JP2021017562A - Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded body - Google Patents

Abstract

To provide a hydrogenated block copolymer which, when formed into a resin composition with a polyolefin, offers excellent abrasion resistance and a high MFR.SOLUTION: Provided is a hydrogenated block copolymer which satisfies the requirements (1) to (7): The hydrogenated copolymer (1) contains at least one hydrogenated copolymer block comprising a vinyl aromatic compound monomer unit (b) and a conjugated diene monomer unit; (2) has a content of a polymer block containing a vinyl aromatic compound monomer unit (a) as a main component of 40 mass% or less; (3) has a Mw of 200,000 or less; (4) has a hydrogenation rate of 20% or more; (5) has, in a GPC curve, a ratio of an area in a range of mw 10,000 to 150,000 to an area in a range of mw 10,000 to 1,000,000 exceeding 50%; (6) has a vinyl bond content of 20 mass% or more; and (7) has a vinyl aromatic compound monomer content in the block of 30 mass% to 79 mass%.SELECTED DRAWING: None

Description

The present invention relates to hydrogenated block copolymers, hydrogenated block copolymer compositions, and molded articles.

Traditionally, materials for automobile interiors have been required to have a balance between wear resistance and mechanical strength. Olefin-based resins are mainly used as such materials.
On the other hand, while realizing the needs for environmental issues such as weight reduction, recyclability, and easy incineration of automobile parts, as well as heat resistance, cold resistance, heat aging resistance, light resistance, and low odor resistance, the appearance is cheap. In recent years, a styrene-based thermoplastic elastomer material (hereinafter, may be simply abbreviated as "TPS material") has been put into practical use in order to eliminate the feeling.

Furthermore, in recent years, with the increasing demand for car sharing and self-driving cars, it is possible to realize high-quality tactile sensation (low hardness) and mechanical strength for automobile interior materials while maintaining a high level of wear resistance. TPS material is required.
In response to such a requirement, for example, Patent Document 1 describes 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. A molded product of the composition has been proposed, and it is disclosed that the molded product has excellent wear resistance.

International Publication No. 03/035705

However, since the random copolymer styrene-based elastomer described in Patent Document 1 has low dispersibility in polypropylene resin, there is a problem that sufficient processability cannot be obtained when it is used as a composition with polypropylene resin. doing. Further, since the strands are cut immediately at the time of extrusion, there is a problem that the extrusion moldability is not sufficient.
Furthermore, in recent years, with the increasing demand for car sharing and self-driving cars mentioned above, high designability is required for automobile interior materials, and in view of such designability, it is required to manufacture a molded product having a complicated shape. Has been done.
A method of producing a molded product having a complicated shape by injection molding is the mainstream, but in this case, a high melt flow rate (hereinafter referred to as MFR) is required for the material of the molded product. Therefore, there is a demand for a resin composition having a higher MFR while maintaining the required performance such as wear resistance.

The present invention provides a hydrogenated block copolymer capable of providing a resin composition having excellent wear resistance and a high MFR, a resin composition containing the hydrogenated block copolymer, and a molded product. The purpose.

As a result of diligent research to solve the above-mentioned problems of the prior art, the present inventors are hydrogenated block copolymers having a specific structure, mainly composed of vinyl aromatic compound monomer units. The content of the polymer block to be used, the weight average molecular weight, the hydrogenation rate, the area of the molecular weight in a specific range on the GPC curve, the vinyl bond amount, and the content of the vinyl aromatic compound monomer unit in the specific polymer block. It has been found that the specified hydrogenated block copolymer can provide a resin composition having improved wear resistance and MFR, and has completed the present invention.
That is, the present invention is as follows.

[1]
A hydrogenated block copolymer containing a vinyl aromatic compound monomer unit and a conjugated diene monomer unit.
A hydrogenated block copolymer that satisfies the following requirements (1) to (7).
(1): (b) Contains at least one hydrogenated copolymer block composed of a vinyl aromatic compound monomer unit and a conjugated diene monomer unit.
(2): The content of the 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 is It is 40% by mass or less.
(3): The weight average molecular weight (Mw) is 200,000 or less.
(4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is 20% or more.
(5): In the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC) measurement, the molecular weight is in the range of 10,000 to 150,000 with respect to the area in which the molecular weight is in the range of 10,000 to 1,000,000. The area ratio exceeds 50%.
(6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more.
(7): The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) is 30% by mass or more and 79% by mass or less.
[2]
The hydrogenated block copolymer according to the above [1], wherein the amount of vinyl bonds in the hydrogenated block copolymer is 30% by mass or more.
[3]
(B) The hydrogenation according to the above [1] or [2], wherein the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block is 45% by mass or more and 79% by mass or less. Block copolymer.
[4]
In the molecular weight curve of a hydrogenated block copolymer obtained by gel permeation chromatography (GPC) measurement, for an area having a molecular weight in the range of 10,000 to 1,000,000.
The hydrogenated block copolymer according to any one of [1] to [3] above, wherein the proportion of the area having a molecular weight in the range of 200,000 to 1,000,000 is 10% or more.
[5]
The hydrogenated block copolymer according to any one of [1] to [4] above, wherein the content of the total vinyl aromatic compound monomer unit is 40% by mass or more and 80% by mass or less.
[6]
(A) The above-mentioned any one of [1] to [5], wherein the content of the polymer block mainly composed of the vinyl aromatic compound monomer unit is 1% by mass or more and 20% by mass or less. Hydrogenated block copolymer.
[7]
(C) Contains 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 [6] above.
[8]
The hydrogenated block copolymer according to any one of [1] to [7] above, wherein at least one peak of tan δ is present at 0 ° C. or higher and 30 ° C. or lower in the viscoelasticity measurement chart.
[9]
The hydrogenated block copolymer according to any one of [1] to [8] (a): 1% by mass or more and 95% by mass or less.
At least one type of olefin resin (b): 5% by mass or more and 99% by mass or less.
, A hydrogenated block copolymer composition.
[10]
The hydrogenated block copolymer composition according to the above [9], wherein the olefin resin (b) contains at least one kind of polypropylene resin.
[11]
A molded product of the hydrogenated block copolymer composition according to the above [9] or [10].

According to the present invention, a hydrogenated block copolymer that gives excellent wear resistance and high MFR when made into a resin composition with polyolefin can be obtained.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. It should be noted that the following embodiments are merely examples for explaining the present invention, and the present invention is not intended to be limited to the following contents, and the present invention can be implemented in various modifications within the scope of the gist thereof.

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

(Vinyl aromatic compound monomer unit)
The hydrogenated block copolymer (a) of the present embodiment contains a vinyl aromatic monomer unit.
The vinyl aromatic compound monomer unit is not limited to the following, and is, for example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-amino. Monomer units derived from ethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like can be mentioned.
In particular, styrene is preferable from the viewpoint of the balance between cost and mechanical strength.
Only one of these may be used alone, or two or more thereof may be used in combination.

(Conjugated diene monomer unit)
The hydrogenated block copolymer (a) of the present embodiment contains a conjugated diene monomer unit.
The conjugated diene monomer unit is a monomer unit derived from a diolefin having a pair of conjugated double bonds. Such diolefins are, but are not limited to, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3. -Pentaniene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like can be mentioned.
In particular, 1,3-butadiene and isoprene are preferable from the viewpoint of a balance between good molding processability and mechanical strength.
These may be used alone or in combination of two or more.

The hydrogenated block copolymer (a) of the present embodiment has a vinyl bond amount in the conjugated diene monomer unit of 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more. More preferably, it is more preferably 35% by mass or more.
When the amount of vinyl bond in the conjugated diene monomer unit of the hydrogenated block copolymer (a) is 20% by mass or more, the hydrogenated block copolymer (a) and the olefin resin (b) described later are used. In the hydrogenated block copolymer composition of the present embodiment in which the above is combined, the hardness and extrusion moldability tend to be improved, and when it is 30% by mass or more, the MFR and abrasion resistance tend to be particularly good. .. The higher the vinyl bond amount, the better the above physical properties.
Further, the vinyl bond amount of the hydrogenated block copolymer (a) can be controlled by using an adjusting agent such as a tertiary amine compound or an ether compound described later.

The hydrogenated block copolymer (a) of the present embodiment preferably has a total vinyl aromatic compound monomer unit content of 40% by mass or more and 80% by mass or less, and 45% by mass or more and 80% by mass or less. It is 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 content of the all-vinyl aromatic compound monomer unit is in the above range, the balance between hardness, extrusion moldability, and wear resistance tends to be good.
In the present embodiment, the content of the total vinyl aromatic compound monomer unit in the hydrogenated block copolymer (a) is the same as that of the block copolymer before hydrogenation and the hydrogenated block after hydrogenation. The polymer can be used as a sample and measured using an ultraviolet spectrophotometer.
The content of the total vinyl aromatic compound monomer unit of the hydrogenated block copolymer (a) is mainly adjusted by adjusting the amount of the vinyl aromatic compound added to the reactor, the reaction temperature, and the reaction time. , Can be controlled within the above numerical range.

