JP7313167B2 - Hydrogenated copolymer, hydrogenated copolymer composition, foam and molding - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hydrogenated copolymer, a hydrogenated copolymer composition, a foam and a molded article.

A copolymer composed of a conjugated diene compound and a vinyl aromatic hydrocarbon has the problem of poor thermal stability, weather resistance, and ozone resistance due to the unsaturated double bond in the copolymer. As a method for solving such problems, a method of hydrogenating unsaturated double bonds has been conventionally known. For example, it is disclosed in Japanese Unexamined Patent Publication No. 56-30447, Japanese Unexamined Patent Publication No. 2-36244, and the like.
On the other hand, hydrogenated products of block copolymers composed of conjugated diene compounds and vinyl aromatic hydrocarbons have the same elasticity as vulcanized natural rubber or synthetic rubber without vulcanization at room temperature, and have the same workability as thermoplastic resins at high temperatures.
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 1 discloses a hydrogenated block copolymer comprising a copolymer having a styrene-based block and a butadiene/styrene-containing block, and a molding material based thereon.
Further, Patent Document 2 discloses a hydrogenated block copolymer composed of a copolymer having a styrene-based block and a block containing butadiene/styrene whose distribution is controlled.

WO2003/035705 WO2003/066697

However, when the hydrogenated diene-based copolymer is combined with various thermoplastic resins and rubber-like substances to form a composition and the composition is used as a molding material, there is a problem that the composition has insufficient properties such as wear resistance, compression set, and oil resistance.
In addition, it is desired that the hydrogenated diene-based copolymer achieve both flexibility and mechanical strength and improve blocking resistance.

Therefore, in the present invention, when used as a molding material, a composition having excellent wear resistance, compression set and oil resistance is obtained, flexibility and mechanical strength are both achieved, and blocking resistance is also excellent. An object of the present invention is to provide a hydrogenated copolymer.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a hydrogenated copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit has a polymer block (a) made of at least one vinyl aromatic unit, a polymer block (b) made of at least one conjugated diene monomer unit, and a random copolymer block (c) made of a conjugated diene monomer unit and a vinyl aromatic monomer unit. A hydrogenated copolymer having a unit content within a predetermined numerical range and a tan δ peak temperature within a predetermined temperature range in a dynamic viscoelastic spectrum,
The inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention is as follows.

[1]
A hydrogenated copolymer comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit,
at least one polymer block (a) consisting of vinyl aromatic monomer units;
at least one polymer block (b) consisting of conjugated diene monomer units;
a random copolymer block (c) consisting of conjugated diene monomer units and vinyl aromatic monomer units;
have
The content of the vinyl aromatic monomer unit is 50% by mass to 80% by mass,
In the dynamic viscoelastic spectrum, it has tan δ peak temperatures at −30 to 50 ° C. and 80 ° C. or higher,
Measurement by gel permeation chromatography using standard polystyrene as calibration curve
has one or more peaks in the molecular weight range of 250,000 or more,
The polymer block (b) composed of the conjugated diene monomer unit is the vinyl aromatic monomer
A polymer block (a) consisting of units, the conjugated diene monomer unit and the vinyl aromatic monomer
present between the random copolymer block (c) consisting of a unit and
The content of the polymer block (b) composed of the conjugated diene monomer unit is 1 to 8% by mass.
Hydrogenated copolymer.
[2]
The content of the polymer block (a) composed of the vinyl aromatic monomer unit is 5% by mass to 4%
The hydrogenated copolymer according to [1] above, which is 0% by mass.
[3]
The hydrogenated copolymer according to [1] or [2] above, wherein the content of the vinyl aromatic monomer unit in the random copolymer block (c) is 35% by mass to 80% by mass.
[4]
The hydrogenated copolymer according to any one of the above [1] to [3], wherein the hydrogenation rate of the conjugated diene monomer units is 85% or more.
[5]
1 to 99 parts by mass of the hydrogenated copolymer according to any one of [1] to [4] ;
99 to 1 part by mass of a thermoplastic resin other than the hydrogenated copolymer and/or a rubber-like polymer other than the hydrogenated copolymer;
A hydrogenated copolymer composition containing.
[6]
A foam containing the hydrogenated copolymer composition described in [5] above.
[7]
A molded article of the hydrogenated copolymer composition described in [5] above.
[8]
The molded body is
The molded article according to [7] above, which is selected from the group consisting of an extruded article, an injection molded article, a hollow molded article, a pressure molded article, a vacuum molded article, a foam molded article, a multilayer extruded article, a multilayer injection molded article, a high frequency fusion molded article, and a slush molded article.

ADVANTAGE OF THE INVENTION According to this invention, the hydrogenated copolymer from which the composition excellent in wear resistance, compression set, and oil resistance is obtained can be provided.
In addition, a hydrogenated copolymer having both flexibility and mechanical strength and improved blocking resistance can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail.
It should be noted that the following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

In this specification, 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 produced by polymerizing a vinyl aromatic compound as a monomer, and its structure is a molecular structure in which two carbon atoms of a substituted ethylene group derived from a substituted vinyl 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 compound as a monomer, and its structure is a molecular structure in which two carbon atoms of an olefin derived from a conjugated diene monomer are bonding sites.

