JP7304202B2 - Hydrogenated block copolymer - Google Patents

Description

The present invention provides a hydrogenated block copolymer having a specific structure, a hydrogenated block copolymer containing the hydrogenated block copolymer, an olefinic resin, another thermoplastic resin or polymer, and a softening agent. Regarding the composition.

A copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon has unsaturated double bonds in the polymer, and is therefore inferior in thermal stability, weather resistance, and ozone resistance. As a method for solving such problems, a method of hydrogenating unsaturated double bonds has long been known (see Patent Documents 1 and 2, for example).

On the other hand, a hydrogenated block copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon has the same elasticity at room temperature as vulcanized natural rubber or synthetic rubber without vulcanization. Since it has workability similar to that of thermoplastic resins at high temperatures, it is widely used in fields such as plastic modification, adhesives, automobile parts, and medical equipment. In recent years, attempts have been made to develop properties similar to these properties in random copolymers comprising a conjugated diene compound and a vinyl aromatic hydrocarbon.

For example, Patent Document 3 discloses a random copolymer of a conjugated diene compound having a vinyl aromatic hydrocarbon content of 3 to 50% by mass and a vinyl aromatic hydrocarbon, and having a molecular weight distribution (Mw/Mn) of 10. and a composition of a hydrogenated diene-based copolymer obtained by hydrogenating a copolymer having a vinyl bond content of 10 to 90% by mass in the conjugated diene portion of the copolymer and a polypropylene resin is disclosed. there is Further, in Patent Document 4, a random copolymer of a conjugated diene compound having a vinyl aromatic hydrocarbon content of 5 to 60% by mass and a vinyl aromatic hydrocarbon, and a conjugated diene part in the copolymer A composition of a hydrogenated diene copolymer obtained by hydrogenating a copolymer having a vinyl bond content of 60% or more and a polypropylene resin is disclosed.

As for the above-mentioned hydrogenated diene-based copolymers, attempts have been made to use them in applications for which soft vinyl chloride resins have conventionally been used. Soft vinyl chloride resins have concerns about halogens during combustion and environmental problems caused by endocrine disruptors caused by plasticizers, and there is an urgent need to develop alternative materials. However, such hydrogenated diene-based copolymers are insufficient in properties such as flexibility and abrasion resistance for applications in which soft vinyl chloride resins have conventionally been used.

The present applicant has developed a substitute material for soft vinyl chloride resin, and has already developed a hydrogenated copolymer excellent in flexibility and abrasion resistance (see Patent Documents 5 and 6, for example).

JP-A-56-30447 JP-A-2-36244 JP-A-2-158643 JP-A-6-287365 WO 03/035705 WO 06/088187

However, in order to further expand its use (for example, automotive interior materials), it is desired to develop a material that has conventional properties (flexibility and abrasion resistance) and is excellent in oil resistance.

Accordingly, an object of the present invention is to provide a hydrogenated block copolymer excellent in flexibility and a hydrogenated block copolymer composition excellent in abrasion resistance and oil resistance.

The inventors of the present invention have made intensive studies to solve the above problems, and found that a hydrogenated copolymer obtained by hydrogenating a non-hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit A block copolymer obtained by hydrogenating a polymer block A mainly composed of vinyl aromatic monomer units and a non-hydrogenated polymer block mainly composed of conjugated diene monomer units The inventors have found that a hydrogenated block copolymer containing at least one coalescing block B and satisfying specific requirements effectively solves the above problems, and have completed the present invention.

That is, the present invention relates to the following.
[1]
A hydrogenated block copolymer of a copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit,
containing at least one polymer block A mainly composed of vinyl aromatic monomer units,
containing at least one hydrogenated polymer block B obtained by hydrogenating a non-hydrogenated polymer block mainly composed of conjugated diene monomer units,
A hydrogenated block copolymer satisfying the following (a) to (d);
(a) the content of the hydrogenated polymer block B is 3% by mass or more and less than 20% by mass;
(b) the content of all vinyl aromatic monomer units is 25% by mass or more and 85% by mass or less;
(c) at least one of the hydrogenated polymer blocks B has a hydrogenated polymer block C having a vinyl bond content of 60% by mass or more;
(d) The weight average molecular weight is 50,000 to 600,000.
[2]
The hydrogenated block copolymer according to [1], containing at least two polymer blocks A.
[3]
The hydrogenated block copolymer according to [1] or [2], wherein 75% or more of the double bonds of the conjugated diene monomer units are hydrogenated.
[4]
The hydrogenated block copolymer according to any one of [1] to [3], wherein the content of polymer block A is 3 to 50% by mass.
[5]
containing at least one hydrogenated copolymer block D of a random copolymer consisting of a conjugated diene monomer unit and a vinyl aromatic monomer unit, the content of which is 40 to 90% by mass, [1 ] The hydrogenated block copolymer according to any one of [4].
[6]
The hydrogenated block copolymer according to any one of [1] to [5], containing a hydrogenated polymer block C at at least one end.
[7]
10 to 90 parts by mass of the hydrogenated block copolymer (a) according to any one of [1] to [6];
10 to 90 parts by mass of at least one olefin resin (b);
For a total of 100 parts by mass of (a) and (b),
0 to 150 parts by mass of a thermoplastic resin other than (a) or a polymer (c) other than (a),
0 to 150 parts by mass of a softening agent (d);
A hydrogenated block copolymer composition containing
[8]
A damping material comprising the hydrogenated block copolymer according to any one of [1] to [6].
[9]
A sound absorbing material comprising the hydrogenated block copolymer according to any one of [1] to [6].
[10]
A damping material comprising the hydrogenated block copolymer composition according to [7].
[11]
A sound absorbing material comprising the hydrogenated block copolymer composition according to [7].
[12]
A molded article made of the hydrogenated block copolymer composition according to [7].

The hydrogenated block copolymer of the present invention or a composition containing it is excellent in flexibility, abrasion resistance and oil resistance, and can be used, for example, as vibration-damping/sound-absorbing materials, moldings (automobile interior materials, automobile exterior materials, etc.). It can be suitably used for the purpose of

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

[Hydrogenated block copolymer]
The hydrogenated block copolymer of the present embodiment is a hydrogenated copolymer containing conjugated diene monomer units and vinyl aromatic monomer units.

In the present embodiment, the nomenclature of each monomer unit constituting the polymer follows the nomenclature of the monomer from which the monomer unit is derived. For example, the term "vinyl aromatic monomer unit" means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is a substituted ethylene derived from a substituted vinyl group. It is a molecular structure in which two carbon atoms of the group serve as bonding sites.
The term "conjugated diene monomer unit" means a structural unit of a polymer produced as a result of polymerizing a conjugated diene monomer, and its structure is an olefinic diatomic unit derived from a conjugated diene monomer. It is a molecular structure in which two carbons are binding sites.

In addition, in the structure of the hydrogenated block copolymer in the present embodiment, "mainly" means that the proportion in a predetermined copolymer or copolymer block is 70% by mass or more. , preferably 80% by mass or more, more preferably 90% by mass or more.

The hydrogenated block copolymer of the present embodiment contains at least one polymer block A (hereinafter sometimes referred to as "polymer block A") mainly composed of vinyl aromatic monomer units, preferably two Hydrogenated polymer block B (hereinafter sometimes referred to as "hydrogenated polymer block B") obtained by hydrogenating a non-hydrogenated polymer block mainly composed of conjugated diene monomer units having the above have at least one.

Further, the hydrogenated block copolymer of the present embodiment satisfies the following (a) to (d).
(a) The content of the hydrogenated polymer block B is 3% by mass or more and less than 20% by mass.
(b) The content of all vinyl aromatic monomer units is 25% by mass or more and 85% by mass or less.
(c) At least one of the hydrogenated polymer blocks B has a hydrogenated polymer block C having a vinyl bond content of 60% by mass or more.
(d) The weight average molecular weight is 50,000 to 600,000.