In the present specification, in the composition of the hydrogenated block copolymer, "mainly" means that the ratio in the predetermined block polymer or the polymer block is 85% by mass or more. However, it means that it is preferably 90% by mass or more, and more preferably 95% by mass or more.
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 hydrogenated polymer block (a) and the hydrogenated weight It can be clearly distinguished from the coalesced block (b).

(Polymer block (a) mainly composed of vinyl aromatic compounds)
The hydrogenated block copolymer (a) of the present embodiment contains at least one polymer block (a) mainly composed of a vinyl aromatic compound monomer unit from the viewpoint of preventing pellet blocking.
In addition, the hydrogenated block copolymer (a) of the present embodiment has (a) a polymer block content of 40% by mass or less, preferably 1% by mass or more and 40% by mass or less, more preferably. It is 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less.
Since the content of the (a) polymer block in the hydrogenated block copolymer (a) of the present embodiment is 40% by mass or less, the hydrogenated block copolymer composition of the present embodiment described later is wear-resistant. The balance between property and hardness is good.

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

(Hydrogenated copolymer block (b))
The hydrogenated block copolymer (a) of the present 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 30% by mass or more and 79% by mass or less, preferably 40% by mass or more and 79% by mass or less, and 45% by mass or more. 79% by mass or less is more preferable, and 45% by mass or more and 70% by mass or less is further preferable.

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 later will be obtained. It exhibits good wear resistance. Further, when it is 45% by mass or more and 79% by mass or less, higher wear resistance is exhibited, and it can be used in applications where the demand for more wear resistance is strict.
Further, when the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 79% by mass or less, extrusion molding of the hydrogenated block copolymer composition of the present embodiment described later will be performed. The properties tend to improve, and the hardness tends to decrease.
In the present embodiment, the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) in the hydrogenated block copolymer (a) is determined by a nuclear magnetic resonance apparatus (NMR) or the like. Can be measured by.
The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is mainly adjusted by adjusting the amount of the vinyl aromatic compound added to the reactor, the amount of conjugated diene, and the reaction temperature. , Can be controlled within the above numerical range.

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

(Hydrogenated polymer block (c) mainly composed of conjugated diene monomer unit)
The hydrogenated block copolymer (a) of the present embodiment preferably contains a hydrogenated polymer block (c) mainly composed of a conjugated diene monomer unit.
In the hydrogenated block copolymer (a) of the present embodiment, the content of the hydrogenated polymer block (c) is the MFR, hardness of the hydrogenated block copolymer (a), and the water of the present embodiment described later. From the viewpoint of the balance of MFR, abrasion resistance, and hardness of the block copolymer composition, 1% by mass or more is preferable, 2% by mass or more and 20% by mass or less is more preferable, and 2% by mass or more and 15% by mass or less is further preferable. Preferably, it is 2% by mass or more and 8% by mass or less, even more preferably.
The content of the hydrogenated polymer block (c) in the hydrogenated block copolymer (a) is within the above numerical range by mainly controlling the amount of conjugated diene added to the reactor and the reaction temperature. Can be controlled.

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 (b) described later. Therefore, the amount of vinyl bond of the conjugated diene monomer unit before hydrogenation in the hydrogenated polymer block (c) affects the compatibility between the hydrogenated block copolymer (a) and the olefin resin (b). From the viewpoint of improving the compatibility and improving the abrasion resistance, MFR, and hardness of the hydrogenated block copolymer composition of the present embodiment, which will be described later, the content should be 50% by mass or more. Is preferable, 55% by mass or more is more preferable, and 60% by mass or more is further preferable.

(Tanδ (tangent loss) in the viscoelasticity measurement chart of hydrogenated block copolymer (a))
The hydrogenated block copolymer (a) of the present embodiment preferably has at least one peak of tan δ (tangent loss) at −25 ° C. or higher and 40 ° C. or lower in the viscoelasticity measurement chart. It is more preferably present at −15 ° C. or higher and 35 ° C. or lower, further preferably −10 ° C. or higher and 30 ° C. or lower, and even more preferably 0 ° C. or higher and 30 ° C. or lower.
The peak of this tan δ is a peak caused by the hydrogenated copolymer block (b) in the hydrogenated block copolymer (a). At least one of these peaks is present in the range of −25 ° C. or higher and 40 ° C. or lower in the hardness of the hydrogenated block copolymer and the hydrogenated block copolymer composition of the present embodiment described later. It is important for wear resistance and good tactile sensation.
As described above, the hydrogenated copolymer block (b) is obtained by hydrogenating a copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit.
In order for at least one peak of tan δ (loss tangent) to exist in the range of -25 ° C or higher and 40 ° C or lower, it is necessary to control the conjugated diene monomer unit / vinyl aromatic monomer unit (mass ratio). It is effective 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 /. It is 40 to 25/75.
It is effective to control the conjugated diene monomer unit / vinyl aromatic monomer unit (mass ratio) so that at least one peak of tan δ (loss tangent) exists in the range of 0 ° C. or higher and 30 ° C. or lower. 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. ~ 30/70.
Tanδ can be measured using a viscoelasticity measuring device (ARES manufactured by TA Instrument Co., Ltd.) under the conditions of a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3 ° C./min. Specifically, it can be measured by the method described in Examples described later.

(Weight average molecular weight of hydrogenated block copolymer (a))
The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) of the present embodiment is 200,000 or less, and the hydrogenated block copolymer composition of the present embodiment, which will be described later, has good wear resistance. From the viewpoint of obtaining a balance between MFR, hardness and pellet blocking property, it is preferably 50,000 or more and 190,000 or less, more preferably 60,000 or more and 180,000 or less, and further preferably 70,000 or more and 170,000 or less.
In the present embodiment, the weight average molecular weight of the hydrogenated block copolymer (a) is measured by gel permeation chromatography (GPC), and a calibration curve obtained from the measurement of commercially available standard polystyrene (of standard polystyrene). Obtained using (created using peak molecular weight).

(Distribution of hydrogenated block copolymer (a) on the molecular weight curve)
In the GPC curve of the hydrogenated block copolymer (a) of the present embodiment, the ratio (%) of the area having a molecular weight in the range of 10,000 to 150,000 to the area having a molecular weight in the range of 10,000 to 1,000,000 is It shall exceed 50%.
From the viewpoint of obtaining a good balance between wear resistance, MFR, hardness, and pellet blocking property, it shall exceed 50%, preferably 60 to 99%, and more preferably 70 to 95%.
The larger the proportion of the area having a molecular weight in the range of 10,000 to 150,000, the higher the MFR and the lower the hardness, and the smaller the ratio, the better the wear resistance and the lower the pellet blocking property.
The ratio of the area of the hydrogenated block copolymer (a) of the present embodiment having a molecular weight of 10,000 to 150,000 in the GPC curve is such that the amounts of the polymerization initiator and the coupling agent are controlled and the appropriate molecular weight is appropriate. By mixing two or more types of polymers having a distribution, the above numerical range can be controlled.

Further, in the GPC curve of the hydrogenated block copolymer (a) of the present embodiment, the ratio (%) of the area having a molecular weight in the range of 200,000 to 1,000,000 to the area having a molecular weight in the range of 10,000 to 1,000,000. Is preferably 10% or more, more preferably 20% or more, from the viewpoint of obtaining a balance between wear resistance and pellet blocking property.
The larger the proportion of the area having a molecular weight in the range of 200,000 to 1,000,000, the better the wear resistance and the lower the pellet blocking property.
In particular, in order to improve wear resistance and pellet blocking, the proportion of the area in which the molecular weight of the hydrogenated block copolymer (a) is in the range of 200,000 or more is preferably in the above numerical range, and is 220,000 or more. It is more preferable that the ratio of the area in the range of 240,000 or more is in the above numerical range, and it is further preferable that the ratio of the area in the range of 240,000 or more is in the above numerical range.
In order to improve the MFR, it is preferable that the ratio of the area of the hydrogenated block copolymer (a) in the range of 1 million or less is in the above numerical range, and the area in the range of 700,000 or less is the above numerical range. It is more preferable that the area in the range of 500,000 or less is the above numerical range, and the area in the range of 300,000 or less is even more preferably the above numerical range.
The ratio of the area of the hydrogenated block copolymer (a) of the present embodiment having a molecular weight of 200,000 to 1,000,000 in the GPC curve is determined by adjusting the amounts of the polymerization initiator and the coupling agent and appropriate molecular weight. By mixing two or more types of polymers having a distribution, the above numerical range can be controlled.

(Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer (a))
The hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (a) of the present embodiment has a good hardness in the hydrogenated block copolymer composition of the present embodiment described later. From the viewpoint of obtaining MFR, it is assumed to be 20% or more, preferably 50% or more, more preferably 85% or more, and further preferably 92% or more.
The hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (a) can be controlled within the above numerical range by adjusting the hydrogenation amount.

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

(Crystallization peak of hydrogenated block copolymer (a))
The hydrogenated block copolymer (a) of the present embodiment has a crystallization peak due to the hydrogenated copolymer block (b) in the range of 25 to 80 ° C. in the differential scanning calorimetry (DSC) chart. It is preferably a hydrogenated additive that is substantially nonexistent.
Here, "the crystallization peak due to the hydrogenated copolymer block (b) is substantially not present in the range of 25 to 80 ° C." means that the hydrogenated copolymer block (b) is in this temperature range. ) The peak calorific value of crystallization due to crystallization is less than 3 J / g, preferably less than 2 J / g, even when the peak due to crystallization does not appear or the peak due to crystallization is observed. It is preferably less than 1 J / g, and more preferably it means that there is no crystallization peak calorific value.

As described above, if the crystallization peak due to the hydrogenated copolymer block (b) does not substantially exist in the range of 25 to 80 ° C., the hydrogenated block copolymer (a) of the present embodiment will have. , Good flexibility can be obtained, and the hydrogenated block copolymer composition of the present embodiment, which will be described later, can be softened, which is suitable.
In order to obtain the hydrogenated block copolymer (a) in which the crystallization peak due to the hydrogenated copolymer block (b) is substantially not present in the range of 25 to 80 ° C., the vinyl bond amount should be adjusted. The copolymer obtained by carrying out the polymerization reaction under the conditions described later using a predetermined modifier for adjusting the copolymerizability of 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 the present embodiment is not particularly limited, and examples thereof include those having a structure represented by the following general formula.
(Bc) _n , c- (bc) _n , b- (cc) _n , (bc) _m- X, (cc) _m- X, c- (ba) _n , c- (ab) _n , c- (ab-a) _n , c- (b-ab) _n , c- (b-c-a) _n , a- (c-b) -C-a) _n , a-c- (ba-a) _n , a-c- (ab) _n , a-c- (ba-a) _n- b, [(a-bc) _n ] _m- X, [a- (bc) _n ] _m- X, [(ab) _n- c] _m- X, [(ab-a) _n- c] _m- X, [(B-ab) _n- c] _m- X, [(c-b-a) _n ] _m- X, [c- (ba) _n ] _m- X, [c- (a-) b-a) _n ] _m- X, [c- (b-ab) _n ] _m- X
In each of the above general formulas, a is a polymer block (a) mainly composed of a vinyl aromatic compound monomer unit, and b is a hydrogenated product composed of a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. The copolymer block (b) and c represent a hydrogenated polymer block (c) mainly composed of a conjugated diene monomer unit.
n is an integer of 1 or more, preferably an integer of 1-5.
m is an integer of 2 or more, preferably an integer of 2 to 11.
X indicates a residue of the coupling agent or a residue of the polyfunctional initiator.

(Other examples of the structure of hydrogenated block copolymer (a))
The hydrogenated block copolymer (a) of the present embodiment may be a modified block copolymer to which an atomic group having a predetermined functional group is bonded.
Moreover, the modified block copolymer may be a secondary modified block copolymer.

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

(solvent)
Hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptane, and methylcyclo. Aliphatic hydrocarbons such as heptane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can be mentioned.

(Polymerization initiator)
The polymerization initiator is not particularly limited, but for example, an aliphatic hydrocarbon alkali metal compound and an aromatic hydrocarbon that are generally known to have anionic polymerization activity with respect to a vinyl aromatic compound and a conjugated diene. Organic alkali metal compounds such as alkali metal compounds and organic amino alkali metal compounds can be applied.
The organic alkali metal compound is not limited to the following, but for example, an aliphatic and aromatic lithium hydrocarbon compound having 1 to 20 carbon atoms is preferable, a compound containing one lithium in one molecule, and a plurality of compounds in one molecule. Dilithium compounds, trilithium compounds, and tetralithium compounds containing lithium can be applied.
Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, trilllithium, diisopropenylbenzene and sec. Examples thereof include reaction products with −butyllithium, reaction products with divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene.
Further, for example, the organic alkali metal compounds disclosed in US Pat. No. 5,708,092, US Pat. No. 2,241,239, and US Pat. No. 5,527,753 are also applied. it can.

(Adjuster)
For example, when an organic alkali metal compound is used as a polymerization initiator and a predetermined modifier is used when copolymerizing a vinyl aromatic compound and a conjugated diene, a vinyl bond due to the conjugated diene incorporated in the polymer is used. The content of (1,2 bond or 3,4 bond) and the random copolymerization of the vinyl aromatic compound and the conjugated diene can be adjusted.
Examples of such a modifier include, but are not limited to, a tertiary amine compound, an ether compound, a metal alcoholate compound, and the like.
As the adjusting agent, only one type may be used alone, or two or more types may be used in combination.

The tertiary amine compound is not limited to the following, but for example, the general formula R1R2R3N (where R1, R2, R3 is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group). The compounds represented by) are applicable.
Specifically, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidin, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-Tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazin, N, N, N', N ", N" -pentamethylethylenetriamine, N, N'-dioctyl-p-phenylenediamine And so on.

The ether compound is not limited to the following, and for example, a linear ether compound, a cyclic ether compound, and the like can be applied.
The linear ether compound is not limited to the following, and includes, for example, ethylene glycol dialkyl ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol. Examples thereof include dialkyl ether compounds of diethylene glycol such as diethyl ether and diethylene glycol dibutyl ether.
The cyclic ether compound is not limited to, for example, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane. , Alkyl ether of furfuryl alcohol and the like.

Examples of the metal alcoholate compound include, but are not limited to, sodium-t-pentoxide, sodium-t-butoxide, potassium-t-pentoxide, potassium-t-butoxide and the like.

(Polymerization method)
Further, for example, a conventionally known method can be applied as a method for polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator.
Although not limited to the following, for example, batch polymerization, continuous polymerization, or a combination thereof may be used. In particular, batch polymerization is 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.
Further, as the atmosphere of the polymerization system, an atmosphere of an inert gas such as nitrogen gas is preferable.
The polymerization pressure may be set to a pressure range in which the monomer and the solvent can be maintained in the liquid phase in the above temperature range, and is not particularly limited.
Further, it is preferable to be careful not to mix impurities such as water, oxygen, carbon dioxide gas and the like that inactivate the catalyst and the living polymer in the polymerization system.

Further, at the end of the polymerization step, a required amount of a bifunctional or higher functional coupling agent may be added to carry out the coupling reaction.
As the bifunctional coupling agent, known ones can be applied and are not particularly limited. For example, alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dichloroethane, Examples thereof include dihalogen compounds such as dibromoethane, dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate and phthalates.
Further, as the trifunctional or higher functional polyfunctional coupling agent, conventionally known ones can be applied and are not particularly limited. For example, trihydric or higher polyalcohols, epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis (N-N'-diglycidyl aminomethyl) polyepoxy compounds such as cyclohexane, general formula R ₄ -nSiX _A silicon halide compound represented by _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), for example, methylsilyl trichloride, t-butyl. Cyril trichloride, silicon tetrachloride and bromines thereof, etc., 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). ), Examples thereof include polyvalent halogen compounds such as methyl tin trichloride, t-butyl tin trichloride, and tin tetrachloride. Further, dimethyl carbonate, diethyl carbonate or the like may be used.

(Degeneration process)
As described above, the hydrogenated block copolymer (a) of the present embodiment may be a modified block copolymer to which atomic groups having functional groups are bonded. It is preferable that the atomic group having a functional group is bonded as a pre-step of the hydrogenation step described later.
The "atomic group having a functional group" is not particularly limited, but for example, a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, and an aldehyde. Group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, From thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxysilicon group, tin halide group, boronic acid group, boron-containing group, boronic acid group, alkoxytin group, phenyltin group, etc. Examples thereof include atomic groups containing at least one selected functional group. In particular, an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is preferable.
The "atomic group having a functional group" is bound by a denaturing agent.
The modifier is not particularly limited, but is, for example, tetraglycidylmethoxylenidamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyl. Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1 , 3-Diethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N-methylpyrrolidone and the like.

The modified block copolymer is not particularly limited, but for example, it can be polymerized by an anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group, or a functional group is formed at the living terminal. It can be obtained by subjecting it to an addition reaction with a modifier containing a functional group.
As another method, an organic alkali metal compound such as an organic lithium compound is reacted (metallation reaction) with the block copolymer, and a modifier having a functional group is added to the block polymer to which the organic alkali metal is added. Obtained by
However, in the case of the latter method, it is also possible to prepare a modified hydrogenated block copolymer by reacting the hydrogenated block copolymer (a) with a metallization reaction and then reacting with a modifier. it can.
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 denaturation reaction varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours.
Depending on the type of modifier used, the amino group or the like may generally be an organometallic salt at the stage of reacting the modifier, but in that case, treat with a compound having active hydrogen such as water or alcohol. Can be converted into an amino group or the like. In such a modified copolymer, a partially unmodified copolymer may be mixed with the modified copolymer.