[Hydrogenated copolymer]
The hydrogenated copolymer of the present embodiment is a hydrogenated copolymer containing conjugated diene monomer units and vinyl aromatic monomer units.
The hydrogenated copolymer of the present embodiment is
a polymer block (a) consisting of at least one vinyl aromatic monomer unit;
at least one polymer block (b) consisting of conjugated diene monomer units;
a random copolymer block (c) consisting of conjugated diene monomer units and vinyl aromatic monomer units;
The content of vinyl aromatic monomer units is 50% by mass to 80% by mass,
The dynamic viscoelastic spectrum obtained for the hydrogenated copolymer has a tan δ peak temperature of -30 to 50°C and 80°C or higher.

In the hydrogenated copolymer of the present embodiment, when the content of the vinyl aromatic monomer unit is 50% by mass or more, excellent blocking resistance (handleability) and scratch resistance can be obtained, and when it is 80% by mass or less, flexibility and impact resilience are excellent, and the hydrogenated copolymer composition has excellent impact resistance.
The content of vinyl aromatic monomer units is preferably 52 to 75% by mass, more preferably 54 to 70% by mass.
The content of vinyl aromatic monomer units can be measured using an ultraviolet spectrophotometer.
The vinyl aromatic monomer unit content of the hydrogenated copolymer may be measured by measuring the vinyl aromatic monomer unit content in the copolymer (non-hydrogenated copolymer) before hydrogenation.

In the hydrogenated copolymer of the present embodiment, the content of the polymer block (a) composed of vinyl aromatic compound monomer units (hereinafter sometimes simply referred to as "vinyl aromatic polymer block (a)") is preferably 5% by mass to 40% by mass.
If the content of the vinyl aromatic polymer block (a) is 5% by mass or more, excellent blocking resistance and impact resilience will be obtained, and if it is 40% by mass or less, excellent scratch resistance will be obtained.
The content of the vinyl aromatic polymer block (a) is more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, even more preferably 13 to 25% by mass.

The content of the vinyl aromatic polymer block (a) in the hydrogenated copolymer of the present embodiment is the vinyl aromatic determined by a method of oxidatively decomposing the copolymer before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (the method described in IM KOLTHOFF, et al., J. Polym. It is a value obtained from the following formula using the mass of the group polymer block component (however, the vinyl aromatic polymer component having an average degree of polymerization of about 30 or less is excluded).
Content of vinyl aromatic polymer block (a) (% by mass)=(mass of vinyl aromatic polymer block (a) in copolymer before hydrogenation/mass of copolymer before hydrogenation)×100
The content of the vinyl aromatic polymer block (a) in the hydrogenated copolymer can be directly measured using a nuclear magnetic resonance spectrometer (NMR) (method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981)), even for the polymer after hydrogenation. It is the content of the vinyl aromatic polymer block (a).
There is a correlation between the content of the vinyl aromatic polymer block (a) of the copolymer before hydrogenation measured by the osmium tetroxide decomposition method described above (referred to as the "Os value") and the content of the vinyl aromatic polymer block (a) of the copolymer after hydrogenation measured by the NMR method (referred to as the "Ns value").
As a result of examining various copolymers having different contents of the vinyl aromatic polymer block (a), the relationship can be represented by the following formula.
Os value = -0.012 (Ns value) 2 + 1.8 (Ns value) -13.0
Therefore, in the present embodiment, when the content of the vinyl aromatic polymer block (a) of the copolymer after hydrogenation is determined by the NMR method, the Ns value is converted to the Os value based on the above formula to determine the content of the vinyl aromatic polymer block (a).
The content of the polymer block (a) composed of vinyl aromatic monomer units in the hydrogenated copolymer of the present embodiment can be controlled within the above numerical range by adjusting the amount and timing of addition of the vinyl aromatic monomer in the polymerization step.

The content of vinyl aromatic monomer units in the random copolymer block (c) in the hydrogenated copolymer of the present embodiment is preferably 35% by mass to 80% by mass.
When the content of the vinyl aromatic monomer unit is 35% by mass or more, the abrasion resistance and scratch resistance are excellent, and when it is 80% by mass or less, the flexibility and resilience are excellent.
The content of vinyl aromatic monomer units in the random copolymer block (c) is more preferably 40 to 75 mass %, still more preferably 45 to 70 mass %.
The content of the vinyl aromatic monomer unit in the random copolymer block (c) can be calculated from the measured values obtained by extracting the polymer before and after polymerizing the random copolymer block (c), quantifying the vinyl aromatic polymer content by an ultraviolet spectrophotometer, and quantifying the vinyl aromatic polymer block component by the "osmium tetroxide decomposition method".
The content of the vinyl aromatic monomer units in the random copolymer block (c) can be controlled within the above numerical range by adjusting the amount and timing of addition of the vinyl aromatic monomer in the polymerization step.