In the hydrogenated block copolymer of the present embodiment and the composition containing the polymer, polymer block A is important in terms of flexibility and abrasion resistance. In the hydrogenated block copolymer of the present embodiment, the content of the polymer block A is preferably 50% by mass or less from the viewpoint of flexibility, and is preferably 3% by mass or more from the viewpoint of abrasion resistance. Preferably, 10% by mass or more is more preferable. When obtaining a hydrogenated block copolymer or the like with particularly good flexibility, the content of the polymer block A is more preferably 10% by mass to 50% by mass, and still more preferably 10% by mass to 40% by mass. Further, when obtaining a hydrogenated block copolymer or the like having particularly good abrasion resistance, the content of the polymer block A is more preferably 15% by mass to 45% by mass, more preferably 20% by mass to 40% by mass. is. Moreover, it is preferable to contain two or more polymer blocks A from the viewpoint of mechanical strength. Although the upper limit of the number of polymer blocks A is not particularly limited, it is, for example, four.

The hydrogenated block copolymer of the present embodiment tends to become more flexible as the total vinyl aromatic monomer unit content decreases.

The hydrogenated block copolymer of the present embodiment is designed to have a total vinyl aromatic monomer unit content of 25% by mass or more and a lower limit (3 to 10% by mass) of the content of the polymer block A. In order to achieve this, by designing the hydrogenated copolymer block D of the random copolymer described later, which has a relatively high proportion of conjugated diene monomer units, to occupy a large proportion in the copolymer, flexible tend to improve. On the other hand, in the hydrogenated block copolymer of the present embodiment, the content of the polymer block A is on the upper limit side (in this case, the upper limit depends on the vinyl aromatic monomer unit in % by mass, and the range is from the upper limit mass % to At the upper limit of −10% by mass), designing two or more polymer blocks A tends to increase the tensile strength.

On the other hand, in the hydrogenated block copolymer of the present embodiment, the content of all vinyl aromatic monomer units is 85% by mass or less, and the content of the polymer block A is on the lower limit side (3 to 10% by mass). ), there is a tendency to increase flexibility by including a hydrogenated copolymer block D of a random copolymer described later. On the other hand, on the upper limit side (40 to 50% by mass) of the content of the polymer block A, the ratio of the hydrogenated copolymer block D of the random copolymer described later in the copolymer is decreased, and the polymer block A By designing two or more, the tensile strength tends to increase.

In the present embodiment, the content of polymer block A is determined by a method of oxidatively decomposing a block copolymer before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., 1, 429 (1946), hereinafter referred to as the osmic acid tetroxide method). In addition, the content of the polymer block A can be determined by using a nuclear magnetic resonance spectrometer (NMR) using a block copolymer before hydrogenation and a block copolymer after hydrogenation as a sample (Y. Tanaka, et al. , RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), hereinafter referred to as the NMR method). In this case, the content of the polymer block A (referred to as Os) measured using the block copolymer before hydrogenation by the osmic acid tetroxide method and the block copolymer after hydrogenation by the NMR method are The content of the polymer block A (referred to as Ns) measured using the method has a correlation represented by the following formula (F).

(Os)=−0.012(Ns) ² +1.8(Ns)−13.0 Formula (F)
Therefore, when the content of the polymer block A in the block copolymer after hydrogenation is determined by the NMR method in the present embodiment, the value of (Os) determined by the above formula (F) is defined in the present embodiment. It is the content of the polymer block A.

The hydrogenated block copolymer of the present embodiment has at least one hydrogenated polymer block B obtained by hydrogenating a non-hydrogenated polymer block mainly composed of conjugated diene monomer units. In the hydrogenated block copolymer of the present embodiment, the content of the hydrogenated polymer block B is 3% by mass or more and less than 20% by mass, preferably from the viewpoint of flexibility, abrasion resistance and oil resistance. 4 to 18% by mass.

In the hydrogenated block copolymer of the present embodiment, the content of all vinyl aromatic monomer units is 25% by mass or more and 85% by mass or less in terms of flexibility, abrasion resistance, etc., preferably 30% by mass or more and 75% by mass or less, more preferably 40% by mass or more and 70% by mass or less. The content of all vinyl aromatic monomer units in the hydrogenated block copolymer was determined by using an ultraviolet spectrophotometer using the block copolymer before hydrogenation and the block copolymer after hydrogenation as samples. can know. Specifically, it can be measured by the method described in Examples below.

In the hydrogenated block copolymer of the present embodiment, at least one of the hydrogenated polymer blocks B has a hydrogenated polymer block C having a vinyl bond content of 60% by mass or more. The vinyl bond content of the conjugated diene of the hydrogenated polymer block C before hydrogenation is 60% or more, preferably 65% to 90%, more preferably 70% in terms of flexibility, abrasion resistance, and oil resistance. ~85%. In the present embodiment, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds , 3,4-vinyl bond content when isoprene is used as the conjugated diene) is hereinafter referred to as the vinyl bond content. The amount of vinyl bonds can be determined by measurement with an infrared spectrophotometer (for example, Hampton method) using the block copolymer before hydrogenation as a sample. Specifically, it can be measured by the method described in Examples below.

Moreover, it is preferable that the hydrogenated block copolymer of the present embodiment contains a hydrogenated polymer block C at least at one end. A structure having a hydrogenated polymer block C of 3% by mass or more and less than 20% by mass relative to the entire hydrogenated block copolymer is favorable in the hydrogenated block copolymer and the hydrogenated block copolymer composition. It is preferable from the viewpoint of obtaining good flexibility. It is presumed that this is because the hydrogenated polymer block C is compatible with the physical cross-linking points formed by the polymer blocks A, and the cohesive force is lowered.

Furthermore, the hydrogenated block copolymer of the present embodiment has a structure having, at least at one end, a hydrogenated polymer block C of less than 20% by mass with respect to the entire hydrogenated block copolymer. It is preferable from the viewpoint of improving compatibility with the system resin (b) and obtaining good flexibility, abrasion resistance, and oil resistance in the hydrogenated block copolymer composition.

The weight-average molecular weight of the hydrogenated block copolymer of the present embodiment is 50,000 to 600,000, preferably 100,000 to 600,000, more preferably 100,000 to 600,000 in terms of the balance of flexibility, abrasion resistance, oil resistance, etc. is 150,000 to 500,000.

The molecular weight distribution of the hydrogenated block copolymer of the present embodiment is 10 or less, generally 1-8, preferably 1.01-5. The molecular weight of the hydrogenated block copolymer is measured by gel permeation chromatography (GPC). It is the weight-average molecular weight determined using The molecular weight distribution of the hydrogenated block copolymer can be similarly determined by GPC measurement, and is the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). Specifically, it can be measured by the method described in Examples below.

The hydrogenated block copolymer of the present embodiment is a hydrogenated block copolymer containing conjugated diene monomer units and vinyl aromatic monomer units. In the hydrogenated block copolymer of the present embodiment, 75% or more of the double bonds of the conjugated diene monomer units are preferably hydrogenated from the viewpoint of flexibility, abrasion resistance, and oil resistance. More preferably 80% or more, still more preferably 85% or more, particularly preferably 90% or more is hydrogenated. Although the upper limit of the hydrogenation rate of the double bond of the conjugated diene monomer unit is not particularly limited, it is, for example, 100% or less. In the hydrogenated block copolymer of the present embodiment, the hydrogenation rate of the aromatic double bond of the vinyl aromatic monomer unit is not particularly limited, but is preferably 50% or less, more preferably 30%. 20% or less, more preferably 20% or less. Each hydrogenation rate of the hydrogenated block copolymer can be known using a nuclear magnetic resonance apparatus (NMR) or the like.

The hydrogenated block copolymer of the present embodiment preferably has at least one hydrogenated copolymer block D which is a random copolymer composed of conjugated diene monomer units and vinyl aromatic monomer units. A hydrogenated product in which substantially no crystallization peak attributed to the hydrogenated copolymer block D exists in the range of -20°C to 80°C in a differential scanning calorimetry (DSC) chart is preferred. Here, the phrase “there is substantially no crystallization peak attributed to the hydrogenated copolymer block D in the range of −20° C. to 80° C.” means that crystals of the hydrogenated copolymer block D portion are present in this temperature range. Even when no peak due to crystallization appears or a peak due to crystallization is observed, the crystallization peak heat quantity due to the crystallization is less than 3 J/g, preferably less than 2 J/g, more preferably 1 J/g. is less than, particularly preferably means that there is no peak heat of crystallization.

