenol A, polyvalent epoxy compounds such as 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, halogenated silicon compounds represented by the general formula R ₄ -nSiX _n (where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride and brominated products thereof, and halogenated tin compounds represented by the general formula R ₄ -nSnX _n (where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), such as polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Dimethyl carbonate, diethyl carbonate, and the like may also be used.

(Modification step)
As described above, the hydrogenated block copolymer (a) of the present embodiment may be a modified block copolymer to which an atomic group having a functional group is bonded. The atomic group having a functional group is preferably bonded in a step prior to the hydrogenation step described below.
The "atomic group having a functional group" is not particularly limited, and examples thereof include atomic groups containing at least one functional group selected from hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylate group, amide group, sulfonic acid group, sulfonate group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxy silicon group, tin halide group, boronic acid group, boron-containing group, boronate base, alkoxy tin group, phenyl tin group, etc. In particular, atomic groups containing at least one functional group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxy silane group are preferred.
The "atomic group having a functional group" is bonded via a modifying agent.
The modifying agent is not particularly limited, but examples thereof include tetraglycidyl meta-xylylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl dimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, and N-methylpyrrolidone.

The modified block copolymer is not particularly limited, but can be obtained, for example, by anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group, forming a functional group at the living end, or by addition reaction of a modifying agent containing a functional group.
As another method, the block copolymer can be obtained by reacting an organic alkali metal compound such as an organolithium compound with the block copolymer (metallation reaction), and then subjecting the block copolymer to an addition reaction with a modifier having a functional group.
However, in the latter method, the hydrogenated block copolymer (a) may be subjected to a metallation reaction, and then reacted with a modifying agent to prepare a modified hydrogenated block copolymer.
The temperature at which the modification reaction is carried out is preferably 0 to 150° C., more preferably 20 to 120° C. The time required for the modification reaction varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours.
Depending on the type of modifying agent used, the amino group etc. may generally be in the form of an organometallic salt at the stage of reacting with the modifying agent, in which case it can be converted to an amino group etc. by treating with a compound having active hydrogen such as water or alcohol. In such modified copolymers, the modified copolymer may contain a partly unmodified copolymer.

The modified block copolymer may be a secondary modified block copolymer obtained by reacting the modified block copolymer with a secondary modifying agent having reactivity with the functional group of the modified block copolymer.
The secondary modifying agent is not particularly limited, but examples thereof include a modifying agent having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group, and the secondary modifying agent has at least two functional groups selected from these functional groups.
However, when the functional group is an acid anhydride group, it may have one acid anhydride group.

As described above, when the secondary modifier is reacted with the modified block copolymer, the amount of the secondary modifier used is preferably 0.3 to 10 mol, more preferably 0.4 to 5 mol, and even more preferably 0.5 to 4 mol, per equivalent of the functional group bonded to the modified block copolymer.
The method of reacting the modified block copolymer with the secondary modifier is not particularly limited and may be any known method. For example, the melt-kneading method described below and the method of dissolving or dispersing and mixing each component in a solvent or the like and reacting them may be mentioned. It is preferable that these secondary modifications are carried out after the hydrogenation step.

Specific examples of suitable secondary modifiers include maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, and bis-(3-triethoxysilylpropyl)-tetrasulfane.

The hydrogenated block copolymer (a) of the present embodiment may be a modified block copolymer graft-modified with an α,β-unsaturated carboxylic acid or a derivative thereof, for example, an anhydride, an ester, an amide, or an imide thereof.
Specific examples of the α,β-unsaturated carboxylic acid or a derivative thereof include, but are not limited to, maleic anhydride, maleic anhydride imide, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or anhydride thereof, and the like.
The amount of the α,β-unsaturated carboxylic acid or its derivative added is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the hydrogenated block copolymer (a).
The reaction temperature in the case of graft modification is preferably from 100 to 300°C, more preferably from 120 to 280°C.
The specific method for graft modification is not particularly limited, but for example, the method described in JP-A-62-79211 can be applied.

(Hydrogenation reaction step)
The hydrogenated block copolymer (a) of this embodiment can be obtained by subjecting the above-mentioned non-hydrogenated unmodified or modified block copolymer to a hydrogenation reaction using a predetermined hydrogenation catalyst.
The hydrogenation catalyst is not particularly limited, and examples of the known catalysts that can be used include (1) supported heterogeneous hydrogenation catalysts in which a metal such as Ni, Pt, Pd, Ru, etc. is supported on carbon, silica, alumina, diatomaceous earth, etc., (2) so-called Ziegler type hydrogenation catalysts which use a transition metal salt such as an organic acid salt or an acetylacetone salt of Ni, Co, Fe, Cr, etc., and a reducing agent such as organoaluminum, and (3) homogeneous hydrogenation catalysts such as so-called organometallic complexes of organometallic compounds such as Ti, Ru, Rh, Zr, etc.
Specifically, the hydrogenation catalysts that can be used include, but are not limited to, those described in JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, and JP-B-2-9041.
Suitable hydrogenation catalysts include titanocene compounds, reducing organometallic compounds, or mixtures thereof.
Examples of the titanocene compound include, but are not limited to, compounds described in JP-A-8-109219. Specific examples include compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride.
Examples of the reducing organometallic compound include, but are not limited to, organoalkali metal compounds such as organolithium compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The hydrogenation reaction will now be described.
The reaction temperature is generally preferably in the range of 0 to 200°C, more preferably in the range of 30 to 150°C.
The pressure of hydrogen used in the hydrogenation reaction is preferably from 0.1 to 15 MPa, more preferably from 0.2 to 10 MPa, and even more preferably from 0.3 to 5 MPa.
The hydrogenation reaction time is usually preferably from 3 minutes to 10 hours, more preferably from 10 minutes to 5 hours.
The hydrogenation reaction may be a batch process, a continuous process, or a combination thereof.
It is preferable to remove catalyst residues, if necessary, from the solution of the hydrogenated block copolymer obtained through the hydrogenation reaction, and separate the hydrogenated block copolymer from the solution.
Examples of the separation method include, but are not limited to, a method in which a polar solvent that is a poor solvent for the hydrogenated modified copolymer, such as acetone or alcohol, is added to the reaction solution after hydrogenation to precipitate and recover the polymer; a method in which the reaction solution is poured into boiling water with stirring and the solvent is removed by steam stripping to recover the polymer; and a method in which the polymer solution is directly heated to distill off the solvent.
The hydrogenated block copolymer (a) of this embodiment may contain various stabilizers, such as phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers.

[Hydrogenated Block Copolymer Composition]
The hydrogenated block copolymer composition of the present embodiment contains the above-mentioned (i) hydrogenated block copolymer: 1% by mass or more and 95% by mass or less, and (ii) at least one type of olefin resin: 5% by mass or more and 99% by mass or less.