The weight average molecular weight of the hydrogenated copolymer of the present embodiment is preferably more than 100,000 and 1,000,000 or less.
When the weight average molecular weight of the hydrogenated copolymer exceeds 100,000, the blocking resistance, impact resilience and scratch resistance are excellent, and when it is 1,000,000 or less, the moldability is excellent.
The weight average molecular weight of the hydrogenated copolymer of the present embodiment is more preferably 130,000 to 800,000, more preferably 150,000 to 500,000.
The weight average molecular weight of the hydrogenated copolymer is measured by gel permeation chromatography (GPC), and a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene can be used.

The molecular weight distribution of the hydrogenated copolymer of the present embodiment preferably has one or more peaks in the molecular weight range of 250,000 or more. If it has one or more peaks in the molecular weight range of 250,000 or more, it has excellent abrasion resistance. More preferably, it has one or more peaks in the range of 300,000 or more, and more preferably has one or more peaks in the range of 350,000 or more. The molecular weight of the hydrogenated copolymer is measured by gel permeation chromatography (GPC), and can be determined using a calibration curve (prepared using the peak molecular weight of the standard polystyrene) obtained from the measurement of a commercially available standard polystyrene. In the molecular weight distribution of the hydrogenated copolymer of the present embodiment, in order to have one or more peaks in the molecular weight range of 250,000 or more, a method of adjusting the amount of the polymerization initiator and a method of using a coupling agent are effective.

In the hydrogenated copolymer of the present embodiment, 85% or more of the double bonds based on the conjugated diene monomer units are preferably hydrogenated.
Since 85% or more of the double bonds based on the conjugated diene monomer units are hydrogenated, excellent blocking resistance and scratch resistance are exhibited.
The amount of hydrogenated double bonds is more preferably 90% or more, still more preferably 92% or more, still more preferably 95% or more.
The hydrogenation rate of the hydrogenated copolymer can be determined using a nuclear magnetic resonance spectrometer (NMR).

The hydrogenated copolymer of the present embodiment has at least one tan δ (loss tangent) peak at −30° C. to 50° C. and at 80° C. or higher in the obtained dynamic viscoelastic spectrum.
The temperature range with one or more tan δ peaks is preferably -25 to 45°C and 85°C or higher, more preferably -20 to 40°C and 90°C or higher, and even more preferably -15 to 35°C and 93°C or higher.
The existence of at least one tan δ peak in the range of −30° C. to 50° C. is necessary from the viewpoint of abrasion resistance of the hydrogenated copolymer composition of the present embodiment. The presence of at least one at 80° C. or higher is necessary from the viewpoint of tensile strength of the hydrogenated copolymer of the present embodiment, heat resistance of the hydrogenated copolymer composition, and scratch resistance.
By controlling the ratio of the vinyl aromatic monomer unit in the random copolymer block (c) to 35 to 80% by mass, the position of at least one tan δ peak in the dynamic viscoelastic spectrum can be within the range of -30°C to 50°C.
Further, at least one tan δ is obtained by controlling the polymer block (a) composed of the vinyl aromatic monomer unit to 5 to 40% by mass relative to the hydrogenated copolymer, and controlling the polymer block (b) composed of the conjugated diene monomer unit to 1% by mass or more between the polymer block (a) and the random copolymer block (c) to the hydrogenated copolymer, or setting the polymer block (a) composed of the vinyl aromatic monomer unit to 40 to 80% by mass relative to the hydrogenated copolymer. The peak position can be within the range of 80° C. or higher.

The hydrogenated copolymer of this embodiment has a polymer block (b) composed of at least one conjugated diene monomer unit.
Having the polymer block (b) is necessary from the viewpoint of the tensile strength and blocking resistance of the hydrogenated copolymer, and the heat resistance and scratch resistance of the hydrogenated copolymer composition.
The content of the polymer block (b) relative to the hydrogenated copolymer is preferably 1 to 10% by mass, more preferably 1 to less than 7% by mass, and even more preferably 1 to less than 5% by mass.
By having the polymer block (b) of 1% by mass or more, the tensile strength and blocking resistance of the hydrogenated copolymer and the heat resistance and scratch resistance of the hydrogenated copolymer composition are excellent, and by being 10% by mass or less, the wear resistance is excellent.

The hydrogenated copolymer of the present embodiment preferably has at least one polymer block (b) between the polymer block (a) and the random copolymer block (c).
By having the polymer block (b) between the polymer block (a) and the random copolymer block (c), the hydrogenated copolymer of the present embodiment has excellent tensile strength and blocking resistance, and the hydrogenated copolymer composition of the present embodiment has excellent heat resistance and scratch resistance.

The structure of the hydrogenated copolymer of the present embodiment is not particularly limited, and may be any structure as long as it has each block of the polymer block (a), the polymer block (b), and the random copolymer block (c).
It should be noted that it preferably has a structure represented by the following formulas (1) to (12).
abc (1)
acb (2)
bac (3)
abac (4)
abca (5)
abcb (6)
acab (7)
acbc (8)
b-a-b-c (9)
bacb (10)
bcac (11)
cabc (12)
In the formulas (1) to (12), each c independently represents a random copolymer block (c) composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit, each a independently represents a polymer block (a) composed of a vinyl aromatic monomer unit, and each b independently represents a polymer block (b) composed of a conjugated diene monomer unit.
From the viewpoint of productivity, workability, and wear resistance, it is preferable to have the structure represented by the formula (1) or (6).
The hydrogenated copolymer of the present embodiment may also be a mixture of hydrogenated block copolymers having different structures.
Further, the hydrogenated copolymer of the present embodiment may be mixed with a vinyl aromatic compound polymer.