A hydrogenated block copolymer that does not have a crystallization peak attributed to the hydrogenated copolymer block D in the range of −20° C. to 80° C. has good flexibility, and a soft vinyl chloride resin is used. Suitable for application development. In order to obtain a hydrogenated block copolymer in which the crystallization peak caused by the hydrogenated copolymer block D does not substantially exist in the range of −20° C. to 80° C. as described above, a vinyl bond as described later Using a non-hydrogenated copolymer obtained by conducting a polymerization reaction under the conditions described later using a modifier that adjusts the amount and random copolymerizability of the conjugated diene compound and the vinyl aromatic compound. , a hydrogenation reaction may be performed.

In the hydrogenated block copolymer of the present embodiment, the content of the hydrogenated copolymer block D is preferably 40% by mass to 90% by mass from the viewpoint of abrasion resistance. More preferably 45% to 80% by mass, particularly preferably 50% to 70% by mass. In the present embodiment, the mass ratio of the conjugated diene monomer unit and the vinyl aromatic monomer unit in the random copolymer constituting the hydrogenated copolymer block D (conjugated diene/vinyl aromatic) is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, still more preferably 85/15 to 15/85.

In the present embodiment, the microstructure (ratio of cis, trans, and vinyl) of the conjugated diene portion in the polymer block before hydrogenation of the hydrogenated copolymer block D can be arbitrarily changed by using a polar compound or the like described later. Generally, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is preferably 10% to 20% from the viewpoint of abrasion resistance.

In this embodiment, the structure of the hydrogenated block copolymer is not particularly limited, and any structure can be used. As a hydrogenated block copolymer comprising at least one, preferably two or more polymer blocks A, at least one hydrogenated polymer block B, and at least one hydrogenated polymer block C, However, for example, those having a structure represented by the following general formula can be mentioned.

(A-C) nD, (A-D) n-C, (DA) n-C, (A-(D-A) n)-C, (A-(B-A) n) -C, (A-(C-A)n)-D, (A-(B-D)n-A)-C, (A-B-D-A)n-C, A-(C-B )nA, A-(C-B-A)n-D, A-(C-B)n-A-D
(In the above formula, A is a polymer block A mainly composed of vinyl aromatic monomer units, B is a hydrogenated polymer block B of a polymer mainly composed of conjugated diene monomer units, and C is a vinyl Hydrogenated polymer blocks C and D of a polymer mainly composed of conjugated diene monomer units having a bond amount of 60% or more are random copolymers composed of conjugated diene monomer units and vinyl aromatic monomer units It is the hydrogenated copolymer block D of.The boundaries of each block do not necessarily need to be clearly distinguished.The vinyl aromatic monomer units in the hydrogenated copolymer block D of the random copolymer are uniformly In the hydrogenated copolymer block D of the random copolymer, the vinyl aromatic monomer units are uniformly distributed and/or Alternatively, a plurality of portions distributed in a tapered shape may coexist, and the hydrogenated copolymer block D of the random copolymer may include a plurality of segments having different vinyl aromatic monomer unit contents. may coexist, and n is an integer of 1 or more, preferably an integer of 1 to 5.)

Among these, in the present embodiment, the structure of the hydrogenated block copolymer has two polymer blocks A and has a hydrogenated polymer block C at the terminal. Preferred, the ADAC structure being particularly preferred.

A conjugated diene in this embodiment is a diolefin having a pair of conjugated double bonds. Examples of conjugated dienes include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2- Examples include methyl-1,3-pentadiene and 1,3-hexadiene. Especially common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more. The vinyl aromatic compound is not particularly limited, but examples include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N , N-diethyl-p-aminoethylstyrene and the like, and these may be used alone or in combination of two or more.

In the present embodiment, the block copolymer before hydrogenation is not particularly limited, but can be obtained, for example, by anionic living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of 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 methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.

In addition, although the initiator is not particularly limited, for example, aliphatic hydrocarbon alkali metal compounds and aromatic hydrocarbons which are generally known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds Alkali metal compounds, organic amino alkali metal compounds, and the like can be mentioned. Examples of alkali metals include, but are not particularly limited to, lithium, sodium, and potassium. Suitable organoalkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, compounds containing one lithium per molecule, and dilithium compounds containing multiple lithium per molecule. , trilithium compounds, and tetralithium compounds. Although not specifically limited, examples include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, Reaction products of diisopropenylbenzene and sec-butyllithium, reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene, and the like.

Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent No. 2,241,239, US Pat. be able to.

In the present embodiment, when a conjugated diene compound and a vinyl aromatic compound are copolymerized using an organic alkali metal compound as a polymerization initiator, a vinyl bond (1, 2- or 3, A tertiary amine compound or an ether compound can be added as a modifier in order to adjust the amount of 4-bonds and random copolymerizability of the conjugated diene compound and the vinyl aromatic compound. Although the tertiary amine compound is not particularly limited, for example, a compound of the general formula R1R2R3N (wherein R1, R2, and R3 are a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group) is mentioned. Specifically, but not limited to, for example, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N'',N''-pentamethylethylenetriamine, N,N' -dioctyl-p-phenylenediamine and the like.

The ether compound is selected from linear ether compounds and cyclic ether compounds. Although the straight-chain ether compound is not particularly limited, for example, dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether and dialkyl ether compounds of diethylene glycol such as diethylene glycol dibutyl ether. The cyclic ether compound is not particularly limited, but examples include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, and 2,2-bis(2-oxolanyl)propane. , alkyl ether of furfuryl alcohol, and the like.

In the present embodiment, the method of copolymerizing a conjugated diene compound and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. good. A batch polymerization method is particularly recommended for obtaining a block copolymer excellent in moldability. The polymerization temperature is generally 0°C to 180°C, preferably 30°C to 150°C. Although the time required for polymerization varies depending on the conditions, it is usually within 48 hours, particularly preferably from 0.1 hour to 10 hours. The atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as the pressure is sufficient to keep the monomers and solvent in the liquid phase within the above polymerization temperature range. Furthermore, care must be taken to prevent impurities such as water, oxygen, and carbon dioxide from entering the polymerization system, which may inactivate the catalyst and living polymer.

The hydrogenated block copolymer of the present embodiment may be subjected to a coupling reaction by adding a necessary amount of a bifunctional or higher coupling agent at the end of the polymerization. Any known bifunctional coupling agent may be used, and is not particularly limited. Examples thereof include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. Moreover, any known polyfunctional coupling agent having a functionality of 3 or more may be used, and there is no particular limitation. For example, trihydric or higher polyalcohols, epoxidized soybean oil, polyepoxy compounds such as diglycidyl bisphenol A, general formula R _4-n SiX _n (where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen and n is an integer of 3 to 4), such as methylsilyl chloride, t-butylsilyl chloride, silicon tetrachloride and bromides thereof, etc., of the general formula R ₄ - _n Halogenated tin compounds represented by SnX _n (wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), such as methyltin trichloride, t-butyltin trichloride, Examples include polyvalent halogen compounds such as tin tetrachloride. Dimethyl carbonate, diethyl carbonate, etc. can also be used.

In order to improve compatibility between the hydrogenated block copolymer and polar resins other than polyolefins, the hydrogenated block copolymer of the present embodiment is a modified hydrogenated block in which atomic groups having functional groups are bonded. It may be a copolymer. The polar resin is not particularly limited, and examples thereof include polyamide-based resins, polyester-based resins, polycarbonate-based resins, polyurethane-based resins, polyphenylene ether-based resins, polyphenylene sulfide-based resins, and polyarylate-based resins. Examples of functional group-containing atomic groups include, but are not limited to, hydroxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxyl group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphate group, phosphate ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group , an isothiocyanate group, a silicon halide group, a silanol group, an alkoxy silicon group, a tin halide group, an alkoxytin group, a phenyltin group and the like. A modified hydrogenated block copolymer in which 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 bonded is preferred.

Examples of modifiers having a functional group include, but are not limited to, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, 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 hydrogenated block copolymer is obtained by subjecting the living end of the block copolymer obtained by the method described above to the addition reaction of a modifying agent that produces functional group-containing atomic groups using an organolithium compound as a polymerization catalyst. It can be obtained by adding hydrogen to the block copolymer obtained.

The temperature of the modification reaction is preferably 0°C to 150°C, more preferably 20°C to 120°C. Although the time required for the modification reaction varies depending on other conditions, it is preferably within 24 hours, particularly preferably 0.1 to 10 hours.