((b) Olefin-based resin)
The olefin resin (b) constituting the hydrogenated block copolymer composition of this embodiment will be described below.
Examples of the olefin resin (ii) include, but are not limited to, homopolymers of α-olefins such as polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, etc. Also included are random copolymers or block copolymers made of a combination of olefins selected from ethylene, propylene, butene, pentene, hexene, octene, etc.
Specific examples thereof include ethylene and/or propylene-α-olefin copolymers such as 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, and propylene-1-octene-ethylene copolymers.
The copolymers with ethylene and/or propylene also include copolymers with other unsaturated monomers.
Examples of the copolymer with other unsaturated monomers include, but are not limited to, copolymers of ethylene and/or propylene with unsaturated organic acids or derivatives thereof, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, arylmaleic imide, and alkylmaleic imide; copolymers of ethylene and/or propylene with vinyl esters, such as vinyl acetate; and copolymers of ethylene and/or propylene with non-conjugated dienes, such as dicyclopentadiene, 4-ethylidene-2-norbornene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene.
From the viewpoints of economy and of obtaining good compatibility in the hydrogenated block copolymer composition of the present embodiment and thus high transparency, it is preferable that the (b) olefin-based resin contains at least one type of polypropylene-based resin.

The olefin resin (ii) may be modified with a predetermined functional group.
The functional group is not particularly limited, but examples thereof include an epoxy group, a carboxy group, an acid anhydride group, and a hydroxyl group.
The functional group-containing compound or modifier for modifying the olefin resin (ii) is not particularly limited, but examples thereof include the following compounds.
Examples of the unsaturated epoxides include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether; and unsaturated organic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, and itaconic anhydride.
Other examples include, but are not limited to, ionomers, chlorinated polyolefins, and the like.

The olefin resin (b) is preferably a polypropylene resin such as a polypropylene homopolymer or an ethylene-propylene random or block copolymer, from the viewpoints of economy and of obtaining good compatibility in the hydrogenated block copolymer composition of the present embodiment and high transparency.
In particular, from the viewpoints of transparency and flexibility, ethylene-propylene random copolymers are more preferable.
The olefin-based resin (ii) may be composed of only one type of material, or may be composed of two or more types in combination.

The hydrogenated block copolymer composition in the present embodiment contains the hydrogenated block copolymer (A) and at least one kind of olefin resin (B), and the content of the hydrogenated block copolymer (A) is 1% by mass or more and 95% by mass or less, more preferably 1% by mass or more and 90% by mass or less, and even more preferably 1% by mass or more and 85% by mass or less.
When the content of the hydrogenated block copolymer (a) is 1% by mass or more, the abrasion resistance of the hydrogenated block copolymer composition tends to be improved and the hardness tends to be reduced, whereas when the content of the hydrogenated block copolymer (a) is 95% by mass or less, the abrasion resistance of the hydrogenated block copolymer composition tends to be improved.

The hydrogenated block copolymer composition of the present embodiment may contain any rubber softener, modifier, additive, and the like in addition to the hydrogenated block copolymer (a) and polyolefin resin (b) described above.
The rubber softener softens the hydrogenated block copolymer composition of the present embodiment and imparts fluidity (moldability) to the composition.
The rubber softener is not limited to the following, but for example, mineral oils and liquid or low molecular weight synthetic softeners can be used, and naphthenic and/or paraffinic process oils or extender oils are particularly suitable.
Mineral oil-based rubber softeners are mixtures of aromatic rings, naphthenic rings, and paraffin chains; those in which the carbon number of the paraffin chains accounts for 50% or more of the total carbon are called paraffinic, those in which the carbon number of the naphthenic rings accounts for 30-45% are called naphthenic, and those in which the aromatic carbon number exceeds 30% are called aromatic.
As the synthetic softener, for example, polybutene, low molecular weight polybutadiene, liquid paraffin, etc. can be used, but the above-mentioned mineral oil-based rubber softeners are more preferable.
When high heat resistance and mechanical properties are required for the hydrogenated block copolymer composition of this embodiment, the mineral oil-based rubber softener to be applied preferably has a kinetic viscosity at 40° C. of 60 cst or more, more preferably 120 cst or more.
The rubber softener may be used alone or in combination of two or more kinds.
The modifier has the function of improving the scratch resistance and adhesiveness of the surface of the hydrogenated block copolymer composition of this embodiment.
The modifier is not limited to the following, but for example, organic polysiloxane can be used, which exerts a surface modifying effect on the hydrogenated block copolymer composition and also functions as an auxiliary agent for improving abrasion resistance.
The form of the modifier may be any of low-viscosity liquid to high-viscosity liquid and solid, but from the viewpoint of ensuring good dispersibility in the hydrogenated block copolymer composition of this embodiment, liquid, i.e., silicone oil, is preferred. Furthermore, the kinetic viscosity is preferably 90 cst or more, more preferably 1000 cst or more, from the viewpoint of suppressing bleeding of the polysiloxane itself. Examples of polysiloxane include, but are not limited to, general-purpose silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, and various modified silicone oils such as alkyl-modified, polyether-modified, fluorine-modified, alcohol-modified, amino-modified, and epoxy-modified. Although not particularly limited, dimethylpolysiloxane is preferred because of its high effect as an abrasion resistance improving assistant. These organic polysiloxanes may be used alone or in combination of two or more.
The additives are not particularly limited as long as they are generally used in compounding a filler, a lubricant, a release agent, a plasticizer, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, a reinforcing agent, a colorant, and a thermoplastic resin or a rubber-like polymer.
Examples of fillers include, but are not limited to, inorganic fillers such as silica, talc, mica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, and barium sulfate, and organic fillers such as carbon black.
Examples of lubricants include, but are not limited to, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearamide.
Examples of the plasticizer include, but are not limited to, organic polysiloxanes and mineral oils.
The antioxidant includes, but is not limited to, a hindered phenol-based antioxidant.
Examples of the heat stabilizer include, but are not limited to, phosphorus-based, sulfur-based and amine-based heat stabilizers.
Examples of light stabilizers include, but are not limited to, hindered amine light stabilizers.
Examples of the ultraviolet absorbing agent include, but are not limited to, benzotriazole-based ultraviolet absorbing agents.
Examples of the reinforcing agent include, but are not limited to, organic fibers, glass fibers, carbon fibers, and metal whiskers.
Examples of colorants include, but are not limited to, titanium oxide, iron oxide, and carbon black.
Other examples include those described in "Rubber and Plastic Compounding Chemicals" (edited by Rubber Digest Co., Ltd.).