In the production process of the hydrogenated copolymer of the present embodiment, a coupling reaction may be carried out using a bifunctional or higher coupling agent when the polymerization of the block copolymer is completed.
A known bifunctional coupling agent can 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, when using a trifunctional or more polyfunctional coupling agent, a known one can be used, and it is not particularly limited.
例えば、３価以上のポリアルコール類；エポキシ化大豆油、ジグリシジルビスフェノールＡ等の多価エポキシ化合物；式Ｒ ₄ －ｎＳｉＸ _n （ただし、Ｒはそれぞれ独立して炭素数１～２０の炭化水素基、Ｘはハロゲン、ｎは３～４の整数を示す）で示されるハロゲン化珪素化合物、例えば、メチルシリルトリクロリド、ｔ－ブチルシリルトリクロリド、四塩化珪素、及びこれらの臭素化物等；式Ｒ ₄ －ｎＳｎＸ _n （ただし、Ｒはそれぞれ独立して炭素数１～２０の炭化水素基、Ｘはハロゲン、ｎは３～４の整数を示す。）で示されるハロゲン化錫化合物、具体的にはメチル錫トリクロリド、ｔ－ブチル錫トリクロリド、四塩化錫等の多価ハロゲン化合物を用いることができる。
Dimethyl carbonate and diethyl carbonate can also be used as polyfunctional coupling agents.

In the above formulas (1) to (12), the distribution of the vinyl aromatic monomer units in the random copolymer block (c) is not particularly limited, and the vinyl aromatic monomer units in the random copolymer block (c) may be uniformly distributed or tapered. In addition, there may be a plurality of portions in which the vinyl aromatic monomer units are uniformly distributed and/or a plurality of portions in which the vinyl aromatic monomer units are distributed in a tapered manner, and a plurality of segments having different vinyl aromatic hydrocarbon contents may be present.

The conjugated diene monomer used in the hydrogenated copolymer of the present embodiment is a diolefin having a pair of conjugated double bonds, and examples thereof include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (that is, isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like.
Preferred are 1,3-butadiene and isoprene.
These may use only 1 type and may use 2 or more types together.
Further, the vinyl aromatic monomer used in the hydrogenated copolymer of the present embodiment is not limited to the following, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and the like. These may use only 1 type and may use 2 or more types together.

In the hydrogenated copolymer of the present embodiment, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene monomer units of the copolymer before hydrogenation can be arbitrarily controlled by using a polar compound or the like described later.
When 1,3-butadiene is used as the conjugated diene monomer, it is generally recommended that the 1,2-vinyl bond content is preferably 5 to 80%, more preferably 10 to 60%, and still more preferably 12 to 50%, and is preferably 12% or more in order to obtain a highly flexible copolymer.
When isoprene is used as the conjugated diene monomer, or when 1,3-butadiene and isoprene are used together, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is generally recommended to be preferably 3 to 75%, more preferably 5 to 60%.
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) is referred to as the "vinyl bond amount".
The amount of vinyl bonds based on the conjugated diene monomer units in the copolymer before hydrogenation can be determined using an infrared spectrophotometer (Hampton method).

The hydrogenated copolymer of the present embodiment can be produced by first producing a copolymer before hydrogenation (non-hydrogenated copolymer) and then hydrogenating the non-hydrogenated copolymer.
The non-hydrogenated copolymer can be produced, for example, by anionic living polymerization using a polymerization 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, alicyclic hydrocarbons such as methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

As the polymerization initiator, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, organic amino alkali metal compounds, etc., which are generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds can be used.
Alkali metals include lithium, sodium, potassium, and the like, and suitable organic alkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and compounds containing one lithium per molecule, dilithium compounds, trilithium compounds, and tetralithium compounds containing multiple lithium per molecule.
Specific examples include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, reaction products of diisopropenylbenzene and sec-butyllithium, and reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene.
Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent No. 2,241,239, US Pat. No. 5,527,753, etc. can also be used.

When a conjugated diene monomer and a vinyl aromatic monomer are copolymerized using an organic alkali metal compound as a polymerization initiator, a tertiary amine compound or an ether compound can be used as a modifier to adjust the amount of vinyl bonds (i.e., 1,2-vinyl bond or 3,4-vinyl bond) resulting from the conjugated diene monomer units incorporated in the polymer and the random copolymerizability of the conjugated diene and the vinyl aromatic compound.
前記第３級アミン化合物は、一般式Ｒ ₁ Ｒ ₂ Ｒ ₃ Ｎ（但し、Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃は、それぞれ独立して炭素数１～２０の炭化水素基又は第３級アミノ基を有する炭素数１～２０の炭化水素基である。）で表される化合物、具体的には、Ｎ，Ｎ－ジメチルアニリン、Ｎ－エチルピペリジン、Ｎ－メチルピロリジン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラエチルエチレンジアミン、１，２－ジピペリジノエタン、トリメチルアミノエチルピペラジン、Ｎ，Ｎ，Ｎ'，Ｎ”，Ｎ”－ペンタメチルエチレントリアミン、Ｎ，Ｎ'－ジオクチル－ｐ－フェニレンジアミン等である。
Moreover, as an ether compound, a linear ether compound and a cyclic ether compound can be used.
Examples of linear ether compounds include ethylene glycol dialkyl ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and diethylene glycol dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Examples of cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers of furfuryl alcohol.