The hydrogenated block copolymer of the present embodiment is graft-modified with an α,β-unsaturated carboxylic acid or a derivative thereof such as an anhydride, an ester, an amidide, or an imidized product thereof, and is bonded to an atomic group having a functional group. can be made Specific examples of the α,β-unsaturated carboxylic acid or derivative thereof are not particularly limited, but examples include maleic anhydride, maleic anhydride imide, acrylic acid or its ester, methacrylic acid or its ester, endo-cis- bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydride. The amount of α,β-unsaturated carboxylic acid or derivative thereof added is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the hydrogenated polymer.

The reaction temperature for graft modification is preferably 100 to 300°C, more preferably 120 to 280°C. For details of the graft modification method, for example, JP-A-62-79211 can be referred to.

By hydrogenating the block copolymer or modified block copolymer obtained above, the hydrogenated block copolymer and the like of the present embodiment can be obtained. The hydrogenation catalyst is not particularly limited, and is conventionally known (1) Supported heterogeneous hydrogenation in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum; (3) Ti, Ru, Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Rh and Zr are used. Specific hydrogenation catalysts are not particularly limited. Hydrogenation catalysts described in JP-A-1-53851 and JP-B-2-9041 can be used. Preferred hydrogenation catalysts include titanocene compounds and/or mixtures with reducing organometallic compounds.

Although the titanocene compound is not particularly limited, for example, compounds described in JP-A-8-109219 can be used. Specific examples include, but are not limited to, coordination having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton, such as biscyclopentadienyltitanium dichloride and monopentamethylcyclopentadienyltitanium trichloride. Compounds having at least one or more children are included. The reducing organometallic compound is not particularly limited, but examples thereof include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

In this embodiment, the hydrogenation reaction is generally carried out in a temperature range of 0°C to 200°C, more preferably 30°C to 150°C. The pressure of hydrogen used in the hydrogenation reaction is 0.1 MPa to 15 MPa, preferably 0.2 MPa to 10 MPa, more preferably 0.3 MPa to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be used either as a batch process, a continuous process, or a combination thereof.

From the solution of the hydrogenated block copolymer obtained as described above, catalyst residues can be removed as necessary to separate the hydrogenated block copolymer from the solution. The method for separating the solvent is not particularly limited, but for example, a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated block copolymer, is added to the reaction solution after hydrogenation to precipitate and recover the polymer. method, a method of pouring the reaction solution into hot water with stirring and removing and recovering the solvent by steam stripping, or 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 can be added to the hydrogenated block copolymer of the present embodiment.

[Hydrogenated block copolymer composition]
The hydrogenated block copolymer composition of the present embodiment comprises 10 to 90 parts by mass of the above-described hydrogenated block copolymer (a) (hereinafter also simply referred to as (a) or component (a)) and at least 1 10 to 90 parts by mass of olefin resin (b) (hereinafter also simply referred to as (b) or component (b)), and (a) for a total of 100 parts by mass of (a) and (b) 0 to 150 parts by mass of a thermoplastic resin other than (a) or a polymer (c) other than (a) (hereinafter simply referred to as (c) or component (c)), and a softening agent (d) (hereinafter simply (d ) or component (d).) 0 to 150 parts by mass.

<(b) Olefin resin>
The olefinic resin (b) that constitutes the hydrogenated block copolymer composition of the present embodiment will be described.

The olefin resin (b) is not particularly limited, but examples include polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl- Examples include homopolymers of α-olefins such as 1-pentene and 1-octene.

Also, although not particularly limited, for example, random copolymers or block copolymers made of a combination of olefins selected from ethylene, propylene, butene, pentene, hexene, octene and the like can be mentioned.

Also, although not particularly limited, for example, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer , ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1- Octene copolymer, propylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, propylene-1-octene-ethylene copolymer and/or ethylene and/or propylene-α-olefin copolymers.

Copolymers with ethylene and/or propylene also include copolymers with other unsaturated monomers shown below.

Although not particularly limited, examples include ethylene and/or propylene and unsaturated compounds such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, aryl maleic acid imide, and alkyl maleic acid imide. Copolymers with organic acids or derivatives thereof, copolymers of ethylene and/or propylene with vinyl esters such as vinyl acetate, further ethylene and/or propylene with dicyclopentadiene, 4-ethylidene-2-norbornene, 4 and copolymers with non-conjugated dienes such as -methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene.

(b) The olefin-based resin preferably contains at least one type of polypropylene-based resin.

Moreover, the olefinic resin (b) may be modified with a predetermined functional group.

Examples of functional groups include, but are not limited to, epoxy groups, carboxy groups, acid anhydrides, and hydroxyl groups.

The functional group-containing compound or modifier for modifying the olefinic resin (b) is not particularly limited, but examples thereof include the following compounds.

For example, unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, etc. and unsaturated organic acids.

Other examples include ionomers and chlorinated polyolefins.

As the olefin-based resin (b), polypropylene homopolymer is used from the viewpoint of economic efficiency and good compatibility of the components in the hydrogenated block copolymer composition of the present embodiment to obtain high transparency. , ethylene-propylene random or block copolymers.

In particular, ethylene-propylene random copolymers are more preferable from the viewpoint of transparency and flexibility.

The olefinic resin (b) may be composed of a single material, or two or more of them may be used in combination.

In the hydrogenated block copolymer composition of the present embodiment, when the total amount of components (a) and (b) is 100 parts by mass, the content of component (b) is 10 to 90 parts by mass, It is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass.

The thermoplastic resin (c) is not particularly limited. polymers of said vinyl aromatic compounds, said vinyl aromatic compounds and other vinyl monomers such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and acrylic methyl. Acrylic acid ester, methacrylic acid and methacrylic acid ester such as methyl methacrylate, acrylonitrile, copolymer resin with methacrylonitrile, rubber-modified styrene resin (HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylic acid ester-butadiene-styrene copolymer resin (MBS);

Also, although not particularly limited, for example, polyethylene, copolymers of ethylene containing 50% by mass or more of ethylene and other monomers copolymerizable therewith, for example, ethylene-propylene copolymers, ethylene-butylene copolymers Coalescence, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolyzate, polyethylene resin such as ethylene-acrylic acid ionomer and chlorinated polyethylene, polypropylene, 50 mass of propylene % or more copolymers of propylene and other monomers copolymerizable therewith, such as, but not limited to, propylene-ethylene copolymers, propylene-ethyl acrylate copolymers and polypropylenes such as chlorinated polypropylenes cyclic olefin resins such as ethylene-norbornene resins, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins and hydrolysates thereof.

Also, although not particularly limited, for example, polymers of acrylic acid and its esters and amides, polyacrylate resins, acrylonitrile and / or methacrylonitrile polymers, other acrylonitrile monomers containing 50% by mass or more Nitrile resin, which is a copolymer with a copolymerizable monomer, nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6 nylon-12 copolymer, etc. Polyamide-based resins, polyester-based resins, thermoplastic polyurethane-based resins, polycarbonate-based polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate, thermoplastics such as polyethersulfone and polyallylsulfone Polysulfone, polyoxymethylene resin, polyphenylene ether resin such as poly(2,6-dimethyl-1,4-phenylene) ether, polyphenylene sulfide, polyphenylene sulfide resin such as poly4,4'-diphenylene sulfide, poly Polybutadiene-based resins such as arylate-based resins, polyetherketone polymers or copolymers, polyketone-based resins, fluorine-based resins, polyoxybenzoyl-based polymers, polyimide-based resins, 1,2-polybutadiene, and trans-polybutadiene. .

Among these thermoplastic resins (c), particularly preferred are polystyrene, styrenic resins such as rubber-modified styrenic resins, polyethylene, ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, and ethylene-butylene. Polyethylenes such as copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid ester copolymers, etc. Polypropylene-based resins such as polymers, polypropylene, propylene-ethylene copolymers, polyamide-based resins, polyester-based resins, and polycarbonate-based resins. The number average molecular weight of these thermoplastic resins is generally 1,000 or more, preferably 5,000 to 5,000,000, more preferably 10,000 to 1,000,000.

In the hydrogenated block copolymer composition of the present embodiment, when the total amount of components (a) and (b) is 100 parts by mass, the content of component (c) is 0 to 150 parts by mass, It is preferably from 0 to 140 parts by mass, more preferably from 0 to 130 parts by mass.