Further, the modified block copolymer described above may be a secondary modified block copolymer. The secondary modified block copolymer can be obtained by reacting the modified block copolymer with a secondary modifier having reactivity with the functional group of the modified block copolymer.
The secondary modifier is not particularly limited, and examples thereof include a modifier 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 examples thereof include functional groups thereof. It shall have at least two functional groups selected from the groups.
However, when the functional group is an acid anhydride group, it may be provided with 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 0.3 to 10 mol per 1 equivalent of the functional group bonded to the modified block copolymer. Is preferable, 0.4 to 5 mol is more preferable, and 0.5 to 4 mol is further preferable.
Known methods can be applied to the method of reacting the modified block copolymer with the secondary modifier, and the method is not particularly limited. For example, a melt-kneading method described later, a method of dissolving or dispersing and mixing each component in a solvent or the like, and the like can be mentioned. It is preferable that these secondary modifications are performed after the hydrogenation step.

Specific examples of the secondary modifier include maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride, toluylene diisocyanate, and tetraglycidyl-1,3-. Bisaminomethylcyclohexane, bis- (3-triethoxysilylpropyl) -tetrasulfan and the like are suitable.

The hydrogenated block copolymer (a) of the present embodiment is a modified block graft-modified with α, β-unsaturated carboxylic acid or a derivative thereof, for example, an anhydride, an esterified product, an amidated product, or an imidized product. It can be a polymer.
Specific examples of α, β-unsaturated carboxylic acid or a derivative thereof are not particularly limited, but for example, maleic anhydride, imide maleic anhydride, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, endo-cis-. Examples thereof include bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid or an anhydride thereof.
The amount of α, β-unsaturated carboxylic acid or a derivative thereof added is preferably 0.01 to 20 parts by mass, more preferably 0.1 per 100 parts by mass of the hydrogenated block copolymer (a). It is 10 parts by mass.
The reaction temperature for graft modification is preferably 100 to 300 ° C, more preferably 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 process)
The hydrogenated block copolymer (a) of the present embodiment is obtained by subjecting the non-hydrogenated or modified block copolymer as described above to a hydrogenation reaction using a predetermined hydrogenated catalyst. ..
The hydrogenation catalyst is not particularly limited, and is, for example, a supported type in which a known catalyst (1) a metal such as Ni, Pt, Pd, Ru is supported on carbon, silica, alumina, silica soil or the like. Heterogeneous hydrogenation catalyst, (2) A so-called Cheegler-type hydrogenation catalyst that uses an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as an acetylacetone salt and a reducing agent such as organic aluminum, (3). ) A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr is used.
Specifically, but not limited to the following, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-377970, Japanese Patent Publication No. 1-53851. The hydrogenated catalyst described in Japanese Patent Publication No. 2-9041 can be used.
Suitable hydrogenation catalysts include titanocene compounds, reducing organometallic compounds, or mixtures thereof.
The titanocene compound is not limited to the following, and for example, the compound described in JP-A-8-109219 can be used. Specifically, at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton such as biscyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride, etc. Examples include compounds having.
Examples of the reducing organic metal compound include, but are not limited to, an organic alkali metal compound such as organic lithium, an organic magnesium compound, an organic aluminum compound, an organic boron compound, and an organic zinc compound.

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

[Hydrogenated block copolymer composition]
The hydrogenated block copolymer composition of the present embodiment includes the above-mentioned (a) hydrogenated block copolymer: 1% by mass or more and 95% by mass or less, and (b) at least one kind of olefin resin: 5% by mass. Includes 99% by mass or less.

((B) Olefin resin)
The olefin resin (b) constituting the hydrogenated block copolymer composition of the present embodiment will be described below.
The olefin resin (b) is not limited to the following, and for example, polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl. Examples thereof include homopolymers of α-olefins such as -1-pentene and 1-octene. Further, a random copolymer composed of a combination of olefins selected from ethylene, propylene, butene, pentene, hexene, octene and the like, or a block copolymer can be mentioned.
Specifically, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1. -Hexen copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer , Propropylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, propylene-1-octene-ethylene copolymer, etc. And / or propylene-α-olefin copolymers.
Further, the copolymer with ethylene and / or propylene also includes a copolymer with other unsaturated monomers.
The copolymer with the other unsaturated monomer is not limited to the following, but for example, ethylene and / or propylene and acrylic acid, methacrylate, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, etc. Copolymers with unsaturated organic acids such as maleic anhydride, aryl maleate imide, alkyl maleate imide or derivatives thereof; copolymers of ethylene and / or propylene with vinyl esters such as vinyl acetate; further ethylene and / Or a copolymer of propylene with a non-conjugated diene such as dicyclopentadiene, 4-ethylidene-2-norbornene, 4-methyl-1,4-hexadien, 5-methyl-1,4-hexadien and the like.
(B) The olefin-based resin contains at least one kind of polypropylene-based resin from the viewpoint of economic efficiency and high transparency with good compatibility in the hydrogenated block copolymer composition of the present embodiment. It is preferable that it is a polymer.

Further, the olefin resin (b) may be modified by a predetermined functional group.
The functional group is not particularly limited, and examples thereof include an epoxy group, a carboxy group, an acid anhydride group, and a hydroxyl group.
The functional group-containing compound or modifying agent for modifying the olefin resin (b) is not particularly limited, and examples thereof include the following compounds.
For example, unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether and allyl glycidyl ether, maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, itaconic anhydride and the like. Examples include unsaturated organic acids such as.
In addition, although not particularly limited, examples thereof include ionomers and chlorinated polyolefins.

The olefin resin (b) is a polypropylene homopolymer or ethylene-propylene from the viewpoint of economical efficiency and high transparency with good compatibility in the hydrogenated block copolymer composition of the present embodiment. -It is preferable that it is a polypropylene-based resin such as random or block copolymer.
In particular, an ethylene-propylene / random copolymer is more preferable from the viewpoint of transparency and flexibility.
The olefin resin (b) may be composed of only one kind of single material, or may be a combination of two or more kinds.

The hydrogenated block copolymer composition in the present embodiment contains a hydrogenated block copolymer (a) and at least one kind of olefin resin (b), and is a 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 further 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 wear resistance of the hydrogenated block copolymer composition tends to be improved and the hardness tends to be lowered. On the other hand, when the content of the hydrogenated block copolymer (a) is 95% by mass or less, the wear resistance of the hydrogenated block copolymer composition tends to be improved.

The hydrogenated block copolymer composition of the present embodiment includes the above-mentioned hydrogenated block copolymer (a) and polyolefin resin (b), as well as any rubber softener, modifier, additive and the like. May be blended.
The softening agent for rubber softens the hydrogenated block copolymer composition of the present embodiment and imparts fluidity (molding processability).
The softening agent for rubber is not limited to the following, and for example, mineral oils and liquid or low molecular weight synthetic softeners can be applied, and naphthene-based and / or paraffin-based process oils or extender oils are particularly preferable.
The softening agent for mineral oil-based rubber is a mixture of an aromatic ring, a naphthenic ring and a paraffin chain, and the paraffin chain having 50% or more of carbon atoms in the paraffin chain is called paraffin-based and has the carbon number of the naphthenic ring. The one having 30 to 45% is called naphthenic type, and the one having more than 30% aromatic carbon number is called aromatic type.
As the synthetic softener, for example, polybutene, low molecular weight polybutadiene, liquid paraffin and the like can be used, but the above-mentioned softener for mineral oil-based rubber is more preferable.
When the hydrogenated block copolymer composition of the present embodiment is required to have high heat resistance and mechanical properties, the applied mineral oil-based rubber softener has a kinematic viscosity of 60 cst or more at 40 ° C. Is preferable, and more preferably 120 cst or more.
As the softening agent for rubber, only one kind may be used alone, or two or more kinds may be used in combination.
The modifier has a function of improving the scratch resistance of the surface of the hydrogenated block copolymer composition of the present embodiment and improving the adhesiveness.
The modifier is not limited to the following, and for example, organic polysiloxane can be applied. This exerts a surface modification effect of the hydrogenated block copolymer composition and functions as an auxiliary agent for improving wear resistance.
The modifier may be in the form of a low-viscosity liquid to a high-viscosity liquid or a solid, but from the viewpoint of ensuring good dispersibility in the hydrogenated block copolymer composition of the present embodiment. , Liquids, i.e. silicone oils are preferred. Further, regarding the kinematic viscosity, 90 cst or more is preferable, and 1000 cst or more is more preferable, from the viewpoint of suppressing bleeding of the polysiloxane itself. The polysiloxane is not limited to the following, but for example, general-purpose silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, and various modifications such as alkyl modification, polyether modification, fluorine modification, alcohol modification, amino modification, and epoxy modification. Silicone oil can be mentioned. Although not particularly limited, dimethylpolysiloxane is preferable because it is highly effective as an auxiliary agent for improving wear resistance. Only one kind of these organic polysiloxanes may be used alone, or two or more kinds thereof may be used in combination.
Additives include fillers, lubricants, mold release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, flame retardants, antistatic agents, reinforcing agents, colorants, thermoplastic resins and There is no particular limitation as long as it is generally used for blending a rubber-like polymer.
Fillers include, but are not limited to, silica, talc, mica, calcium silicate, hadrotalsite, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate. , Inorganic fillers such as barium sulfate, and organic fillers such as carbon black.
Examples of the lubricant include, but are not limited to, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearoamide and the like.
The plasticizer is not limited to the following, and examples thereof include organic polysiloxane and mineral oil.
Examples of the antioxidant include, but are not limited to, hindered phenolic antioxidants.
The heat stabilizer is not limited to the following, and examples thereof include phosphorus-based, sulfur-based and amine-based heat stabilizers.
The light stabilizer is not limited to the following, and examples thereof include hindered amine-based light stabilizers.
The ultraviolet absorber is not limited to the following, and examples thereof include benzotriazole-based ultraviolet absorbers.
Examples of the reinforcing agent include, but are not limited to, organic fibers, glass fibers, carbon fibers, metal whiskers, and the like.
Examples of the colorant include, but are not limited to, titanium oxide, iron oxide, carbon black, and the like.
In addition, those described in "Rubber / Plastic Combination Chemicals" (edited by Rubber Digest) and the like can be mentioned.