A method of copolymerizing a conjugated diene monomer and a vinyl aromatic monomer using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof.
In particular, from the viewpoint of moldability, a continuous polymerization method is preferable for adjusting the molecular weight distribution to an appropriate range.
The polymerization temperature is generally 0°C to 180°C, preferably 30°C to 150°C.
The time required for polymerization varies depending on the conditions, but it is usually within 48 hours, particularly preferably 0.1 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 it is within the range of pressure sufficient to maintain 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 copolymer of the present embodiment is obtained by hydrogenating the copolymer produced by the above method.
The hydrogenation catalyst is not particularly limited, and the following compounds (1) to (3) conventionally used as a hydrogenation catalyst can be used. That is, (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc., (2) so-called Ziegler-type hydrogenation catalysts in which organic acid salts of Ni, Co, Fe, Cr, etc. or transition metal salts such as acetylacetone salts are used together with reducing agents such as organic aluminum, and (3) homogeneous hydrogenation catalysts, such as so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh, and Zr.
As specific hydrogenation catalysts, the hydrogenation catalysts described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 1-37970, etc. can be used.
Preferred hydrogenation catalysts include titanocene compounds and mixtures of titanocene compounds and reducing organometallic compounds. As the titanocene compound, compounds described in Japanese Patent Laid-Open No. 8-109219 can be used. Specific examples include compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton, such as biscyclopentadienyltitanium dichloride and monopentamethylcyclopentadienyltitanium trichloride.
Examples of the reducing organometallic compounds include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
The hydrogenation reaction for producing the hydrogenated copolymer of the present embodiment is generally carried out at a temperature range of 0 to 200°C, preferably 30 to 150°C.
The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, still more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be batch process, continuous process, or a combination thereof.

A solution containing the hydrogenated copolymer is obtained by the hydrogenation reaction of the copolymer.
If necessary, catalyst residues are removed from the solution containing the hydrogenated copolymer to separate the hydrogenated copolymer from the solution.
Methods for separating the solvent include, for example, a method in which a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated copolymer, is added to the reaction solution after hydrogenation to precipitate and recover the polymer; a method in which the reaction solution is poured into hot water while stirring and the solvent is removed by steam stripping to recover; or a method in which the solvent is distilled off by directly heating the polymer solution.

Stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added to the hydrogenated copolymer of the present embodiment.

The hydrogenated copolymer of the present embodiment may be graft-modified with an α,β-unsaturated carboxylic acid or a derivative thereof such as an anhydride, ester, amid or imid thereof.
Such a graft-modified hydrogenated copolymer can also be used in the hydrogenated copolymer composition of the present embodiment, which will be described later.
Examples of the α,β-unsaturated carboxylic acid or derivative thereof include, but are not limited to, 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 preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the hydrogenated polymer.

[Hydrogenated copolymer composition]
The hydrogenated copolymer composition of the present embodiment contains 1 to 99 parts by mass of the above-described hydrogenated copolymer of the present embodiment, a thermoplastic resin other than the hydrogenated copolymer of the present embodiment, and/or 99 to 1 part by mass of a rubber-like polymer other than the hydrogenated copolymer of the present embodiment.
By combining the hydrogenated copolymer of the present embodiment with a thermoplastic resin and/or a rubber-like polymer other than the hydrogenated copolymer, a hydrogenated copolymer composition suitable for various molding materials can be obtained.
In the hydrogenated copolymer composition of the present embodiment, the blending ratio of the hydrogenated copolymer and the thermoplastic resin and/or the rubber-like polymer is, in mass ratio, hydrogenated copolymer/(thermoplastic resin and/or rubber-like polymer) = 1/99 to 99/1, preferably 2/98 to 90/10, more preferably 5/95 to 70/30.
When the hydrogenated copolymer of the present embodiment is mixed with a thermoplastic resin and/or a rubber-like polymer other than the hydrogenated copolymer, a hydrogenated copolymer composition having excellent impact resistance and moldability can be obtained.