<(d) Softener>
The softening agent (d) that constitutes the hydrogenated block copolymer composition of the present embodiment will be described.

The softener (d) used in the present embodiment is preferably a rubber softener that softens the composition and imparts workability. The softener for rubber is not particularly limited, but examples thereof include mineral oil and liquid or low-molecular-weight synthetic softeners, among which naphthenic and/or paraffinic process oils or extender oils are preferred. Mineral oil-based rubber softeners are mixtures of aromatic rings, naphthenic rings and paraffin chains. Those containing 30 to 45% are called naphthenic, and those containing more than 30% aromatic carbon atoms are called aromatic. A synthetic softening agent may be used in the hydrogenated block copolymer composition of the present embodiment, and is not particularly limited. For example, polybutene, low molecular weight polybutadiene, liquid paraffin, etc. can be used. Among them, the mineral oil-based rubber softener described above is preferable.

In the hydrogenated block copolymer composition of the present embodiment, when the total amount of components (a) and (b) is 100 parts by mass, the content of component (d) is 0 to 150 parts by mass, It is preferably from 0 to 130 parts by mass, more preferably from 0 to 100 parts by mass. When the amount of the softening agent (d) is equal to or less than the above upper limit, bleeding out can be suppressed and the surface texture becomes good.

In the obtained viscoelasticity measurement chart, the hydrogenated block copolymer composition of the present embodiment has a tan δ (loss tangent) peak of preferably 0° C. to 40° C., more preferably 5° C. to 35° C., still more preferably exists at least one at 10°C to 30°C. The tan δ peak is the hydrogenated copolymer block D of a random copolymer consisting of a conjugated diene monomer unit and a vinyl aromatic monomer unit in the polymer chain of the hydrogenated block copolymer and the softener ( d) is the peak attributed to The existence of at least one such peak in the range of 0° C. to 40° C. is preferable from the viewpoint of the balance between abrasion resistance and flexibility of the hydrogenated block copolymer composition. In the present embodiment, the position of the tan δ peak due to the polymer block A mainly composed of vinyl aromatic monomer units bonded in the polymer chain such as the hydrogenated block copolymer is particularly Although not limited, it generally lies within the temperature range above 80°C and 150°C.

In addition to the components (a), (b), (c), and (d), the hydrogenated block copolymer composition of the present embodiment may optionally contain any additive. . The type of additive is not particularly limited as long as it is generally used for compounding thermoplastic resins and rubber-like polymers.

For example, pigments and coloring agents such as carbon black and titanium oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, lubricants such as ethylenebisstearamide, release agents, phthalates and adipine Acid ester compounds, fatty acid esters such as azelaic acid ester compounds, plasticizers such as mineral oils, antioxidants such as hindered phenol antioxidants, phosphorus heat stabilizers, etc., hindered amine light stabilizers, benzotriazole ultraviolet rays Absorbents, antistatic agents, reinforcing agents such as organic fibers, glass fibers, carbon fibers, metal whiskers, other additives, and mixtures thereof may be used.

The hydrogenated block copolymer composition of the present embodiment may optionally contain any filler and flame retardant. Fillers and flame retardants are not particularly limited as long as they are generally used for compounding thermoplastic resins and rubber-like polymers.

Examples of fillers include, but are not limited to, silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fibers, glass beads, glass balloons, glass flakes, and graphite. , Titanium oxide, Potassium titanate whiskers, Carbon fiber, Alumina, Kaolin clay, Silicic acid, Calcium silicate, Quartz, Mica, Talc, Clay, Zirconia, Potassium titanate, Alumina, Inorganic fillers such as metal particles, Wood chips , wood powder, pulp and other organic fillers.

The shape of the filler is not particularly limited and may be scaly, spherical, granular, powdery, amorphous, or the like. These can be used singly or in combination.

Next, the flame retardant is not particularly limited, and examples thereof include halogen-based flame retardants mainly composed of bromine compounds, phosphorus-based flame retardants mainly composed of aromatic compounds, and inorganic-based flame retardants mainly composed of metal hydroxides. Inorganic flame retardants have become mainstream due to environmental concerns and the like, and are preferred. The inorganic flame retardant is not particularly limited, and examples thereof include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide, metal oxides such as zinc borate and barium borate, and other calcium carbonate, clay, and basic carbonate. Mainly water-containing metal compounds such as magnesium and hydrotalcite can be exemplified. In the present embodiment, among the above flame retardants, metal hydroxides such as magnesium hydroxide are preferable from the viewpoint of improving flame retardancy. The above-mentioned flame retardants also include so-called flame retardant aids, which exhibit a synergistic effect when used in combination with other flame retardants, although they have a low flame retardancy effect on their own.

Fillers and flame retardants may also be of a type that has been previously surface-treated with a surface-treating agent such as a silane coupling agent.

Two or more of these fillers and flame retardants may be used in combination, if necessary. When used in combination, there is no particular limitation, and filler components may be used together, flame retardant components may be used together, or a filler and a flame retardant may be used in combination.

In the hydrogenated block copolymer composition of the present embodiment, in addition to the above components (a), (b), (c), and (d), if necessary, other "rubber/plastic compounding chemicals" (rubber Edited by Digest Co., Ltd.) or a mixture thereof may be added.

In the hydrogenated block copolymer composition of the present embodiment, each component can be crosslinked as necessary. Examples of the cross-linking method include a chemical method by adding a cross-linking agent such as a peroxide or sulfur and, if necessary, a co-cross-linking agent, radiation cross-linking, and the like. Examples of cross-linking processes include static methods and dynamic vulcanization methods.

Examples of cross-linking agents include, but are not limited to, organic peroxides, sulfur, phenol-based, isocyanate-based, thiuram-based, morpholine disulfides, etc. These include stearic acid, oleic acid, zinc stearate, A cross-linking aid such as zinc oxide, a co-cross-linking agent, a vulcanization accelerator, etc. can be used in combination. Examples of the organic peroxide cross-linking agent include, but are not limited to, hydroperoxide, dialkyl peroxide, diallyl peroxide, diacyl peroxide, peroxyester, ketone peroxide, and the like. A physical cross-linking method using an electron beam, radiation, or the like can also be used.

The method for producing the hydrogenated block copolymer composition of the present embodiment is not particularly limited, and known methods can be used. For example, a melt-kneading method using a general kneader such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder, etc. After dissolving or dispersing and mixing each component, the solvent is heated. A method of removing, etc. is used. In the present embodiment, a melt-mixing method using an extruder is preferable from the viewpoint of productivity and good kneadability. The shape of the hydrogenated block copolymer composition to be obtained is not particularly limited, and examples thereof include pellets, sheets, strands, chips, and the like. Moreover, after melt-kneading, it can be directly molded.

[Use]
The damping material or sound absorbing material of the present embodiment comprises the hydrogenated block copolymer described above or the hydrogenated block copolymer composition described above. Further, the molded article of the present embodiment is made of the hydrogenated block copolymer composition described above.

When obtaining a foamed molded product of the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment, methods applicable to the present embodiment include chemical methods, physical methods, and the like. Cells can be distributed inside the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, or a foaming agent such as a physical foaming agent. By using a foam material, it is possible to achieve weight reduction, flexibility improvement, design improvement, and the like. Examples of inorganic foaming agents include, but are not limited to, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, sodium borohydride, and metal powder.

Examples of organic blowing agents include, but are not limited to, azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N,N'-dinitrosopentamethylenetetramine, N,N'- Examples include dinitroso-N,N'-dimethylterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p,p'-oxybisbenzenesulfonylhydrazide, p-toluenesulfonyl semicarbazide and the like.

Physical foaming agents include, but are not limited to, hydrocarbons such as pentane, butane, and hexane, halogenated hydrocarbons such as methyl chloride and methylene chloride, gases such as nitrogen and air, trichlorofluoromethane, and dichlorodifluoromethane. , trichlorotrifluoroethane, chlorodifluoroethane, and fluorinated hydrocarbons such as hydrofluorocarbons.