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 the present embodiment is not limited to the following, but for example, mixing of a Banbury mixer, a single-screw screw extruder, a twin-screw screw extruder, a conider, a multi-screw screw extruder, or the like. A method of melt-kneading each component (the above-mentioned hydrogenated block copolymer (a), polyolefin resin (b), and other additives) using a machine, and after dissolving or dispersing and mixing each component, heat the solvent. A method of removing or the like is used.
In particular, the melt-kneading method using an extruder is suitable from the viewpoint of productivity and good kneading.
The shape of the hydrogenated block copolymer composition of the present embodiment is not limited to the following, but may be any shape such as pellet shape, sheet shape, strand shape, chip shape and the like. .. Further, after melt-kneading, a molded product may be directly produced.

[Molded product using hydrogenated block copolymer composition]
The molded product of the present embodiment is the molded product of the hydrogenated block copolymer composition of the present embodiment described above.
The hydrogenated block copolymer composition of the present embodiment is not particularly limited, and is, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotary molding, powder slush molding. , Foam molding, laminated molding, calendar molding, blow molding, etc., can be processed into a practically useful molded product.
The molded body of the present embodiment is not particularly limited, but for example, a sheet, a film, an injection molded body of various shapes, a hollow molded body, a pneumatic molded body, a vacuum molded body, an extrusion molded body, a foam molded body, a non-woven fabric or a fiber. A wide variety of molded products such as shaped molded products and synthetic leather can be mentioned.
These molded products can be used, for example, for automobile parts, food packaging materials, medical appliances, home appliance parts, electronic device parts, building materials, industrial parts, household goods, toy materials, footwear materials, textile materials and the like.

Automotive parts include, but are not limited to, side moldings, grommet, shift knobs, weather strips, window frames and their sealants, armrests, assist grips, door grips, steering wheel grips, console boxes, headrests, instruments. Panels, bumpers, spoilers, airbag covers, etc.
Examples of medical devices include, but are not limited to, medical tubes, medical hoses, catheters, blood bags, infusion bags, platelet storage bags, artificial dialysis bags, and the like.
The building material is not limited to the following, and examples thereof include wall materials and floor materials.
In addition, although not particularly limited, examples thereof include industrial hoses, food hoses, vacuum cleaner hoses, electric cooling packings, electric wires and other various covering materials, grip covering materials, and soft dolls.
The molded product of the present embodiment may be appropriately subjected to processing such as foaming, powdering, stretching, adhesion, printing, painting, and plating.
Since the hydrogenated block copolymer composition of the present embodiment exhibits excellent effects of flexibility, low resilience, transparency, and kink resistance, it is extremely used as a material for hollow molded bodies such as hoses and tubes. It is useful.

(Reinforcing filler formulation)
In the hydrogenated block copolymer or the hydrogenated block copolymer composition of the present embodiment (hereinafter, may be referred to as component (A)), a silica-based inorganic filler, a metal oxide, a metal hydroxide, A reinforcing filler compound can be prepared by blending at least one reinforcing filler selected from metal carbon oxide and carbon black (hereinafter, may be referred to as component (C)).
The blending amount of the component (C) in the reinforcing filler formulation is preferably 0.5 to 100 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition. It is 5 to 100 parts by mass, more preferably 20 to 80 parts by mass.
When the reinforcing filler formulation is prepared using the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)) of the present embodiment, 100 parts by mass of the component (A) is prepared. However, it is different from the hydrogenated block copolymer of the present embodiment and the olefin resin (b) in an amount of 0 to 500 parts by mass, preferably 5 to 300 parts by mass, and more preferably 10 to 200 parts by mass. , Thermoplastic resin and / or rubber-like polymer (hereinafter, may be referred to as component (B)) is further preferably included.

Examples of the thermoplastic resin and / or rubber-like copolymer (component (B)) include a conjugated diene monomer having a vinyl aromatic monomer unit content of more than 60% by mass and a vinyl aromatic monomer. Block copolymer resin and hydrogenated product thereof (however, different from the hydrogenated block copolymer (A) of the present embodiment); the polymer of the vinyl aromatic monomer; the vinyl aromatic single amount. Body and other vinyl monomers (eg, ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and acrylic methyl, methacrylate esters such as methacrylate and methyl methacrylate, acrylonitrile, Copolymerized resin with (methacrylonitrile, etc.); Rubber-modified styrene resin (HIPS); Acrylonitrile-butadiene-styrene copolymer resin (ABS); Methacrylate ester-butadiene-styrene copolymer resin (MBS); Polyethylene; Ethylene- Ethylene and other copolymerizable monomers such as propylene copolymers, ethylene-butylene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers and their hydrolyzates. Copolymers having an ethylene content of 50% by mass or more; polyethylene-based resins such as ethylene-acrylate ionomer and chlorinated polyethylene; polypropylene; propylene-ethylene copolymer, propylene-ethyl acrylate copolymer and chlorine Polypropylene resin such as polypropylene, cyclic olefin resin such as ethylene-norbornene resin, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin and their hydrolyzate, etc., which can be copolymerized with propylene. Copolymers with a propylene content of 50% by mass or more composed of monomers; copolymers of acrylic acid and its esters and amides; polyacrylate-based resins; polymers of acrylonitrile and / or methacrylonitrile; with acrylonitrile-based monomers A nitrile resin which is a copolymer having an acrylonitrile-based monomer content of 50% by mass or more composed of other copolymerizable monomers; nylon-46, nylon-6, nylon-66 nylon-610, nylon- Polyamide-based resins such as 11, nylon-12, nylon-6, and nylon-12 copolymers; polyester-based resins; thermoplastic polyurethane-based resins; poly-4,4'-dioxydiphenyl-2,2'-propane carbonate Polycarbonic copolymers such as; polyether Thermoplastic polysulfone such as sulfone and polyallyl sulfone; polyoxymethylene resin; polyphenylene ether resin such as poly (2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide, poly 4,4'-diphenylene Polyphenylene sulfide-based resin such as sulfide; polyallylate-based resin; polyether ketone polymer or copolymer; polyketone-based resin; fluorine-based resin; polyoxybenzoyl-based polymer; polyimide-based resin; 1,2-polybutadiene, transpolybutadiene Such as polybutadiene resin and the like.
These components (B) may be those to which a polar group-containing atomic group such as a hydroxyl group, an epoxy group, an amino group, a carboxylic acid group, or an acid anhydride group is bonded.

The silica-based inorganic filler used as the reinforcing filler (component (C)) is a solid particle containing the chemical formula SiO ₂ as a main component, and is, for example, silica, clay, talc, kaolin, mica, or wollastonite. , Inorganic fibrous substances such as montmorillonite, zeolite, and glass fiber. Further, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica-based inorganic filler can also be used. As the silica-based inorganic filler, silica and glass fiber are preferable. As the silica, dry method white carbon, wet method white carbon, synthetic silicate-based white carbon, colloidal silica and the like can be used.
The silica-based inorganic filler preferably has an average particle size of 0.01 to 150 μm, and in order for the silica-based inorganic filler to be dispersed in the reinforcing filler formulation and sufficiently exerting its addition effect, it is necessary. The average dispersed particle size is preferably 0.05 to 1 μm, more preferably 0.05 to 0.5 μm.