The hydrogenated block copolymer composition of the present embodiment can be produced by a conventionally known method.
The method for producing the hydrogenated block copolymer composition of this embodiment is not limited to the following, but examples thereof include a method of melt-kneading each component (the hydrogenated block copolymer (a), the polyolefin resin (b), and other additives) using a mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, or a multi-screw extruder, and a method of dissolving or dispersing and mixing each component and then removing the solvent by heating.
In particular, the melt kneading method using an extruder is preferable from the viewpoints of productivity and good kneading properties.
The shape of the hydrogenated block copolymer composition of the present embodiment is not limited to the following, and may be any shape, such as pellets, sheets, strands, chips, etc. After melt-kneading, a molded article may be produced directly.

[Molded article using hydrogenated block copolymer composition]
The molded article of the present embodiment is a molded article of the hydrogenated block copolymer composition of the present embodiment described above.
The hydrogenated block copolymer composition of the present embodiment can be processed into a practically useful molded article by, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, blow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, lamination molding, calendar molding, blow molding, or the like, without any particular limitation.
The molded article of the present embodiment is not particularly limited, but examples thereof include a wide variety of molded articles such as sheets, films, injection molded articles of various shapes, hollow molded articles, compressed air molded articles, vacuum molded articles, extrusion molded articles, foam molded articles, nonwoven fabrics and fibrous molded articles, and synthetic leather.
These molded articles can be used, for example, for automobile parts, food packaging materials, medical instruments, home appliance parts, electronic device parts, building materials, industrial parts, household goods, toy materials, footwear materials, textile materials, and the like.

Examples of automotive parts include, but are not limited to, side moldings, grommets, shift knobs, weather strips, window frames and their sealing materials, arm rests, assist grips, door grips, handle grips, console boxes, head rests, instrument panels, bumpers, spoilers, and air bag covers.
Examples of medical devices include, but are not limited to, medical tubes, medical hoses, catheters, blood bags, infusion bags, platelet storage bags, and artificial dialysis bags.
Examples of building materials include, but are not limited to, wall materials, floor materials, and the like.
Other examples include, but are not limited to, industrial hoses, food hoses, vacuum cleaner hoses, electrical cooling packing, various covering materials for electrical wires and the like, covering materials for grips, soft dolls, and the like.
The molded article of this embodiment may be appropriately subjected to processing such as foaming, powdering, stretching, bonding, printing, painting, plating, and the like.
The hydrogenated block copolymer composition of the present embodiment exhibits excellent effects such as flexibility, low impact resilience, transparency, and kink resistance, and is therefore extremely useful as a material for hollow molded articles such as hoses and tubes.

(Reinforcing filler compound)
A reinforcing filler blend can be prepared by blending at least one reinforcing filler selected from a silica-based inorganic filler, a metal oxide, a metal hydroxide, a metal carbonate, and carbon black (hereinafter, may be referred to as component (C)) with the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment (hereinafter, may be referred to as component (A)).
The amount of component (C) in the reinforcing filler composition is preferably 0.5 to 100 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 20 to 80 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition.
When the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)) of the present embodiment is used to prepare the reinforcing filler blend, it is preferable that the component (A) further contains 0 to 500 parts by mass, preferably 5 to 300 parts by mass, and more preferably 10 to 200 parts by mass of a thermoplastic resin and/or a rubber-like polymer (hereinafter, sometimes referred to as component (B)) different from the hydrogenated block copolymer of the present embodiment and the olefin-based resin (b), relative to 100 parts by mass of component (A).

Examples of the thermoplastic resin and/or rubber-like polymer (component (B)) include block copolymer resins of a conjugated diene monomer and a vinyl aromatic monomer having a vinyl aromatic monomer unit content of more than 60 mass% and hydrogenated products thereof (however, different from the hydrogenated block copolymer (A) of the present embodiment); polymers of the vinyl aromatic monomers; copolymer resins of the vinyl aromatic monomers and other vinyl monomers (e.g., ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid, acrylic acid esters such as methyl acrylate, methacrylic acid, methyl methacrylate, acrylonitrile, methacrylonitrile, etc.); rubber-modified styrene-based resins (HIPS); acrylonitrile, Nitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resin (MBS); polyethylene; copolymers consisting of ethylene and other copolymerizable monomers and having an ethylene content of 50 mass% or more, such as ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and hydrolysates thereof; polyethylene-based resins such as ethylene-acrylic acid ionomer and chlorinated polyethylene; polypropylene; polypropylene-based resins such as propylene-ethylene copolymer, propylene-ethyl acrylate copolymer, and chlorinated polypropylene, and cyclic resins such as ethylene-norbornene resin. Copolymers of propylene and other copolymerizable monomers with a propylene content of 50% by mass or more, such as olefin resins, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins, and hydrolysates thereof; polymers of acrylic acid and its esters and amides; polyacrylate resins; polymers of acrylonitrile and/or methacrylonitrile; nitrile resins which are copolymers of acrylonitrile monomers and other copolymerizable monomers with an acrylonitrile monomer content of 50% by mass or more; polyamide resins such as nylon-46, nylon-6, nylon-66 nylon-610, nylon-11, nylon-12, nylon-6, and nylon-12 copolymers; polyester resins; heat Examples of the resin include thermoplastic polyurethane-based resins; polycarbonate-based polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polysulfones such as polyethersulfone and polyallylsulfone; polyoxymethylene-based resins; polyphenylene ether-based resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide-based resins such as polyphenylene sulfide and poly4,4'-diphenylene sulfide; polyarylate-based resins; polyether ketone polymers or copolymers; polyketone-based resins; fluorine-based resins; polyoxybenzoyl-based polymers; polyimide-based resins; and polybutadiene-based resins such as 1,2-polybutadiene and trans-polybutadiene.
These components (B) may be those having an atomic group containing a polar group such as a hydroxyl group, an epoxy group, an amino group, a carboxylic acid group, or an acid anhydride group bonded thereto.

The silica-based inorganic filler used as the reinforcing filler (component (C)) is a solid particle whose main component is the chemical formula _SiO2 , and examples thereof include inorganic fibrous substances such as silica, clay, talc, kaolin, mica, wollastonite, montmorillonite, zeolite, and glass fiber. In addition, silica-based inorganic fillers with hydrophobic surfaces and mixtures of silica-based inorganic fillers and inorganic fillers other than silica-based inorganic fillers can also be used. As the silica-based inorganic filler, silica and glass fiber are preferred. As the silica, dry-process white carbon, wet-process white carbon, synthetic silicate-based white carbon, and colloidal silica can be used.
The silica-based inorganic filler preferably has an average particle size of 0.01 to 150 μm. In order for the silica-based inorganic filler to disperse in the reinforcing filler compound and to fully exert the effect of adding it, the average dispersed particle size is preferably 0.05 to 1 μm, and more preferably 0.05 to 0.5 μm.