Molded articles of the hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment are provided on the surface of the molded article as necessary for the purpose of improving appearance, weather resistance, scratch resistance, etc. Decoration such as printing, painting, and embossing can be performed. When surface treatment is performed for the purpose of improving printability, paintability, etc., the method of surface treatment is not particularly limited, and physical methods, chemical methods, etc. can be used. treatment, plasma treatment, flame treatment, acid/alkali treatment, and the like. Among these, the corona discharge treatment is preferable from the viewpoints of ease of implementation, cost, possibility of continuous treatment, and the like.

The hydrogenated block copolymer or hydrogenated block copolymer composition of the present embodiment can be used for various applications as described above, but when used as a molded article, the molding method is not particularly limited. For example, extrusion molding, injection molding, blow molding, air pressure molding, vacuum molding, foam molding, multi-layer extrusion molding, multi-layer injection molding, high frequency fusion molding, slush molding, calender molding, and the like can be used. Examples of molded articles include, but are not limited to, sheets, films, tubes, non-woven fabrics, fibrous molded articles, and synthetic leather. Molded articles made of the hydrogenated block copolymer and hydrogenated block copolymer composition of the present embodiment are not particularly limited, but examples include food packaging materials, medical device materials, home electric appliances and parts thereof, electronic devices and their parts. It can be used as materials for parts, automobile parts, industrial parts, household goods, toys, etc., materials for footwear, fiber materials, materials for adhesives, asphalt modifiers, etc. Specific examples of automotive parts include, but are not limited to, trims, side moldings, grommets, knobs, weather strips, window frames and their sealing materials, armrests, door grips, handle grips, console boxes, bed rests, and instruments. Examples include panels, bumpers, spoilers, and storage covers for airbag devices. Specific examples of the medical device include, but are not limited to, blood bags, platelet storage bags, infusion (medicine) bags, artificial dialysis bags, medical tubes, catheters, and the like. Other industrial or food hoses, vacuum cleaner hoses, electrical cooling packing, electric wires and other coating materials, grip coating materials, soft dolls, etc., adhesive tapes, sheets, film substrates, surface protection film substrates and the like It can be used as adhesives for films, adhesives for carpets, films for stretch packaging, heat-shrinkable films, covering materials for coated steel pipes, sealants, and the like.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Further, in the following examples, properties and physical properties of non-hydrogenated polymers or hydrogenated block copolymers were measured by the following methods.

I. Properties of hydrogenated block copolymer I-1) Total vinyl aromatic (styrene) monomer unit content The total vinyl aromatic (styrene) monomer unit content is the block copolymer before hydrogenation. was used and measured with an ultraviolet spectrophotometer (device name: UV-2450; manufactured by Shimadzu Corporation, Japan).

I-2) Content (Os value) of polymer block A mainly composed of vinyl aromatic units
The content of the polymer block A mainly composed of vinyl aromatic compound monomer units is determined by using a block copolymer before hydrogenation, M. Kolthoff, et al. , J. Polym. Sci. 1,429 (1946) by the osmium tetroxide decomposition method. A 0.1 g/125 mL tertiary butanol solution of the osmic acid solution was used to decompose the block copolymer before hydrogenation. The content of polymer block A (polystyrene block) mainly composed of vinyl aromatic monomer units obtained here is referred to as "Os value".
When measuring the content of the polymer block A mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer, a nuclear magnetic resonance device (device name: JMN-270WB; manufactured by JEOL Ltd., Japan) ) to obtain the Y. Tanaka, et al. , RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Specifically, a sample obtained by dissolving 30 mg of the hydrogenated block copolymer in 1 g of heavy chloroform was measured by ¹ H-NMR. The content (Ns value) of the polymer block A (polystyrene block) mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer obtained by ¹ H-NMR was determined as a chemical shift of 6.9 with respect to the total integrated value. It was obtained from the ratio of the integrated value of ~6.3 ppm, and then the Ns value was converted to the Os value. The calculation method for the hydrogenated block copolymer is shown below.
・ Block styrene (St) strength: (6.9 to 6.3 ppm) integrated value / 2
・ Random styrene (St) strength: (7.5 to 6.9 ppm) integrated value -3 (block St strength)
Ethylene-butylene (EB) strength: total integrated value -3 {(block St strength) + (random St strength)}/8
· Polystyrene block content (Ns value) obtained by ¹ H-NMR = 104 (block St intensity) / [104 {(block St intensity) + (random St intensity)} + 56 (EB intensity)]
・Os value = -0.012 (Ns) ² +1.8 (Ns) -13.0

I-3) Vinyl bond amount Using a block copolymer before hydrogenation, hydrogenated polymer block B (polybutadiene block) was measured. The amount of vinyl bonds in the case of copolymers was calculated by the Hampton method, and the amount of vinyl bonds in the case of homopolymers was calculated by the Morero method.

I-4) Content of Hydrogenated Polymer Block B (Polybutadiene Block) The content of the vinyl aromatic polymer was quantified by an altimeter and calculated from the measured value.

I-5) Content of hydrogenated copolymer block D of random copolymer Quantitative determination of the components and the content of the hydrogenated polymer block B described above were performed, and calculation was performed from the measured values.

I-6) Contents of conjugated diene monomer unit and vinyl aromatic monomer unit in hydrogenated copolymer block D of random copolymer Vinyl aromatic in hydrogenated copolymer block D of random copolymer The content of the monomer units is determined by extracting the polymer before and after the hydrogenated copolymer block D of the random copolymer is polymerized, and quantifying the content of the vinyl aromatic polymer with an ultraviolet spectrophotometer, and the "tetroxide The vinyl aromatic polymer block component was quantified by the osmium decomposition method, and calculated from the measured value.

I-7) Method for Confirming Presence or Absence of One End of Hydrogenated Polymer Block C The presence or absence of one end of hydrogenated polymer block C is determined by the polymer after the first step after the initiation of polymerization and the step immediately before the completion of polymerization. The polymers before and after were extracted, and the vinyl aromatic polymer was quantified by an ultraviolet spectrophotometer, confirming that the block was hydrogenated polymer block C mainly composed of conjugated diene monomer units.

I-8) Method for confirming the number of each polymer block The number of each polymer block can be determined by extracting the polymer before and after each polymerization step and quantifying the vinyl aromatic polymer with an ultraviolet spectrophotometer. It was confirmed which of the polymer blocks A, B, and D the polymer polymerized in 1 corresponds to, and the number of each block.

I-9) Weight Average Molecular Weight and Molecular Weight Distribution Weight average molecular weight and molecular weight distribution were measured using a GPC apparatus (manufactured by Waters, USA). Tetrahydrofuran was used as a solvent, and the measurement was performed at 35°C. A calibration curve prepared using commercially available standard polystyrene (prepared by measuring the peak molecular weight of standard polystyrene) was used to determine the weight average molecular weight from the peak molecular weight of the chromatogram. The molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

I-10) Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany). measured by

I-11) 100% modulus (100% Mo)
100% modulus was taken as an index of flexibility. According to JIS K6251, the tensile properties of the compression test piece of the hydrogenated block copolymer were measured, and the stress at 100% elongation (hereinafter referred to as 100% modulus) was measured. The smaller the 100% modulus, the better the flexibility, and it is preferably 70 kg/cm ² or less. The tensile speed was 500 mm/min, and the measurement temperature was 23°C.

I-12) Tensile strength (Tb), elongation at break (Eb)
Tensile strength (Tb) and elongation at break (Eb) were measured according to JIS K6251 with a No. 3 dumbbell and a crosshead speed of 500 mm/min. Practically, the tensile strength is preferably 300 kg/cm ² or more. A breaking elongation of 250% or more is practically preferable.

II. Properties of Hydrogenated Block Copolymer Composition II-1) Flexibility According to JIS K6251, the tensile properties of a compression test piece of the hydrogenated block copolymer composition were measured. Flexibility was indexed by the stress at 100% stretching (hereinafter referred to as 100% Mo). The smaller the 100% Mo is, the better the flexibility, and 110 kg/cm ² or less is preferable. The tensile speed was 500 mm/min, and the measurement temperature was 23°C.

II-2) Abrasion resistance Using a Gakushin type friction tester (manufactured by Tester Sangyo Co., Ltd., AB-301 type), the molded sheet surface (leather textured surface) was rubbed with a friction cloth Kanakin No. 3 cotton and a load of 500 g. After rubbing, the grain depth was measured, and the grain depth residual rate (calculated by the following formula 1) was judged according to the following criteria. The grain depth was measured with a surface roughness meter E-35A manufactured by Tokyo Seimitsu Co., Ltd.