The metal oxide used as the reinforcing filler (component (C)) is a solid particle whose main component is the chemical formula MxOy (M is a metal atom and x and y are integers of 1 to 6 each) as a constituent unit. Alumina, titanium oxide, magnesium oxide, zinc oxide and the like. Further, a mixture of the metal oxide and an inorganic filler other than the metal oxide may be used.
Metal hydroxides used as reinforcing fillers are aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide. , Hydrate of tin oxide, hydrate of inorganic metal compound such as borosand, etc. Hydrate-based inorganic filler, among which magnesium hydroxide and aluminum hydroxide are preferable.
Examples of the metallic carbon oxide used as the reinforcing filler include calcium carbonate and magnesium carbonate.
Further, as a reinforcing filler, carbon black of each class such as FT, SRF, FEF, HAF, ISAF, SAF can be used, the nitrogen adsorption specific surface area is 50 mg / g or more, and the DBP (dibutyl phthalate) oil absorption amount is 80 mL. / 100 g of carbon black is preferred.

In the reinforcing filler formulation using the hydrogenated block copolymer or the hydrogenated block copolymer composition of the present embodiment, the silane coupling agent (hereinafter, may be referred to as component (D)) is used. You may use it.
The silane coupling agent is for making the interaction between the hydrogenated block copolymer and the reinforcing filler close, and has an affinity for one or both of the hydrogenated block copolymer and the reinforcing filler. A compound having a sex or binding group.
Preferred silane coupling agents include those having a polysulfide bond in which two or more mercapto groups and / or sulfur are linked together with silanol group or alkoxysilane, and specifically, bis- [3- (triethoxysilyl). )-Propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, 3-mercaptopropyl-trimethoxysilane, Examples thereof include 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropylbenzothiazoletetrasulfide and the like.
From the viewpoint of obtaining the desired action and effect, the blending amount of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and further, with respect to the reinforcing filler formulation. It is preferably 1 to 15% by mass.

The hydrogenated block copolymer of the present embodiment or the reinforcing filler compound containing the hydrogenated block copolymer composition and the reinforcing filler is vulcanized with a vulcanizing agent, that is, crosslinked and vulcanized. It may be a composition.
Examples of the sulfide are radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, sulfur compounds (sulfur monochloride, sulfur dichloride, disulfide compounds, high molecular weight polysulfur compounds, etc.). Can be used.
The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition. Is.
Organic peroxides used as vulcanizing agents (hereinafter, may be referred to as component (E)) have odor and scorch stability (crosslinking does not occur under the conditions when each component is mixed, but the crosslinking reaction conditions From the viewpoint of (characteristic of rapid cross-linking when vulcanized), 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) Hexin-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.
Other than the above, dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide. , Tert-Butyl cumyl peroxide and the like can also be used.

When vulcanizing, as a vulcanization accelerator (hereinafter, may be referred to as component (F)), sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole. A system, a thiourea system, a dithiocarbamate system compound and the like may be used in an amount as required.
Further, as a vulcanization aid, zinc oxide, stearic acid and the like can be used in an amount as required.
Further, when the above-mentioned organic peroxide is used to crosslink the reinforcing filler formulation, sulfur; p-quinonedioxime, p, p'-dibenzoylquinonedioxime, particularly as a vulcanization accelerator, is used. Peroxy cross-linking aids such as N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedi maleimide (hereinafter referred to as component (G)) ); Polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate; vinyl butyrate, vinyl stearate, etc. Polyfunctional vinyl monomer (hereinafter, may be referred to as component (H)) and the like can also be used in combination with an organic peroxide.
Such a vulcanization accelerator is usually preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition. Used in proportions of parts.
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, bending resistance and oil resistance in the vulcanized state.

In order to improve the processability of the reinforcing filler compound, a rubber softener (hereinafter, may be referred to as component (I)) may be blended.
Mineral oil and liquid or low molecular weight synthetic softeners are suitable as softeners for rubber. Of these, naphthenic and / or paraffinic process oils or extender oils, which are generally used for softening, increasing the volume, and improving workability of rubber, are preferable.
The softening agent for mineral oil-based rubber is a mixture of an aromatic ring, a naphthenic ring and a paraffin chain, and the paraffin chain having 50% or more of carbon atoms in the paraffin chain is called paraffin-based and has the carbon number of the naphthenic ring. The one having 30 to 45% is called naphthenic type, and the one having more than 30% aromatic carbon number is called aromatic type. A synthetic softener may be used in the reinforcing filler formulation, and polybutene, low molecular weight polybutadiene, liquid paraffin and the like can be used. However, the above-mentioned softener for mineral oil-based rubber is preferable.
The amount of the softening agent for rubber (component (I)) in the reinforcing filler formulation is 0 with respect to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). It is preferably ~ 100 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 30 to 90 parts by mass. If the amount of the softening agent for rubber exceeds 100 parts by mass, bleed-out is likely to occur, and the surface of the composition may become sticky.

The reinforcing filler compound containing the hydrogenated block copolymer or the hydrogenated block copolymer composition of the present embodiment can be suitably used as a building material, an electric wire coating material, a vibration damping material, or the like. Further, the vulcanized composition is suitable for tire applications and materials such as anti-vibration rubber, belts, industrial products, footwear, and foams by taking advantage of its characteristics.

(Crosslinked product)
The hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment is crosslinked in the presence of a vulcanizing agent to form a crosslinked product, that is, a crosslinked hydrogenated block copolymer or a crosslinked hydrogenated block copolymer. It can be a composition.
By cross-linking the hydrogenated block copolymer or the hydrogenated block copolymer composition of the present embodiment, heat resistance [high temperature C-Set (compression set)] and bending resistance can be improved.
When a crosslinked product of the reinforcing filler formulation containing the hydrogenated block copolymer composition of the present embodiment is prepared, particularly, the hydrogenated block copolymer or the hydrogenated block copolymer composition ( The blending ratio of the component (A)) with the thermoplastic resin and / or the rubber-like polymer (component (B)) is the mass ratio of the component (A) / component (B), which is 10/90 to 100/0. Is preferable, more preferably 20/80 to 90/10, and even more preferably 30/70 to 80/20.

In the present embodiment, the method of crosslinking is not particularly limited, but it is preferable to perform so-called “dynamic crosslinking”.
Dynamic cross-linking is a method of simultaneously causing dispersion and cross-linking by kneading various formulations in a molten state under temperature conditions at which a vulcanizing agent reacts. Y. It is described in detail in the literature of Coran et al. (Rub. Chem. And Technol. Vol. 53.141- (1980)). Dynamic cross-linking is usually performed using a closed kneader such as a Banbury mixer or a pressurized kneader, or a single-screw or twin-screw extruder. The kneading temperature is usually 130 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 cross-linking, an organic peroxide or a phenol resin cross-linking agent is used, and the amount thereof is usually a hydrogenated block copolymer or a hydrogenated block copolymer composition (components (components). A)) 0.01 to 15 parts by mass, preferably 0.04 to 10 parts by mass with respect to 100 parts by mass.
As the organic peroxide used as a vulcanizing agent, the component (E) can be used. When cross-linking using an organic peroxide, the component (F) can be used as a vulcanization accelerator, and the component (G), the component (H), and the like can also be used in combination. .. The amount of these vulcanization accelerators used is usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). It is preferably 0.1 to 15 parts by mass.

The crosslinked product using the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)) of the present embodiment is provided with a softening agent and heat resistance as necessary within a range that does not impair the purpose. Additives such as stabilizers, antistatic agents, weather-resistant stabilizers, antiaging agents, fillers, colorants, and lubricants can be added. The component (I) can be used as a softening agent to be blended to adjust the hardness and fluidity of the final product.
The softening agent may be added at the time of kneading each component, or may be contained in the copolymer in advance at the time of producing the hydrogenated block copolymer, that is, an oil-extended rubber may be prepared.
The amount of the softening agent added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). , More preferably 20 to 100 parts by mass.
Further, as the filler, the component (C) which is the above-mentioned reinforcing filler can be used. The amount of the filler added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). , More preferably 20 to 100 parts by mass.
The crosslinked product has a gel content (however, does not contain insoluble components such as insoluble substances such as inorganic fillers), preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and further preferably 20 to 60% by mass. It is recommended to dynamically crosslink to%. Regarding the gel content, 1 g of the crosslinked product was refluxed with a Soxhlet extractor using boiling xylene for 10 hours, the residue was filtered through an 80 mesh wire mesh, and the dry mass (g) of the insoluble material remaining on the mesh was measured. The ratio (% by mass) of the insoluble matter to 1 g of the sample obtained is defined as the gel content. The gel content can be controlled by adjusting the type and amount of the vulcanizing agent and the conditions (temperature, residence time, share, etc.) at the time of vulcanization.
Similar to the vulcanization composition of the reinforcing filler compound, the crosslinked product can be applied to tire applications, anti-vibration rubber, belts, industrial products, footwear, foams, etc., and further, medical equipment materials and foods. It can also be used as a 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 to the following examples and comparative examples.
Various physical properties were measured by the methods shown below.