The metal oxide used as the reinforcing filler (component (C)) is a solid particle having a structural unit of the chemical formula MxOy (M is a metal atom, and x and y are each an integer of 1 to 6), as the main component, and is, for example, alumina, titanium oxide, magnesium oxide, zinc oxide, etc. Also, a mixture of a metal oxide and an inorganic filler other than a metal oxide may be used.
The metal hydroxides used as the reinforcing filler are hydrated inorganic fillers such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, hydrated tin oxide, and hydrates of inorganic metal compounds such as borax, among which magnesium hydroxide and aluminum hydroxide are preferred.
Examples of the metal carbonate used as a reinforcing filler include calcium carbonate and magnesium carbonate.
As the reinforcing filler, carbon black of various classes such as FT, SRF, FEF, HAF, ISAF, and SAF can be used, and carbon black having a nitrogen adsorption specific surface area of 50 mg/g or more and a DBP (dibutyl phthalate) oil absorption of 80 mL/100 g is preferred.

In the reinforcing filler compound using the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment, a silane coupling agent (hereinafter, sometimes referred to as component (D)) may be used.
The silane coupling agent is used to enhance the interaction between the hydrogenated block copolymer and the reinforcing filler, and is a compound having a group that has affinity or binding properties for either or both of the hydrogenated block copolymer and the reinforcing filler.
Preferred silane coupling agents include those having a polysulfide bond in which two or more mercapto groups and/or sulfur groups are linked together with a silanol group or an alkoxysilane. Specific examples thereof include bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, and the like.
From the viewpoint of obtaining the intended effect, the amount of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 1 to 15% by mass, based on the reinforcing filler compound.

The reinforcing filler blend containing the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment and a reinforcing filler may be vulcanized, i.e., crosslinked, with a vulcanizing agent to form a vulcanized composition.
As the vulcanizing agent, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, sulfur compounds (sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, etc. can be used.
The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass, and preferably 0.1 to 15 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition.
As the organic peroxide used as a vulcanizing agent (hereinafter, sometimes referred to as component (E)), from the viewpoint of odor properties and scorch stability (the property of not crosslinking under the conditions for mixing the respective components, but rapidly crosslinking under crosslinking reaction conditions), 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, and di-tert-butyl peroxide are preferred.
In addition to the above, dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, and the like can also be used.

In addition, when vulcanizing, a vulcanization accelerator (hereinafter, sometimes referred to as component (F)) such as a sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, or dithiocarbamate-based compound may be used in an amount according to need.
Furthermore, as a vulcanization aid, zinc oxide, stearic acid, etc. can also be used in an appropriate amount.
In addition, when the reinforcing filler compound is crosslinked using the organic peroxide, sulfur; peroxy crosslinking assistants such as p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenyl guanidine, and trimethylolpropane-N,N'-m-phenylenedimaleimide (hereinafter, sometimes referred to as component (G)); polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate; and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate (hereinafter, sometimes referred to as component (H)) may be used in combination with the organic peroxide as a vulcanization accelerator.
Such a vulcanization accelerator is usually used in a proportion of preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition.
As a method for vulcanizing the reinforcing filler compound with a vulcanizing agent, a conventional method can be applied, and for example, vulcanization is performed at a temperature of 120 to 200° C., preferably 140 to 180° C. The vulcanized reinforcing filler compound exhibits heat resistance, flex resistance, and oil resistance in the vulcanized state.

In order to improve the processability of the reinforcing filler compound, a rubber softener (hereinafter sometimes referred to as component (I)) may be compounded.
Suitable rubber softeners include mineral oils and liquid or low molecular weight synthetic softeners, among which naphthenic and/or paraffinic process oils or extender oils, which are generally used to soften, increase the volume and improve the processability of rubber, are preferred.
Mineral oil-based rubber softeners are mixtures of aromatic rings, naphthenic rings, and paraffin chains, and those in which the carbon number of the paraffin chain is 50% or more of the total carbon are called paraffinic, those in which the carbon number of the naphthenic ring is 30-45% are called naphthenic, and those in which the aromatic carbon number is more than 30% are called aromatic. Synthetic softeners may be used in the reinforcing filler compound, and polybutene, low molecular weight polybutadiene, liquid paraffin, etc. can be used. However, the above-mentioned mineral oil-based rubber softeners are preferred.
The amount of the rubber softener (component (I)) in the reinforcing filler composition is preferably 0 to 100 parts by mass, more preferably 1 to 90 parts by mass, and even more preferably 30 to 90 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)). If the amount of the rubber softener exceeds 100 parts by mass, bleeding out is likely to occur, and the surface of the composition may become sticky.

The reinforcing filler compound containing the hydrogenated block copolymer or hydrogenated block copolymer composition of this embodiment can be suitably used as a building material, an electric wire coating material, a vibration-damping material, etc. Furthermore, taking advantage of its characteristics, the vulcanized composition is suitable for tire applications, vibration-proof rubber, belts, industrial products, footwear, foams, etc.

(Cross-linked material)
The hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment can be crosslinked in the presence of a vulcanizing agent to form a crosslinked product, i.e., a crosslinked hydrogenated block copolymer or a crosslinked hydrogenated block copolymer composition.
By crosslinking the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment, the heat resistance [high temperature C-Set (compression set)] and flex resistance can be improved.
When preparing a crosslinked product of the reinforcing filler blend containing the hydrogenated block copolymer composition of this embodiment, the blending ratio of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)) to the thermoplastic resin and/or rubber-like polymer (component (B)) is preferably 10/90 to 100/0, more preferably 20/80 to 90/10, and even more preferably 30/70 to 80/20, in terms of the mass ratio of component (A)/component (B).

In this embodiment, the crosslinking method is not particularly limited, but it is preferable to carry out so-called "dynamic crosslinking".
Dynamic crosslinking is a technique in which various compounds are kneaded in a molten state under temperature conditions in which a vulcanizing agent reacts, thereby simultaneously causing dispersion and crosslinking, and is described in detail in a document by A. Y. Coran et al. (Rub. Chem. and Technol. vol. 53.141-(1980)). Dynamic crosslinking is usually carried out using an internal kneader such as a Banbury mixer or a pressure kneader, or a single-screw or twin-screw extruder. The kneading temperature is usually 130 to 300°C, preferably 150 to 250°C, and the kneading time is usually 1 to 30 minutes.
As the vulcanizing agent used for dynamic crosslinking, an organic peroxide or a phenol resin crosslinking agent is used, and the amount used is usually 0.01 to 15 parts by mass, and preferably 0.04 to 10 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)).
The organic peroxide used as the vulcanizing agent can be the above-mentioned component (E). When crosslinking is performed using an organic peroxide, the above-mentioned component (F) can be used as a vulcanization accelerator, and the above-mentioned components (G) and (H) can also be used in combination. The amount of these vulcanization accelerators used is usually 0.01 to 20 parts by mass, and preferably 0.1 to 15 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)).