Texture depth residual rate = (texture depth after friction) / (texture depth before friction) x 100 (Equation 1)

◎: After 10,000 times of rubbing, the grain depth residual rate is 75% or more ○: After 10,000 times of rubbing, the grain depth residual rate is less than 75% and 50% or more △: After 10,000 times of rubbing , The grain depth residual rate is less than 50% 25% or more ×: After 10,000 times of friction, the grain depth residual rate is less than 25%

II-3) Oil Resistance According to JIS K6258, a test piece was immersed in IRM903 oil manufactured by Nippon Sun Oil Co., Ltd., and the mass before and after immersion was measured. Assuming that the mass of the test piece before immersion was 100%, the mass fraction (%) increased by immersion was calculated as the swelling rate. If the test piece does not swell at all with the test oil, the value is 0%, but the larger the swelling, the larger the number. . The swelling ratio is preferably less than 100%, more preferably 50% or less.

◎: swelling rate is 50% or less ○: swelling rate is 50% or more and less than 100% △: swelling rate is 100% or more and less than 150% ×: swelling rate is 150% or more

<Preparation of hydrogenation catalyst>
In the following examples and comparative examples, the hydrogenation catalyst used for the hydrogenation reaction of the copolymer was prepared by the following method.

A reaction vessel purged with nitrogen was charged with 1 liter of dried and purified cyclohexane, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. and reacted at room temperature for about 3 days. A hydrogenation catalyst was thus obtained.

[Preparation of hydrogenated block copolymer]
[Production Reference Example 1]
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 34 parts by mass of butadiene and 43 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 86%. The resulting polymer had a styrene content of 52% by mass, a polystyrene block content of 5% by mass, a vinyl bond content in the polybutadiene block portion of 86% by mass, a weight average molecular weight of 165,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The obtained hydrogenated block copolymer (Polymer 1) had a hydrogenation rate (hydrogenation rate of double bonds of conjugated diene monomer units) of 99%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 2>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. Thereafter, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 34 parts by mass of butadiene and 43 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 85%. The resulting polymer had a styrene content of 52% by mass, a polystyrene block content of 5% by mass, a vinyl bond content in the polybutadiene block portion of 85% by mass, a weight average molecular weight of 175,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The obtained hydrogenated block copolymer (Polymer 2) had a hydrogenation rate (hydrogenation rate of double bonds of conjugated diene monomer units) of 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 3>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 34 parts by mass of butadiene and 43 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 85%. The resulting polymer had a styrene content of 52% by mass, a polystyrene block content of 5% by mass, a vinyl bond content in the polybutadiene block portion of 85% by mass, a weight average molecular weight of 170,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The obtained hydrogenated block copolymer (Polymer 3) had a hydrogenation rate (hydrogenation rate of double bonds of conjugated diene monomer units) of 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 4>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. Then, a cyclohexane solution (concentration of 20% by mass) containing 53 parts by mass of butadiene and 24 parts by mass of styrene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added and heated to 50°C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added and polymerized at 50° C. for 1 hour. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 30% by mass, a polystyrene block content of 5% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 170,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the resulting hydrogenated block copolymer (polymer 4) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 5>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 16 parts by mass of butadiene and 75 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 80% by mass, a polystyrene block content of 5% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 170,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the resulting hydrogenated block copolymer (Polymer 5) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Example 6>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 43 parts by mass of butadiene and 33 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 53% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 143,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The obtained hydrogenated block copolymer (Polymer 6) had a hydrogenation rate (hydrogenation rate of double bonds of conjugated diene monomer units) of 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Example 7>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 38 parts by mass of butadiene and 38 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 77%. The resulting polymer had a styrene content of 58% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 77% by mass, a weight average molecular weight of 151,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (polymer 7) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 8>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. Thereafter, a cyclohexane solution (concentration: 20% by mass) containing 61 parts by mass of butadiene and 15 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 81%. The obtained polymer had a styrene content of 35% by mass, a polystyrene block content of 20% by mass, a vinyl bond content of the polybutadiene block portion of 81% by mass, a weight average molecular weight of 149,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (polymer 8) was 96%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 9>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 12.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 47 parts by mass of butadiene and 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 81%. The resulting polymer had a styrene content of 35% by mass, a polystyrene block content of 25% by mass, a vinyl bond content in the polybutadiene block portion of 81% by mass, a weight average molecular weight of 149,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The obtained hydrogenated block copolymer (Polymer 9) had a hydrogenation rate (hydrogenation rate of double bonds of conjugated diene monomer units) of 96%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 10>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 40.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) are added to 0 parts by mass of 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of butadiene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 40.5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 85%. The resulting polymer had a styrene content of 81% by mass, a polystyrene block content of 81% by mass, a vinyl bond content in the polybutadiene block portion of 85% by mass, a weight average molecular weight of 158,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 10) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 11>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. Thereafter, a cyclohexane solution (concentration: 20% by mass) containing 61 parts by mass of butadiene and 25 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 35% by mass, a polystyrene block content of 10% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 163,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 11) was 97%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 12>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 0.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 36 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 0.5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 46% by mass, a polystyrene block content of 1% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 165,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 12) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 13>
Batch polymerization was carried out using a stirred and jacketed tank reactor with an internal volume of 10 L. First, a cyclohexane solution (concentration: 20% by mass) containing 2.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 34 parts by mass of butadiene and 43 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 2.5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 48% by mass, a polystyrene block content of 5% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 165,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 13) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 14>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of butadiene and 51 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this point was measured and found to be 76%. The resulting polymer had a styrene content of 61% by mass, a polystyrene block content of 10% by mass, a vinyl bond content in the polybutadiene block portion of 76% by mass, a weight average molecular weight of 152,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the resulting hydrogenated block copolymer (Polymer 14) was 99%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 15>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 28 parts by mass of butadiene and 38 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 15 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The obtained polymer had a styrene content of 68% by mass, a polystyrene block content of 30% by mass, a vinyl bond content of the polybutadiene block portion of 80% by mass, a weight average molecular weight of 144,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 15) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 16>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 25 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 19 parts by mass of butadiene and 27 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 25 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 82%. The resulting polymer had a styrene content of 77% by mass, a polystyrene block content of 50% by mass, a vinyl bond content in the polybutadiene block portion of 82% by mass, a weight average molecular weight of 152,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 16) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 17>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 23.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) are added to 0 parts by mass of 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of butadiene and 20 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 23.5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 67% by mass, a polystyrene block content of 47% by mass, a vinyl bond content of the polybutadiene block portion of 80% by mass, a weight average molecular weight of 150,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the resulting hydrogenated block copolymer (Polymer 17) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 18>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 0.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 42 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 0.5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The obtained polymer had a styrene content of 56% by mass, a polystyrene block content of 1% by mass, a vinyl bond content of the polybutadiene block portion of 80% by mass, a weight average molecular weight of 150,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 18) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 19>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 43 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 8 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 82%. The resulting polymer had a styrene content of 63% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 82% by mass, a weight average molecular weight of 153,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the resulting hydrogenated block copolymer (Polymer 19) was 99%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 20>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 25 parts by mass of butadiene and 37 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 18 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this point was measured and found to be 76%. The resulting polymer had a styrene content of 57% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 76% by mass, a weight average molecular weight of 160,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 20) was 99%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Example 21>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 43 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 8 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 65%. The resulting polymer had a styrene content of 63% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 65% by mass, a weight average molecular weight of 151,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 21) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 22>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.08 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 79%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 79% by mass, a weight average molecular weight of 60,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 22) was 99%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 23>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.04 parts by mass of n-butyllithium per 100 parts by mass of all the monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 81%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 81% by mass, a weight average molecular weight of 302,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 23) was 97%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Example 24>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.02 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The obtained polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content of the polybutadiene block portion of 80% by mass, a weight average molecular weight of 550,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 24) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 25>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 43 parts by mass of butadiene and 33 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 53% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 143,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 25) was 78%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 26>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 43 parts by mass of butadiene and 33 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 53% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 143,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 26) was 70%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 27>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 70%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content of the polybutadiene block portion of 70% by mass, a weight average molecular weight of 150,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 27) was 50%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Manufacturing Reference Example 28>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) are added to 0 parts by mass of 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 43 parts by mass of butadiene and 33 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. Finally, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 30%. The resulting polymer had a styrene content of 53% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 143,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 28) was 98%. Table 1 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 1>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added and polymerized at 50° C. for 1 hour. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 30%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 30% by mass, a weight average molecular weight of 151,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the resulting hydrogenated block copolymer (Polymer 29) was 98%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 2>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) are added to 0 parts by mass of 1 mol of n-butyllithium. 0.9 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added and polymerized at 50° C. for 1 hour. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 55%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 55% by mass, a weight average molecular weight of 151,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 30) was 98%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 3>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.1 part by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide was added per 1 mol of n-butyllithium, followed by polymerization at 50°C for 1 hour. . The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content in the polybutadiene block portion of 80% by mass, a weight average molecular weight of 30,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 31) was 98%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 4>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.03 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 31 parts by mass of butadiene and 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The resulting polymer had a styrene content of 65% by mass, a polystyrene block content of 20% by mass, a vinyl bond content of the polybutadiene block portion of 80% by mass, a weight average molecular weight of 650,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 32) was 98%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 5>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 22 parts by mass of butadiene and 33 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 25 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 70%. The resulting polymer had a styrene content of 53% by mass, a polystyrene block content of 20% by mass, a vinyl bond content of the polybutadiene block portion of 70% by mass, a weight average molecular weight of 153,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 33) was 98%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 6>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 0.5 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. Thereafter, a cyclohexane solution (concentration: 20% by mass) containing 65 parts by mass of butadiene and 19 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 0.5 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 74%. The resulting polymer had a styrene content of 20% by mass, a polystyrene block content of 1% by mass, a vinyl bond content in the polybutadiene block portion of 74% by mass, a weight average molecular weight of 149,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 34) was 99%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 7>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration of 20% by mass) containing 45 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 0 per 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, a cyclohexane solution (concentration: 20% by mass) containing 5 parts by mass of butadiene was added and polymerized at 70° C. for 1 hour. Next, a cyclohexane solution containing 45 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. Finally, a cyclohexane solution (concentration: 20% by mass) containing 5 parts by mass of butadiene was added, and 0.08 mol of sodium-t-pentoxide per 1 mol of n-butyllithium was added, followed by polymerization at 50°C for 1 hour. bottom. The amount of vinyl bonds in the polybutadiene portion of the polymer sampled at this time was measured and found to be 80%. The obtained polymer had a styrene content of 90% by mass, a polystyrene block content of 90% by mass, a vinyl bond content of the polybutadiene block portion of 80% by mass, a weight average molecular weight of 150,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 35) was 98%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