The thermoplastic resin other than the hydrogenated polymer of the present embodiment, which is used in the hydrogenated copolymer composition of the present embodiment, is not limited to the following. For example, a block copolymer resin of a conjugated diene monomer and a vinyl aromatic monomer having a vinyl aromatic monomer unit content of more than 60% by mass and a hydrogenated product thereof (but different from the hydrogenated copolymer of the present embodiment); a polymer of the vinyl aromatic monomer; Copolymer resins with other vinyl monomers (e.g., ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and acrylic methyl, methacrylic acid esters such as methacrylic acid and methyl methacrylate, acrylonitrile, methacrylonitrile, etc.); rubber-modified styrene resins (HIPS); acrylonitrile-butadiene-styrene copolymer resins (ABS); MBS); polyethylene; copolymers composed of ethylene and other copolymerizable monomers, such as ethylene-propylene copolymers, ethylene-butylene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, and hydrolysates thereof, and having an ethylene content of 50% by mass or more; polyethylene-based resins such as ethylene-acrylic acid ionomers and chlorinated polyethylene; polypropylene; , ethylene-norbornene resins and other cyclic olefin resins, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins and hydrolysates thereof, copolymers containing propylene and other copolymerizable monomers having a propylene content of 50 mass% or more; polymers of acrylic acid and its esters and amides; polyacrylate resins; polymers of acrylonitrile and/or methacrylonitrile; Nitrile resin, which is a copolymer having a nitrile-based monomer content of 50% by mass or more; polyamide-based resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, and nylon-6 nylon-12 copolymers; polyester-based resins; thermoplastic polyurethane-based resins; Plastic polysulfone; Polyoxymethylene resin; Polyphenylene ether resin such as poly(2,6-dimethyl-1,4-phenylene) ether; Polyphenylene sulfide resin such as polyphenylene sulfide and poly4,4'-diphenylene sulfide; Polyarylate resin; Examples include polybutadiene-based resins such as dienes.
These thermoplastic resins may have polar group-containing atomic groups such as hydroxyl groups, epoxy groups, amino groups, carboxylic acid groups, and acid anhydride groups bonded thereto.
The number average molecular weight of the thermoplastic resin used in the hydrogenated copolymer composition of the present embodiment is preferably 1,000 or more, more preferably 5,000 to 5,000,000, and still more preferably 10,000 to 1,000,000.
The number average molecular weight of the thermoplastic resin can be measured by GPC in the same manner as the measurement of the molecular weight of the hydrogenated copolymer of the present embodiment.

Further, when the hydrogenated copolymer of the present embodiment is mixed with a rubber-like polymer other than the hydrogenated copolymer, a hydrogenated copolymer composition having excellent tensile strength, elongation properties, and moldability can be obtained.
Examples of the rubber-like polymer used in the hydrogenated copolymer composition of the present embodiment include, but are not limited to the following, butadiene rubber and hydrogenated products thereof; styrene-butadiene rubber and hydrogenated products thereof (but different from the hydrogenated copolymer of the present embodiment); isoprene rubber; acrylonitrile-butadiene rubber and hydrogenated products thereof; Olefinic elastomers such as ten rubber, ethylene-hexene rubber, ethylene-octene rubber; Olefinic TPE with EPDM, EPM, etc. as a soft phase; Butyl rubber; Acrylic rubber; Fluoro rubber; Silicone rubber; Chlorinated polyethylene rubber; styrene-based elastomers having a styrene content of 60% by mass or less, such as styrene-butadiene-isoprene block copolymers and hydrogenated products thereof; natural rubbers;
These rubber-like polymers may be modified rubbers provided with functional groups (carboxyl group, carbonyl group, acid anhydride group, hydroxyl group, epoxy group, amino group, silanol group, alkoxysilane group, etc.).
The number average molecular weight of the rubber-like polymer used in the hydrogenated copolymer composition of the present embodiment is preferably 10,000 or more, more preferably 20,000 to 1,000,000, and still more preferably 30,000 to 800,000.
The number average molecular weight of the rubber-like polymer can be measured by GPC in the same manner as the measurement of the molecular weight of the hydrogenated copolymer of the present embodiment described above.

Two or more of the thermoplastic resin and rubber-like polymer used in the above-described hydrogenated copolymer composition of the present embodiment can be used in combination, if necessary.
When two or more types are used in combination, two or more thermoplastic resins or two or more rubber-like polymers may be used, or a thermoplastic resin and a rubber-like polymer may be used in combination.
Specifically, a rubber-like polymer may be used in combination to increase the impact resistance of a resinous composition (i.e., a composition in which the resin accounts for the majority), or to reduce the hardness of the composition, or a resin may be used in combination to increase the strength and heat resistance of the rubber-like composition (i.e., a composition in which the rubbery polymer accounts for the majority).

Any additive may be added to the hydrogenated copolymer and hydrogenated copolymer composition of the present embodiment, if necessary.
The additive is not particularly limited as long as it is generally blended with thermoplastic resins and rubber-like polymers, and examples thereof include those described in "Rubber and Plastic Compounding Chemicals" (edited by Rubber Digest Co., Ltd., Japan).
Specifically, reinforcing fillers, inorganic fillers such as calcium sulfate and barium sulfate; pigments such as carbon black and iron oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylenebisstearamide; plasticizers such as organic polysiloxane and mineral oil; antioxidants such as hindered phenol antioxidants and phosphorus heat stabilizers; hindered amine light stabilizers and benzotriazole ultraviolet absorbers; flame retardants;

In the method for producing the hydrogenated copolymer composition of the present embodiment, the method for mixing the hydrogenated copolymer with the thermoplastic resin and/or the rubber-like polymer 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, or a method of dissolving or dispersing and mixing each component and then removing the solvent by heating can be used.
In order to produce the hydrogenated copolymer composition of 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 copolymer composition is not particularly limited, but examples include pellets, sheets, strands, chips, and the like. Moreover, after melt-kneading, it can be directly molded.