The crosslinked product using the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)) of this embodiment may be blended with additives such as softeners, heat stabilizers, antistatic agents, weather stabilizers, antioxidants, fillers, colorants, lubricants, etc., as necessary, within the range that does not impair the object of the crosslinked product. As the softener blended to adjust the hardness and fluidity of the final product, the above-mentioned component (I) can be used.
The softener may be added when the components are kneaded, or may be incorporated in the hydrogenated block copolymer in advance during production of the copolymer, that is, in the preparation of an oil-extended rubber.
The amount of the softener added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)).
The filler may be the reinforcing filler, component (C), described above. The amount of the filler added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition (component (A)).
It is recommended that the crosslinked product be dynamically crosslinked so that the gel content (not including insoluble components such as inorganic fillers) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass. The gel content is determined by refluxing 1 g of the crosslinked product in a Soxhlet extractor using boiling xylene for 10 hours, filtering the residue through an 80-mesh wire screen, and measuring the dry mass (g) of the insoluble matter remaining on the mesh, and the gel content is the ratio (mass%) of the insoluble matter to 1 g of the sample. The gel content can be controlled by adjusting the type and amount of the vulcanizing agent and the vulcanization conditions (temperature, residence time, shear, etc.).
The crosslinked product can be used in tires, anti-vibration rubber, belts, industrial products, footwear, foams, and the like, in the same manner as the vulcanized composition containing the reinforcing filler, and can also be used as a medical instrument material or food packaging material.

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited in any way to the following examples and comparative examples.
Various physical properties were measured by the methods shown below.

[Method of identifying copolymer structure and method of measuring physical properties]
((1) Content of total vinyl aromatic compound (styrene) monomer units in hydrogenated block copolymer (a))
The total vinyl aromatic compound (styrene) monomer unit content of the block copolymer before hydrogenation was measured with an ultraviolet spectrophotometer (Shimadzu Corporation, UV-2450).

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

((3-1) Amount of vinyl bonds in hydrogenated block copolymer (a))
The block copolymer before hydrogenation was used and the measurement was performed using an infrared spectrophotometer (FT/IR-4100, manufactured by JASCO Corporation). The vinyl bond content in the copolymer was calculated by the Hampton method.

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

((3-3) Amount of vinyl bonds in polymer block (c))
It was calculated from the vinyl bond amounts of (3-1) and (3-2) above.

((4) Weight average molecular weight of hydrogenated block copolymer (a))
The weight average molecular weight of the hydrogenated block copolymer (a) was measured by GPC [apparatus: HLC-82209PC (manufactured by Tosoh Corporation), column: TSK Geguard column Super HZ-L (4.6 mm×20 cm)×3 columns].
The solvent used was tetrahydrofuran, and the measurement was carried out at a temperature of 35°C.
The weight average molecular weight was determined by using the molecular weight of the peak in the chromatogram and a calibration curve (created using the peak molecular weight of the standard polystyrene) determined from the measurement of commercially available standard polystyrene.
When there are multiple peaks in the chromatogram, the average molecular weight calculated from the molecular weight of each peak and the composition ratio of each peak (calculated from the area ratio of each peak in the chromatogram) was used as the weight average molecular weight.
The weight average molecular weight immediately before the addition of ethyl benzoate was also measured. For the case where ethyl benzoate was not added, the weight average molecular weight was calculated from the GPC of the polymer obtained by inactivating a sample of the polymer with methanol immediately before the addition of ethyl benzoate, and for the case where ethyl benzoate was added, the weight average molecular weight was measured by GPC using the hydrogenated block copolymer (A) prepared.
The molecular weight distribution was also measured by GPC.

((5) The ratio (%) of the area in the molecular weight range of 10,000 to 150,000 and the ratio (%) of the area in the molecular weight range of 200,000 to 100 in the GPC curve of the hydrogenated block copolymer (a)
The measurement was performed by GPC [apparatus: HLC-82209PC (manufactured by Tosoh Corporation), column: TSK Geguard column Super HZ-L (4.6 mm×20 cm)×3 columns].
The solvent used was tetrahydrofuran.
The measurements were carried out at a temperature of 35°C.
The area value (%) of the hydrogenated block copolymer (A) having a molecular weight in the range of 10,000 or more and 150,000 or less means a value calculated from the ratio of the area value of the hydrogenated block copolymer (A) having a molecular weight in the range of 10,000 or more and 150,000 or less to the area value of the molecular weight in the range of 10,000 to 1,000,000 in a GPC curve.
The area value (%) of the hydrogenated block copolymer (a) in the molecular weight range of 200,000 or more and 1,000,000 or less means a value calculated from the ratio of the area value of the hydrogenated block copolymer (a) in the molecular weight range of 200,000 or more and 1,000,000 or less to the area value of the molecular weight range of 10,000 to 1,000,000 in a GPC curve.

((6) Hydrogenation ratio of double bonds of conjugated diene monomer units of hydrogenated block copolymer (a))
The hydrogenation rate of the double bonds of the conjugated diene monomer units was measured using the hydrogenated block copolymer with a nuclear magnetic resonance spectrometer (ECS400, manufactured by JEOL RESONANCE).

((7) Content of Vinyl Aromatic Compound Monomer Unit in Copolymer Block (b))
The block copolymer before hydrogenation was used as a sample and was measured using a nuclear magnetic resonance (NMR) apparatus (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), hereinafter referred to as the "NMR method") to calculate the difference between the content of all vinyl aromatic compound (styrene) monomer units in the hydrogenated block copolymer (A) and the content of polymer blocks mainly composed of vinyl aromatic compound monomer units in the hydrogenated block copolymer (A).

[Method of measuring characteristics]
((1) tan δ peak temperature)
First, a "press molded sheet" manufactured as described below was cut into a size of 12.5 mm in width and 40 mm in length to prepare a measurement sample.
Next, this measurement sample was set in a torsion type geometry of an ARES device (trade name, manufactured by TA Instruments Co., Ltd.), and measurements were performed under conditions of an effective measurement length of 25 mm, strain of 0.5%, frequency of 1 Hz, and heating rate of 3° C./min.
The tan δ peak temperature was determined from a peak detected by automatic measurement using an RSI Orchestrator (manufactured by TA Instruments Co., Ltd., trade name).

((2) Hardness)
In accordance with JIS K6253, the instantaneous value and the value after 10 seconds were measured using a durometer type A.
The hardness value was measured at the moment when the probe of the hardness tester was lowered onto the sample, and 10 seconds after the probe was lowered.
In Tables 1 and 2 below, the hardness is shown as (JIS-A, instantaneous) and (JIS-A, 10s), respectively.
The hardness value is preferably 96 or less.

((3) Melt flow rate (MFR, unit: g/10 min))
The measurement was carried out in accordance with JIS K7210 at a temperature of 230° C. and a load of 2.16 kg.
Further, an MFR value of less than 25 (g/10 min) was given a score of 0, 25 to less than 35 (g/10 min) was given a score of 1, 35 to less than 45 (g/10 min) was given a score of 2, and 45 (g/10 min or more) was given a score of 3.