<Production Comparative Example 8>
Batch polymerization was carried out using a stirred tank reactor with an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium per 100 parts by mass of all monomers and N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) are added to 0 parts by mass of 1 mol of n-butyllithium. 0.7 mol was added and polymerized at 70° C. for 1 hour. After that, 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 70° C. for 1 hour. Finally, a cyclohexane solution containing 10 parts by mass of styrene was added and polymerized at 70° C. for 1 hour. The most obtained polymer had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a weight average molecular weight of 152,000, and a molecular weight distribution of 1.1.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. After that, methanol was added, and then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass based on 100 parts by mass of the polymer.
The hydrogenation rate (hydrogenation rate of the double bond of the conjugated diene monomer unit) of the obtained hydrogenated block copolymer (Polymer 36) was 99%. Table 2 shows the properties of the obtained hydrogenated block copolymer.

[Production of hydrogenated block copolymer composition]
A hydrogenated block copolymer composition was produced using the hydrogenated block copolymer obtained in the above production example and the following components (b) to (d).

<Component (b)>
Olefin resin: Polypropylene resin, PM801A (manufactured by SunAllomer)

<Component (c)>
Thermoplastic resin: styrene thermoplastic elastomer, N504 (manufactured by Nippon Elastomer)

<Component (d)>
Softener: paraffin oil, PW-90 (manufactured by Idemitsu Kosan Co., Ltd.)

[ Reference Examples 1 and 2 and Comparative Example 1]
Hydrogenated block copolymer compositions having the compositions shown in Tables 3 and 6 were produced.
The obtained hydrogenated block copolymer (Polymer 3, 5 or 36) and the above olefin resin were extruded by a twin-screw extruder (device name: TEX30; Japan Steel Works, Ltd.) at the ratios shown in Tables 3 and 6. (manufacturer) and pelletized to obtain a hydrogenated block copolymer composition. The extrusion conditions were a cylinder temperature of 230° C. and a screw rotation speed of 300 rpm. A test piece was prepared by injection molding the resulting hydrogenated block copolymer composition. The physical properties of the test piece were measured and the results are shown in Tables 3 and 6.

[Examples 8-15, 20-23, 25-29, 31-32, Reference Examples 3-7, 16-19, 24, 30, 33-36 and Comparative Examples 2-9]
Hydrogenated block copolymer compositions having compositions shown in Tables 3 to 6 were produced.
The obtained hydrogenated block copolymers (polymers 1 to 36), the olefin resin, the thermoplastic resin, and the softening agent are mixed in the proportions shown in Tables 3 to 6 in a twin-screw extruder (apparatus name : PCM30; manufactured by Ikegai Iron Works, Japan) and pelletized to obtain a hydrogenated block copolymer composition. The extrusion conditions were a cylinder temperature of 230° C. and a screw rotation speed of 300 rpm. A test piece was prepared by injection molding the resulting hydrogenated block copolymer composition. The physical properties of the test piece were measured, and the results are shown in Tables 3-6.

The hydrogenated block copolymer and composition thereof of the present invention are excellent in flexibility, abrasion resistance and oil resistance.

Taking advantage of these features, the hydrogenated block copolymer and the composition thereof of the present invention are molded products (automobile interior materials, automobile exterior materials, medical device materials, various containers such as food packaging containers, home appliances, industrial parts, etc.) , toys, etc.).

Claims (9)

A hydrogenated block copolymer of a copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit,
At least two polymer blocks A having a vinyl aromatic monomer unit ratio of 90% by mass or more ,
containing at least one hydrogenated polymer block B obtained by hydrogenating a non-hydrogenated polymer block having a proportion of conjugated diene monomer units of 90% by mass or more ;
A hydrogenated block copolymer satisfying the following (a) to (d),
(a) the content of the hydrogenated polymer block B is 3% by mass or more and less than 20% by mass;
(b) the content of all vinyl aromatic monomer units is 40 % by mass or more and 70 % by mass or less;
(c) at least one of the hydrogenated polymer blocks B has a hydrogenated polymer block C having a vinyl bond content of 60% by mass or more;
(d) Weight average molecular weight of 100,000 to 600,000
80% or more of the double bonds of the conjugated diene monomer unit are hydrogenated,
A hydrogenated block copolymer containing the hydrogenated polymer block C at least at one end. 2. The hydrogenated block copolymer according to claim 1 , wherein the content of polymer block A is 3 to 50% by mass. At least one hydrogenated copolymer block D of a random copolymer composed of conjugated diene monomer units and vinyl aromatic monomer units is contained, and the content thereof is 40 to 90% by mass,
The mass ratio (conjugated diene/vinyl aromatic) of the conjugated diene monomer unit and the vinyl aromatic monomer unit in the random copolymer constituting the hydrogenated copolymer block D is 85/15 to 15/85. The hydrogenated block copolymer according to claim 1 or 2 . 10 to 90 parts by mass of the hydrogenated block copolymer (a) according to any one of claims 1 to 3 ;
10 to 90 parts by mass of at least one olefin resin (b);
For a total of 100 parts by mass of (a) and (b),
0 to 150 parts by mass of a thermoplastic resin other than (a) or a polymer (c) other than (a),
0 to 150 parts by mass of a softening agent (d);
A hydrogenated block copolymer composition containing A damping material comprising the hydrogenated block copolymer according to any one of claims 1 to 3 . A sound absorbing material comprising the hydrogenated block copolymer according to any one of claims 1 to 3 . A vibration damping material comprising the hydrogenated block copolymer composition according to claim 4 . A sound absorbing material comprising the hydrogenated block copolymer composition according to claim 4 . A molded article comprising the hydrogenated block copolymer composition according to claim 4 .