[Foam]
The foam of the present embodiment contains the hydrogenated copolymer composition of the present embodiment described above.
The foaming method for obtaining the foam of the present embodiment includes a chemical method and a physical method, and in any case, by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, or a physical foaming agent, cells may be distributed inside the hydrogenated copolymer composition.
By forming the hydrogenated copolymer composition into a foam, it is possible to reduce the weight, improve the flexibility, and improve the design.
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'-dinitroso-N,N'-dimethylterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p,p'-oxybisbenzenesulfonylhydrazide, and p-toluenesulfonyl. semicarbazide and the like.
Examples of physical blowing 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;
These foaming agents may be used alone or in combination of two or more.
The blending amount of the foaming agent is preferably 0.1 to 8 parts by mass, more preferably 0.3 to 6 parts by mass, still more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the hydrogenated copolymer or hydrogenated copolymer composition.

Any additive may be added to the foam of the present embodiment, if necessary.
The type of additive is not particularly limited as long as it is generally blended in thermoplastic resins and rubber-like polymers. For example, various additives described in the above-mentioned "Rubber/Plastic Chemicals" (edited by Rubber Digest Co., Ltd., Japan) can be used.
Moreover, the foam of the present embodiment may 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, or the like; and a physical cross-linking method using an electron beam, radiation, or the like.
The cross-linking process includes, for example, a static method such as radiation cross-linking (a method of cross-linking without kneading), a dynamic cross-linking method, and the like.
As a specific method for obtaining a crosslinked foam, for example, a sheet is prepared using a mixture of a polymer and a foaming agent or a crosslinking agent, and when this sheet is heated to about 160° C., a crosslinking reaction occurs simultaneously with foaming, thereby obtaining a crosslinked foam.
As a cross-linking agent, an organic peroxide or a vulcanization accelerator can be used, and a peroxy cross-linking auxiliary agent, a polyfunctional vinyl monomer, or the like can be used in combination.
The amount of these vulcanization accelerators to be used is usually preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the hydrogenated copolymer or hydrogenated copolymer composition.

Organic peroxides used as cross-linking agents include 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyisopropyl)benzene, and 1,1-bis(tert-butylperoxy), from the viewpoint of odor and scorch stability (the properties of not cross-linking under the conditions of mixing each component but rapidly cross-linking under the cross-linking reaction conditions). )-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate and di-tert-butyl peroxide are preferred.
In addition to the above, for example, dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

When vulcanizing, a sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, dithiocarbamate-based compounds, etc. may be used as a vulcanization accelerator in an appropriate amount.
Zinc white, stearic acid, or the like can also be used as a vulcanizing aid in an appropriate amount.

Further, when the above-described organic peroxide is used to crosslink the hydrogenated copolymer composition of the present embodiment containing a reinforcing filler, the vulcanization accelerator may be, for example, sulfur; Polyfunctional methacrylate monomers such as benzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate; polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can also be used in combination with organic peroxides.
Such a vulcanization accelerator is usually used in an amount of preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the hydrogenated copolymer or hydrogenated copolymer composition.

[Molded body]
The hydrogenated copolymer composition of the present embodiment can be made into various molded articles by a molding method. Examples of the molded article include extrusion molded articles, injection molded articles, hollow molded articles, pressure molded articles, vacuum molded articles, foam molded articles, multilayer extruded articles, multilayer injection molded articles, high frequency fusion molded articles, and slush molded articles.
In addition, the foam of the present embodiment described above can also be used for sheets, films, injection-molded articles of various shapes, blow-molded articles, pressure-molded articles, vacuum-molded articles, extrusion-molded articles, and the like.
In particular, it is suitable for fruit and egg packaging materials, meat trays, food packaging and containers such as lunch boxes, etc., which require flexibility. Examples of materials for food packaging and containers include olefin resins such as PP, vinyl aromatic compound polymers such as PS, rubber-modified styrenic resins such as HIPS, and hydrogenated copolymers or modified hydrogenated copolymers of the present embodiment (/block copolymers composed of a conjugated diene and a vinyl aromatic compound or hydrogenated products thereof (however, different from the hydrogenated copolymer of the present invention) as necessary).
In addition, the foam of the present embodiment described above can also be combined with a hard resin molded product to form a cushioning composite molded product by injection molding such as an insert/mold gap enlarging method as disclosed in Japanese Patent Application Laid-Open No. 6-234133.

[Use]
The hydrogenated copolymer or hydrogenated copolymer composition of the present embodiment can be used for various purposes by blending various additives as necessary.
Applications of molded products such as reinforcing filler compounds, crosslinked products, foams, multilayer films and multilayer sheets include, for example, building materials, vibration damping/soundproofing materials, wire coating materials, high frequency fusion compositions, slush molding materials, adhesive compositions, asphalt compositions, automotive interior materials, automotive exterior materials, medical device materials, various containers such as food packaging containers, household appliances, industrial parts, toys, and the like.