((4) Abrasion Resistance)
Using a Gakushin type friction tester (Model AB-301, manufactured by Tester Sangyo Co., Ltd.), the surface of the molded sheet (embossed leather surface) prepared by the method described below in [Preparation of injection molded sheet] was rubbed with a friction cloth, Kanakin No. 3 cotton, under a load of 500 g, and the volume loss after rubbing was evaluated according to the following criteria.
◎ (3 points): After 10,000 frictions, the volume loss is 0.01 mL or less. ○ (2 points): After 10,000 frictions, the volume loss is more than 0.01 mL and less than 0.1 mL. △ (1 point): After 10,000 frictions, the volume loss is more than 0.1 mL and less than 0.2 mL. × (0 point): After 10,000 frictions, the volume loss is more than 0.2 mL.

(5) Ease of pulling strands (extrusion moldability)
Using the hydrogenated block copolymer composition described below, a strand was extruded through a die nozzle of a single screw extruder TEX-30 type vent manufactured by The Japan Steel Works, Ltd., and the ease of pulling was visually evaluated on a three-level scale.
A strand that could be pulled at high speed was rated as "3," a strand that broke easily when pulled at high speed but did not break when pulled at low speed was rated as "2," and a strand that broke easily even when pulled at low speed was rated as "1."
The higher the number in the three-level evaluation, the better the extrusion moldability.

((6) Blocking Resistance of Pellet)
The blocking resistance was measured by the following method.
60 g of sample pellets made of a hydrogenated block copolymer and having the same shape (cylindrical shape, diameter 3 mm×3 mm) were placed in a metal cylinder having a diameter of 5 cm, and a weight of 1160 g was placed thereon.
In this state, the cylinder was heated in a Geer oven at 42° C. for 20 hours, and then the adhesion state of the pellets in the cylinder was observed.
Specifically, the pellet agglomerate removed from the cylinder crumbled (however, pellets with poor blocking resistance did not crumble), and the weight of an agglomerate consisting of three or more pellets was measured, and the ratio (%) of the weight of the pellet agglomerate to the total weight of the pellets (60 g) was calculated.
The blocking resistance was evaluated based on the following criteria.
Incidentally, the evaluation was carried out after adding calcium stearate equivalent to 1500 ppm to each sample pellet.
3: The pellets can be loosened, but the mass of 3 or more pellets is less than 50% of the total mass. 2: The pellets can be loosened, but the mass of 3 or more pellets is 50% or more of the total mass. 1: The pellets are solidified and cannot be loosened at all.

[Production of hydrogenated block copolymer]
(Preparation of hydrogenation catalyst)
In the examples and comparative examples described later, the hydrogenation catalyst used in producing the hydrogenated block copolymer was prepared by the following method.
A reaction vessel equipped with a stirrer was purged with nitrogen and charged with 1 liter of dried and purified cyclohexane.
Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added.
While thoroughly stirring the mixture, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was allowed to react at room temperature for about 3 days, thereby obtaining a hydrogenation catalyst.

<Hydrogenated Block Copolymer>
Hydrogenated block copolymers (i)-1 to (i)-30 and (i)-A to (i)-G constituting the hydrogenated block copolymer composition were prepared as follows.

Example 1
(Hydrogenated Block Copolymer (a)-1)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.096 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-1.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-1 was 98%. Other properties are shown in Table 1.

[ Reference Example 2]
(Hydrogenated block copolymer (a)-2)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.097 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per mole of n-butyllithium were added and polymerized at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.048 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 21% by mass, and a weight average molecular weight of 131,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-2.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-2 was 96%. Other properties are shown in Table 1.

[ Reference Example 3]
(Hydrogenated block copolymer (a)-3)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.097 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per mole of n-butyllithium were added and polymerized at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerization was carried out for 2 hours at 60° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 21% by mass, and a weight average molecular weight of 120,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-3.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-3 was 98%. Other properties are shown in Table 1.

Example 4
(Hydrogenated block copolymer (a)-4)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-4.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-4 was 97%. Other properties are shown in Table 1.

Example 5
(Hydrogenated Block Copolymer (a)-5)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 4 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.097 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 39 parts by mass of butadiene and 57 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 61% by mass, a polystyrene block content of 4% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-5.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-5 was 97%. Other properties are shown in Table 1.

[ Reference Example 6]
(Hydrogenated Block Copolymer (a)-6)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration 2) containing 41 parts by mass of butadiene and 59 parts by mass of styrene was
0% by mass) was added.
Next, 0.097 parts by mass of n-butyl lithium and N
,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA")
1.8 moles of sodium t-pentoxide per mole of n-butyllithium
0.08 mol of ethyl benzoate was added per mol of n-butyllithium, and polymerization was carried out for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and polymerization was carried out for 2 hours at 70° C.
The reaction was allowed to proceed for 10 minutes at room temperature, after which methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 59% by mass, a polystyrene block content of 0% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and the mixture was subjected to hydrogenation under a hydrogen pressure of 0.7 MPa.
The hydrogenation reaction was carried out at a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-6.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-6 was 97%. Other properties are shown in Table 1.

Example 7
(Hydrogenated block copolymer (a)-7)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.097 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration 20% by mass) containing 36 parts by mass of butadiene and 51 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 60° C. for 10 minutes. 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out at 70° C. for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 61 mass%, a polystyrene block content of 10 mass%, a vinyl bond amount of 52 mass% (vinyl bond amount of copolymer block (b) 51 mass%, vinyl bond amount of polymer block (c) 70 mass%), and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-7.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-7 was 95%. Other properties are shown in Table 1.

Example 8
(Hydrogenated block copolymer (a)-8)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.099 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of butadiene was added and polymerized at 60° C. for 20 minutes. 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out at 70° C. for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 57% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 53% by mass (vinyl bond amount of copolymer block (b) 51% by mass, vinyl bond amount of polymer block (c) 70% by mass), and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the copolymer to obtain a hydrogenated block copolymer (a)-8.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-8 was 98%. Other properties are shown in Table 1.

Example 9
(Hydrogenated block copolymer (a)-9)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.101 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration 20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of butadiene was added and polymerized at 60° C. for 20 minutes. 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out at 70° C. for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 51 mass%, a polystyrene block content of 10 mass%, a vinyl bond amount of 55 mass% (vinyl bond amount of copolymer block (b) 51 mass%, vinyl bond amount of polymer block (c) 70 mass%), and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-9.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-9 was 97%. Other properties are shown in Table 1.

Example 10
(Hydrogenated block copolymer (a)-10)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 126,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-10.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-10 was 96%. Other properties are shown in Table 1.

Example 11
(Hydrogenated block copolymer (a)-11)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.225 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 152,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-11.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-11 was 98%. Other properties are shown in Table 2.