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

((2) Content of polymer block (polystyrene block) mainly composed of vinyl aromatic compound monomer unit in hydrogenated block copolymer (a))
The method according to (Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54,685 (1981)) using a block copolymer before hydrogenation and using a nuclear magnetic resonance apparatus (NMR). Hereinafter, "NMR method". It is called.) Measured.

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

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

((3-3) Amount of vinyl bond in polymer block (c))
It was calculated from the values of the vinyl bond amounts in (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 [equipment: HLC-82209PC (manufactured by Tosoh Corporation), column: TSKgegard volume SuperHZ-L (4.6 mm × 20 cm) × 3 pieces].
Tetrahydrofuran was used as the solvent. The measurement was performed at a temperature of 35 ° C.
The weight average molecular weight was determined by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained by measuring the peak molecular weight of the chromatogram from the measurement of commercially available standard polystyrene.
When there are a plurality of peaks in the chromatogram, the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram) was defined as the weight average molecular weight.
The weight average molecular weight immediately before the addition of ethyl benzoate was also measured. The measurement method was calculated from the GPC of the polymer obtained by inactivating the polymer sampled immediately before the addition of ethyl benzoate with methanol and adding ethyl benzoate to the one to which ethyl benzoate was not added. Was measured by GPC using the prepared hydrogenated block copolymer (a).
The molecular weight distribution was also measured by GPC in the same manner.

((5) Ratio (%) of the area of the hydrogenated block copolymer (a) in the range of molecular weight 10,000 to 150,000 to the area of the GPC curve in the range of molecular weight 10,000 to 1,000,000, 200,000. Percentage of areas in the range of 100 or more (%))
The measurement was performed by GPC [device: HLC-82209PC (manufactured by Tosoh Corporation), column: TSKggrade volume SuperHZ-L (4.6 mm × 20 cm) × 3).
Tetrahydrofuran was used as the solvent.
The measurement was performed at a temperature of 35 ° C.
The area value (%) of the molecular weight of the hydrogenated block copolymer (a) in the range of 10,000 or more and 150,000 or less is the molecular weight of the hydrogenated block copolymer (a) of 10,000 or more and 150,000 in the GPC curve. It refers to a value obtained from the ratio of the area value in the following range to the area value in the molecular weight range of 10,000 to 1,000,000.
The area value (%) of the molecular weight of the hydrogenated block copolymer (a) in the range of 200,000 or more and 1 million or less is the molecular weight of the hydrogenated block copolymer (a) of 200,000 or more and 1 million or more in the GPC curve. It refers to a value obtained from the ratio of the area value in the following range to the area value in the molecular weight range of 10,000 to 1,000,000.

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

((7) Content of vinyl aromatic compound monomer unit in copolymer block (b))
The method described in (Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981)) using a nuclear magnetic resonance apparatus (NMR) using a block copolymer before hydrogenation as a sample. Hereinafter, "NMR method". The measured content of the total vinyl aromatic compound (styrene) monomer unit in the hydrogenated block copolymer (a) and the vinyl aromatic compound single amount in the hydrogenated block copolymer (a). It was calculated from the difference in the content of the polymer block mainly composed of body units.

[Characteristic measurement method]
((1) tan δ peak temperature)
First, a "press-molded sheet" manufactured as described later was cut into a size of 12.5 mm in width and 40 mm in length to prepare a sample for measurement.
Next, this measurement sample was set in the twist type geometry of the device ARES (manufactured by TA Instruments Co., Ltd., trade name), and the effective measurement length was 25 mm, strain was 0.5%, frequency was 1 Hz, and ascending. It was determined under the condition of a temperature rate of 3 ° C./min.
The tan δ peak temperature was a value obtained from the peak detected by the automatic measurement of RSI Orchestrator (manufactured by TA Instruments Co., Ltd., trade name).

((2) Hardness)
According to JIS K6253, the instantaneous value and the value after 10 seconds were measured with a durometer type A.
The hardness value at the moment when the probe of the hardness measuring instrument was lowered onto the sample and the hardness value 10 seconds after the lowering was measured.
In Tables 1 and 2 below, hardness (JIS-A, instantaneous) and hardness (JIS-A, 10s) are described, respectively.
The hardness value is preferably 96 or less.

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

((4) Wear resistance)
Using a Gakushin type friction tester (manufactured by Tester Sangyo Co., Ltd., AB-301 type), the surface (skin textured surface) of the molded sheet prepared by [Production of injection molded sheet] described later is used as a friction cloth Kanakin No. 3 cotton. , It was rubbed with a load of 500 g, and it was judged according to the following criteria based on the amount of volume reduction after friction.
◎ (3 points): Volume reduction is 0.01 mL or less after 10,000 rubbing times ○ (2 points): Volume reduction is more than 0.01 mL and 0.1 mL or less after 10,000 rubbing times Δ (1 point): Volume loss exceeds 0.1 mL and 0.2 mL or less after 10,000 rubbing times × (0 points): Volume loss is 0.2 mL after 10,000 rubbing times Super

((5) Ease of pulling strands (extrusion moldability))
Using the hydrogenated block copolymer composition described later, the ease of pulling the strands extruded through the die nozzle of the single-screw extruder TEX-30 type vent manufactured by Japan Steel Works, Ltd. can be visually checked in three steps. evaluated.
The one that pulls the strand at high speed is evaluated as "3", and the one that cannot be cut if the strand is pulled at high speed is evaluated as "2", and the one that cannot be cut at low speed is evaluated as "2". The thing was evaluated as "1".
The larger the number on the three-point scale, the better the extrusion moldability.

((6) Pellet blocking resistance)
The blocking resistance was measured by the following method.
60 g of sample pellets of the same shape (cylindrical shape having a diameter of about 3 mm × 3 mm) made of a hydrogenated block copolymer were placed in a metal cylinder having a diameter of 5 cm, and a weight of 1160 g was placed on the sample pellets.
In this state, after heating in a gear oven heated to 42 ° C. for 20 hours, the state of adhesion of pellets in the cylinder was observed.
Specifically, since the pellet mass taken out from the cylinder collapses (however, the pellet with poor blocking resistance does not collapse as it is), the weight of the mass consisting of three or more pellets is measured, and the total weight of the pellet is measured. The ratio (%) of the weight of the pellet mass to (60 g) was determined.
The quality of blocking resistance was evaluated based on the following criteria.
In addition, each sample pellet was evaluated after adding 1500 ppm of calcium stearate.
3: Loosening, but less than 50% of the total mass of pellets consisting of 3 or more pellets 2: Loosening, but 50% or more of the mass of pellets of 3 or more grains 1: Solidified and not loosened at all

[Manufacturing of hydrogenated block copolymer]
(Preparation of hydrogenated catalyst)
In Examples and Comparative Examples described later, hydrogenated catalysts used for producing hydrogenated block copolymers were prepared by the following methods.
A reaction vessel equipped with a stirrer was replaced with nitrogen, and 1 liter of dried and purified cyclohexane was charged therein.
Next, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added.
An n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring, and the mixture was reacted at room temperature for about 3 days. As a result, a hydrogenated catalyst was obtained.

<Hydrogenated block copolymer>
Hydrogenated block copolymers (a) -1 to (a) -30 and (a) -A to (a) -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 reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, n-butyllithium is 0.096 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-butyllithium. 1.8 mol with respect to 1 mol and 0.08 mol with respect to 1 mol of n-butyllithium were further added with sodium-t-pentoxide and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60 ° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added to 1 mol of n-butyllithium, and the mixture was reacted at 70 ° C. for 10 minutes. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond content of 51% by mass, and a weight average molecular weight of 151,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. Block copolymer (a) -1 was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -1 was 98%. Other characteristics are shown in Table 1.