Example 12
(Hydrogenated block copolymer (a)-12)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.108 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.2 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.02 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 29% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-12.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-12 was 95%. Other properties are shown in Table 2.

Example 13
(Hydrogenated block copolymer (a)-13)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.108 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.5 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.06 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 40% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-13.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-13 was 95%. Other properties are shown in Table 2.

Example 14
(Hydrogenated block copolymer (a)-14)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.108 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-14.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-14 was 86%. Other properties are shown in Table 2.

Example 15
(Hydrogenated block copolymer (a)-15)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.108 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-15.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-15 was 90%. Other properties are shown in Table 2.

Example 16
(Hydrogenated block copolymer (a)-16)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.108 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-16.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-16 was 60%. Other properties are shown in Table 2.

Example 17
(Hydrogenated block copolymer (a)-17)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.108 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-17.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-17 was 40%. Other properties are shown in Table 2.

[ Reference Example 18]
(Hydrogenated block copolymer (a)-18)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.102 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 52 parts by mass of butadiene and 38 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 48% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 60% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-18.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-18 was 97%. Other properties are shown in Table 2.

[ Reference Example 19]
(Hydrogenated block copolymer (a)-19)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 19 parts by mass of butadiene and 71 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 81% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 40% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-19.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-19 was 96%. Other properties are shown in Table 2.

[ Reference Example 20]
(Hydrogenated block copolymer (a)-20)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 39.6 parts by mass of butadiene and 50.4 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 50% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 55% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-20.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-20 was 96%. Other properties are shown in Table 2.

Example 21
(Hydrogenated block copolymer (a)-21)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 42.3 parts by mass of butadiene and 47.7 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 52% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-21.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-21 was 96%. Other properties are shown in Table 3.

[ Reference Example 22]
(Hydrogenated block copolymer (a)-22)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.045 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 136,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-22.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-22 was 96%. Other properties are shown in Table 3.

Example 23
(Hydrogenated block copolymer (a)-23)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.06 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 140,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-23.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-23 was 96%. Other properties are shown in Table 3.

Example 24
(Hydrogenated block copolymer (a)-24)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 33% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-24.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-24 was 96%. Other properties are shown in Table 3.

Example 25
(Hydrogenated block copolymer (a)-25)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 30 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.102 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 71% by mass, a polystyrene block content of 30% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 133,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (a)-25.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-25 was 96%. Other properties are shown in Table 3.

Example 26
(Hydrogenated block copolymer (a)-26)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 57 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-26.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-26 was 96%. Other properties are shown in Table 3.

[ Reference Example 27]
(Hydrogenated block copolymer (a)-27)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 3 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.090 parts by mass of n-butyl lithium and N
,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA")
1.8 moles of sodium t-pentoxide per mole of n-butyllithium
0.08 mole of butyl lithium was added per mole of butyl lithium, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration 200) containing 36 parts by mass of butadiene and 42 parts by mass of styrene was
0 mass%) was added and polymerization was carried out for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per 1 mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 39% by mass, a polystyrene block content of 3% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and the mixture was subjected to hydrogenation under a hydrogen pressure of 0.7 MPa.
The hydrogenation reaction was carried out at a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-27.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-27 was 96%. Other properties are shown in Table 3.

[ Reference Example 28]
(Hydrogenated block copolymer (a)-28)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.112 parts by mass of n-butyl lithium and N
,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA")
1.8 moles of sodium t-pentoxide per mole of n-butyllithium
0.08 mole of butyl lithium was added per mole of butyl lithium, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration 2
0 mass%) was added and polymerization was carried out for 2 hours at 60° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 42% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 60% by mass, and a weight average molecular weight of 135,000.
Further, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and the mixture was subjected to hydrogenation under a hydrogen pressure of 0.7 MPa.
The hydrogenation reaction was carried out at a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-28.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-28 was 97%. Other properties are shown in Table 3.

[ Reference Example 29]
(Hydrogenated block copolymer (a)-29)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 16.7 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.112 parts by mass of n-butyl lithium and N
,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA")
1.8 moles of sodium t-pentoxide per mole of n-butyllithium
0.08 mole of butyl lithium was added per mole of butyl lithium, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration 200 ml) containing 33 parts by mass of butadiene and 50 parts by mass of styrene was
0 mass%) was added and polymerization was carried out for 2 hours at 60° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 50% by mass, a polystyrene block content of 13.7% by mass, a vinyl bond content of 75% by mass, and a weight average molecular weight of 13.7.
The figure was ten thousand.
Further, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and the mixture was subjected to hydrogenation under a hydrogen pressure of 0.7 MPa.
The hydrogenation reaction was carried out at a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-29.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-29 was 97%. Other properties are shown in Table 3.

[ Reference Example 30]
(Hydrogenated block copolymer (a)-30)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.075 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerization was carried out for 2 hours at 60° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 65% by mass, a polystyrene block content of 15% by mass, a vinyl bond amount of 23% by mass, and a weight average molecular weight of 150,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-30.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-30 was 97%. Other properties are shown in Table 3.

Comparative Example 1
(Hydrogenated Block Copolymer (a)-A)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 45 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.092 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 23 parts by mass of butadiene and 32 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 77% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-A.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-A was 98%. Other properties are shown in Table 4.

Comparative Example 2
(Hydrogenated Block Copolymer (A)-B)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.116 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.15 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 162,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-B.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-B was 96%. Other properties are shown in Table 4.

Comparative Example 3
(Hydrogenated Block Copolymer (A)-C)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.080 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.25 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 210,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-C.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-C was 95%. Other properties are shown in Table 4.

Comparative Example 4
(Hydrogenated Block Copolymer (A)-D)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.096 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.2 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 10% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-D.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-D was 98%. Other properties are shown in Table 4.

Comparative Example 5
(Hydrogenated Block Copolymer (A)-E)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.096 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-E.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-E was 15%. Other properties are shown in Table 4.

Comparative Example 6
(Hydrogenated Block Copolymer (A)-F)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.096 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 72 parts by mass of butadiene and 18 parts by mass of styrene was added and polymerized for 2 hours at 60° C. Next, 0.105 mol of ethyl benzoate was added per mol of n-butyllithium, and the reaction was carried out for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 28% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 66% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-F.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-F was 97%. Other properties are shown in Table 4.

Comparative Example 7
(Hydrogenated Block Copolymer (A)-G)
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.09 parts by mass of n-butyllithium per 100 parts by mass of the total monomers, 1.8 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mole of n-butyllithium, and 0.08 moles of sodium-t-pentoxide per 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 17 parts by mass of butadiene and 73 parts by mass of styrene was added and polymerization was carried out for 2 hours at 60° C. Thereafter, methanol was added to terminate the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 83% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 36% by mass, and a weight average molecular weight of 151,000.
Further, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer in an amount of 100 ppm (Ti standard) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.
Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (a)-G.
The hydrogenation rate of the resulting hydrogenated block copolymer (a)-G was 97%. Other properties are shown in Table 4.