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

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

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

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

[Example 6]
(Hydrogenated block copolymer (a) -6)
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 41 parts by mass of butadiene and 59 parts by mass of styrene was added.
Next, n-butyllithium is 0.097 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-butyllithium. 1.8 mol with respect to 1 mol and 0.08 mol with respect to 1 mol of n-butyllithium were further added with sodium-t-pentoxide, and the mixture was polymerized at 60 ° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added to 1 mol of n-butyllithium, and the mixture was reacted at 70 ° C. for 10 minutes. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 59% by mass, a polystyrene block content of 0% by mass, a vinyl bond content of 51% by mass, and a weight average molecular weight of 151,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. A block copolymer (a) -6 was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -6 was 97%. Other characteristics are shown in Table 1.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Example 28]
(Hydrogenated block copolymer (a) -28)
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, n-butyllithium is 0.112 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-butyllithium. 1.8 mol with respect to 1 mol and 0.08 mol with respect to 1 mol of n-butyllithium were further added with sodium-t-pentoxide, and the mixture was polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 32 parts by mass of butadiene and 58 parts by mass of styrene was added and polymerized at 60 ° C. for 2 hours. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 42% by mass, a polystyrene block content of 10% by mass, a vinyl bond content of 60% by mass, and a weight average molecular weight of 135,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. A block copolymer (a) -28 was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -28 was 97%. Other characteristics are shown in Table 3.

[Example 29]
(Hydrogenated block copolymer (a) -29)
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 16.7 parts by mass of styrene was added.
Next, n-butyllithium is 0.112 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-butyllithium. 1.8 mol with respect to 1 mol and 0.08 mol with respect to 1 mol of n-butyllithium were further added with sodium-t-pentoxide, and the mixture was polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 50 parts by mass of styrene was added, and the mixture was polymerized at 60 ° C. for 2 hours. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 50% by mass, a polystyrene block content of 13.7% by mass, a vinyl bond content of 75% by mass, and a weight average molecular weight of 137,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. A block copolymer (a) -29 was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -29 was 97%. Other characteristics are shown in Table 3.

[Example 30]
(Hydrogenated block copolymer (a) -30)
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added.
Next, n-butyllithium is 0.075 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-butyllithium. 1.8 mol was added to 1 mol and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerized at 60 ° C. for 2 hours. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 65% by mass, a polystyrene block content of 15% by mass, a vinyl bond content of 23% by mass, and a weight average molecular weight of 150,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. A block copolymer (a) -30 was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -30 was 97%. Other characteristics are shown in Table 3.

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

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

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

[Comparative Example 4]
(Hydrogenated block copolymer (a) -D)
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, 0.096 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and n, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") are n-butyllithium. 0.2 mol was added to 1 mol, and the mixture was polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60 ° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added to 1 mol of n-butyllithium, and the mixture was reacted at 70 ° C. for 10 minutes. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond content of 10% by mass, and a weight average molecular weight of 151,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. A block copolymer (a) -D was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -D was 98%. Other characteristics are shown in Table 4.

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

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

[Comparative Example 7]
(Hydrogenated block copolymer (a) -G)
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, n-butyllithium is 0.09 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-butyllithium. 1.8 mol with respect to 1 mol and 0.08 mol with respect to 1 mol of n-butyllithium were further added with sodium-t-pentoxide and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 17 parts by mass of butadiene and 73 parts by mass of styrene was added and polymerized at 60 ° C. for 2 hours. Then, methanol was added to stop the polymerization reaction.
The block copolymer obtained as described above had a styrene content of 83% by mass, a polystyrene block content of 10% by mass, a vinyl bond content of 36% by mass, and a weight average molecular weight of 151,000.
Further, to the obtained block copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the block copolymer based on Ti, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The addition reaction was carried out.
Next, as a stabilizer, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, and hydrogenated. A block copolymer (a) -G was obtained.
The hydrogenation rate of the obtained hydrogenated block copolymer (a) -G was 97%. Other characteristics 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 produced as described above are used independently and 160 using a 4-inch roll. Rolling was performed at ° C., and then press molding was performed at 200 ° C. and 100 kg / cm ² by a hydraulic press to prepare a press-formed sheet having a thickness of 2 mm.

The values of the following items 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 characteristic value)
-Content of total vinyl aromatic compound monomer unit (mass%)
(A) Content (mass%) of polymer block mainly composed of vinyl aromatic compound monomer unit
(B) Content (% by mass) of hydrogenated copolymer block composed of vinyl aromatic compound monomer unit and conjugated diene monomer unit
(C) Content (mass%) of hydrogenated polymer block mainly composed of conjugated diene monomer unit
(B) Amount of vinyl bond (mass%) of hydrogenated copolymer block
(C) Amount of vinyl bond (mass%) of hydrogenated polymer block
・ Weight average molecular weight immediately before addition of ethyl benzoate (10,000)
・ Molecular weight distribution
(Molecular weight distribution of ethyl benzoate added products immediately before addition)
・ Weight average molecular weight of (a) (10,000)
-Area value (%) in the range of molecular weight 10,000 to 150,000 with respect to the area in the range of molecular weight 10,000 to 1,000,000 in the GPC chart.
-Area value (%) in the range of molecular weight 200,000 to 1,000,000 with respect to an area in the range of molecular weight 10,000 to 1,000,000 in the GPC chart.
-Vinyl bond amount (mass%) in conjugated diene monomer unit
-Hydrogenation rate (%) of the double bond of the conjugated diene monomer unit
-Content (mass%) of vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above.
-Content (mass%) of conjugated diene monomer unit in the hydrogenated copolymer block of (b) above.
(Characteristic)
・ Melt flow rate (230 ° C, 2.16 kg)
・ Peak temperature of tan δ (tangent loss) in viscoelasticity measurement chart ・ A hardness (instantaneous, 10s)
・ Pellet blocking property

The polymer blocks (a) to (c) represent the following polymer blocks, respectively.
Polymer block (a): Polymer block mainly composed of vinyl aromatic compound monomer unit Copolymer block (b): Hydroponic consisting of vinyl aromatic compound monomer unit and conjugated diene monomer unit Copolymer block Polymer block (c): Hydrogenated polymer block mainly composed of conjugated diene monomer unit

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

(Olefin resin (b))
PM900C (PP / SunAllomer; MFR = 30) was used as the olefin resin (b).

[Manufacturing of injection molded sheet]
[Example 31]
The pelletized hydrogenated block copolymer (a) -1 and the olefin resin (b) are blended in the proportions (% by mass) shown in Table 5 below, and are used in a twin-screw extruder (TEX-30). A hydrogenated block copolymer composition was obtained by kneading and pelletizing.
The extrusion conditions were a cylinder temperature of 230 ° C. and a screw rotation speed of 300 rpm. Using the obtained composition, injection molding was performed at 210 ° C. to prepare a sheet having a thickness of 2 mm, and a physical property measurement piece was obtained. The results of physical property measurement are shown in the table.

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

The hydrogenated block copolymers of Examples 1 to 30 and the hydrogenated block copolymer compositions of Examples 31 to 62 have an excellent balance between wear resistance and MFR, and have good hardness and moldability.

The hydrogenated block copolymer of the present invention and its composition are used 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, and the like. , Has industrial availability.

Claims (11)

A hydrogenated block copolymer containing a vinyl aromatic compound monomer unit and a conjugated diene monomer unit.
A hydrogenated block copolymer that satisfies the following requirements (1) to (7).
(1): (b) Contains at least one hydrogenated copolymer block composed of a vinyl aromatic compound monomer unit and a conjugated diene monomer unit.
(2): The content of the 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 is It is 40% by mass or less.
(3): The weight average molecular weight (Mw) is 200,000 or less.
(4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is 20% or more.
(5): In the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC) measurement, the molecular weight is in the range of 10,000 to 150,000 with respect to the area in which the molecular weight is in the range of 10,000 to 1,000,000. The area ratio exceeds 50%.
(6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more.
(7): The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) is 30% by mass or more and 79% 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. (B) In the hydrogenated copolymer block,
The content of the vinyl aromatic compound monomer unit is 45% by mass or more and 79% by mass or less.
The hydrogenated block copolymer according to claim 1 or 2. In the molecular weight curve of a hydrogenated block copolymer obtained by gel permeation chromatography (GPC) measurement, for an area having a molecular weight in the range of 10,000 to 1,000,000.
The hydrogenated block copolymer according to any one of claims 1 to 3, wherein the proportion of the area having a molecular weight in the range of 200,000 to 1,000,000 is 10% or more. The hydrogenated block copolymer according to any one of claims 1 to 4, wherein the content of the total vinyl aromatic compound monomer unit is 40% by mass or more and 80% by mass or less. 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 any one of claims 1 to 5. (C) Contains 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 claims 1 to 6. The hydrogenated block copolymer according to any one of claims 1 to 7, wherein at least one peak of tan δ is present at 0 ° C. or higher and 30 ° C. or lower in the viscoelasticity measurement chart. The hydrogenated block copolymer according to any one of claims 1 to 8 (a): 1% by mass or more and 95% by mass or less.
At least one type of olefin resin (b): 5% by mass or more and 99% by mass or less.
, A hydrogenated block copolymer composition. The olefin resin (b) is
Contains at least one polypropylene-based resin,
The hydrogenated block copolymer composition according to claim 9. A molded product of the hydrogenated block copolymer composition according to claim 9 or 10.