[Preparation of press-molded sheet]
The hydrogenated block copolymers (a)-1 to (a)-30, and (a)-A to (a)-G prepared as described above were each rolled out at 160°C using a 4-inch roll, and then press-molded using a hydraulic press at 200°C and 100 kg/ ^cm2 to prepare press-molded sheets having a thickness of 2 mm.

The following values were measured for the hydrogenated block copolymers (a)-1 to 30 and (a)-A to G of the above-mentioned [Examples 1 to 30] and [Comparative Examples 1 to 7].
(Physical properties)
Total vinyl aromatic compound monomer unit content (mass%)
(a) Content (mass%) of polymer block mainly composed of vinyl aromatic compound monomer units
(b) Content (mass%) of hydrogenated copolymer block composed of vinyl aromatic compound monomer units and conjugated diene monomer units
(c) Content (mass%) of hydrogenated polymer block mainly composed of conjugated diene monomer units
The amount of vinyl bonds (% by mass) in the (b) hydrogenated copolymer block
The amount of vinyl bonds (mass%) in the (c) hydrogenated polymer block
Weight average molecular weight just before adding ethyl benzoate (10,000)
Molecular weight distribution
(Molecular weight distribution of ethyl benzoate added product immediately before addition)
Weight average molecular weight of (a) (10,000)
- The area value (%) of the molecular weight range of 10,000 to 150,000 relative to the area of the molecular weight range of 10,000 to 1,000,000 in the GPC chart
The area value (%) of the molecular weight range of 200,000 to 1,000,000 relative to the area of the molecular weight range of 10,000 to 1,000,000 in the GPC chart
Amount of vinyl bonds in conjugated diene monomer units (mass%)
Hydrogenation rate of double bonds of conjugated diene monomer units (%)
The content (mass%) of vinyl aromatic compound monomer units in the hydrogenated copolymer block (b)
The content (mass%) of the conjugated diene monomer unit in the hydrogenated copolymer block (b)
(Characteristics)
Melt flow rate (230°C, 2.16kg)
Peak temperature of tan δ (loss tangent) in the viscoelasticity measurement chart A hardness (instantaneous, 10s)
- Blocking properties of pellets

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

[Production of hydrogenated block copolymer composition]
Hydrogenated block copolymer compositions were produced using the above-mentioned hydrogenated block copolymers (a)-1 to 30 and (a)-A to G and the following olefin resin (b).

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

[Preparation of injection molded sheet]
Example 31
The pelletized hydrogenated block copolymer (a)-1 and the olefin resin (b) were blended in the ratio (mass%) shown in Table 5 below, kneaded in a twin-screw extruder (TEX-30), and pelletized to obtain a hydrogenated block copolymer composition.
The extrusion conditions were a cylinder temperature of 230° C. and a screw rotation speed of 300 rpm. The composition obtained was injection molded at 210° C. to prepare a sheet having a thickness of 2 mm, and a specimen for measuring physical properties was obtained. The results of the physical property measurements are shown in the table.

[Example 31, Reference Examples 32 to 33, Examples 34 to 35, Reference Example 36, Examples 37 to 47, Reference Examples 48 to 50, Example 51, Reference Example 52, Examples 53 to 56, Reference Examples 57 to 59, Reference Example 60 , Examples 61 to 62, Comparative Examples 8 to 14]
Hydrogenated block copolymer compositions were produced in the same manner as in Example 31, except that the components were changed as shown in Tables 5 to 8, and the physical properties of the compositions were measured.
The results of the physical property measurements are shown in Tables 5 to 8.

The hydrogenated block copolymers of Example 1 , Reference Example 2, Reference Example 3, Examples 4 to 5, Reference Example 6, Examples 7 to 17, Reference Examples 18 to 20, Example 21 , Reference Example 22, Examples 23 to 26, Reference Examples 27 to 29, and Reference Example 30, and the hydrogenated block copolymer compositions of Example 31 , Reference Examples 32 to 33, Examples 34 to 35, Reference Example 36, Examples 37 to 47, Reference Examples 48 to 50, Example 51 , Reference Example 52, Examples 53 to 56, Reference Examples 57 to 59, Reference Example 60 , and Examples 61 to 62 have an excellent balance between abrasion resistance and MFR, and have good hardness and moldability.

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

Claims (8)

A hydrogenated block copolymer comprising vinyl aromatic compound monomer units and conjugated diene monomer units,
A hydrogenated block copolymer satisfying the following requirements (1) to (7):
(1): (b) Contains at least one hydrogenated copolymer block composed of vinyl aromatic compound monomer units and conjugated diene monomer units.
(2): (a) has a polymer block mainly composed of a vinyl aromatic compound monomer unit, and the content of the polymer block mainly composed of a vinyl aromatic compound monomer unit (a) is 1 mass % or more and 40 mass % or less.
(3): The weight average molecular weight (Mw) is 200,000 or less.
(4): The hydrogenation rate of the double bonds of the conjugated diene monomer units is 20% or more.
(5): In a molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC) measurement, the ratio of the area in the molecular weight range of 10,000 to 150,000 to the area in the molecular weight range of 10,000 to 1,000,000 is more than 50% and 88% or less, and the ratio of the area in the molecular weight range of 200,000 to 1,000,000 to the area in the molecular weight range of 10,000 to 1,000,000 is 10% or more .
(6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more.
(7): The content of vinyl aromatic compound monomer units in the (b) hydrogenated copolymer block is 45% by mass or more and 79% by mass or less;
The hydrogenated block copolymer has a total vinyl aromatic compound monomer unit content of 40% by mass or more and 80% by mass or less. The hydrogenated block copolymer according to claim 1, wherein the amount of vinyl bonds in the hydrogenated block copolymer is 30% by mass or more. The content of the polymer block mainly composed of the vinyl aromatic compound monomer unit (a) is 1% by mass or more and 20% by mass or less.
The hydrogenated block copolymer according to claim 1 or 2 . (c) containing 1% by mass or more of a hydrogenated polymer block mainly composed of a conjugated diene monomer unit;
The hydrogenated block copolymer according to claim 1 . The hydrogenated block copolymer according to any one of claims 1 to 4 , wherein at least one tan δ peak in a viscoelasticity measurement chart is present at a temperature between 0°C and 30°C. The hydrogenated block copolymer (a) according to any one of claims 1 to 5 : 1% by mass or more and 95% by mass or less;
At least one type of olefin resin (ii): 5% by mass or more and 99% by mass or less;
A hydrogenated block copolymer composition comprising: The olefin-based resin (b) is
At least one polypropylene-based resin is included.
The hydrogenated block copolymer composition according to claim 6 . A molded article of the hydrogenated block copolymer composition according to claim 6 or 7 .