EXAMPLES The present embodiment will be specifically described below with specific examples and comparative examples, but the present embodiment is not limited by the following examples and comparative examples.

[I. Hydrogenated copolymer]
In Examples 1 to 12 and Comparative Examples 1 to 2 and 4 to 7 which will be described later, a non-hydrogenated copolymer was polymerized and then hydrogenated to obtain a hydrogenated copolymer.
The physical properties and properties of the non-hydrogenated copolymers or hydrogenated copolymers were measured by the following methods.

(I-1) Styrene content The styrene content of the non-hydrogenated copolymer and the non-hydrogenated polymer was measured using an ultraviolet spectrophotometer (device name: UV-2450; manufactured by Shimadzu Corporation, Japan).

(I-2) Content of styrene block (a) (Os value)
The polystyrene block (H) content of the non-hydrogenated copolymer is determined according to I.V. 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 for decomposition of the non-hydrogenated copolymer. In addition, the styrene block content obtained here is called "Os value."

When measuring the content of the styrene block (a) of the hydrogenated copolymer, a nuclear magnetic resonance apparatus (device name: ECS-400; manufactured by JEOL RESONANCE Co., Ltd., Japan) was used. Tanaka, et al. , RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981).
Specifically, 30 mg of the hydrogenated copolymer dissolved in 1 g of deuterated chloroform was used as a sample, and 1H-NMR was measured.
The polystyrene block content (Ns value) of the hydrogenated copolymer obtained by NMR was determined from the ratio of the chemical shift integrated value of 6.9 to 6.3 ppm to the total integrated value, and then the Ns value was converted to the Os value.
The calculation method is shown below.
・Styrene block strength:
(6.9 to 6.3 ppm) integrated value / 2
Styrene strength in random block (c):
(7.5 to 6.9 ppm) integrated value -3 (styrene block strength)
・Butadiene strength:
Total integrated value -3 {(styrene block strength) + (styrene strength in random block (c))}/8
・Styrene block content (Ns value) obtained by NMR
= 104 (styrene block strength) / [104 {(styrene block strength) + (styrene strength in random block (c))} + 56 (butadiene strength)]
・ Os value = -0.012 (Ns) 2 + 1.8 (Ns) - 13.0

(I-3) Content of butadiene block (b) The content of butadiene block (b) was calculated by calculating the ratio of the mass of butadiene polymerized in the absence of styrene to the mass of the total hydrogenated copolymer.

(I-4) Styrene Content in Random Block (c) When measuring the styrene content in the random block (c) of the hydrogenated copolymer, a nuclear magnetic resonance apparatus (device name: ECS-400; manufactured by JEOL RESONANCE Co., Ltd., Japan) was used. Tanaka, et al. , RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981).
Specifically, 30 mg of the hydrogenated copolymer dissolved in 1 g of deuterated chloroform was used as a sample, and 1H-NMR was measured.
The random styrene content (Ns value) of the hydrogenated copolymer obtained by NMR was obtained from the ratio of the chemical shift integrated value of 6.9 to 6.3 ppm to the total integrated value, and then the Ns value was converted to the Os value.
The calculation method is shown below.
・Styrene block strength:
(6.9 to 6.3 ppm) integrated value / 2
Styrene strength in random block (c):
(7.5 to 6.9 ppm) integrated value -3 (styrene block strength)
・Butadiene strength:
Total integrated value -3 {(styrene block strength) + (styrene strength in random block (c))}/8
・Styrene content (Ns value) in random block (c) obtained by NMR
=104 (styrene strength in random block (c))/[104 {(styrene block strength) + (styrene strength in random block (c))} + 56 (butadiene strength)]
・ Os value = -0.012 (Ns) 2 + 1.8 (Ns) - 13.0

Styrene content in random block (c) = (styrene content in random block (c) (Os value)/(100 - styrene block (a) content (Os value) - butadiene block (b) content)) x 100

(I-5) Vinyl bond amount of non-hydrogenated copolymer and non-hydrogenated polymer Using an infrared spectrophotometer (device name: FT/IR-4100; manufactured by JASCO Corporation, Japan), the amount of vinyl bonds was calculated by the Hampton method in the case of copolymers, and by the Morero method in the case of homopolymers.

(I-6) Hydrogenation rate of double bond of conjugated diene monomer unit The hydrogenation rate was measured using a nuclear magnetic resonance spectrometer (device name: ECS-400; manufactured by JEOL RESONANCE, Japan).

(I-7) Presence or Absence of Peaks in the Range of Molecular Weights of 250,000 or More The molecular weights and molecular weight distributions of the hydrogenated copolymer and the hydrogenated polymer were measured using a GPC apparatus (manufactured by Tosoh, Japan).
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 presence or absence of peaks in the range of molecular weights of 250,000 or more.

(I-8) Dynamic viscoelasticity spectrum First, the hydrogenated copolymer was pressed while being heated to 200°C, molded into a sheet of 200 mm × 100 mm × 2 mm, and cut into a size of 12.5 mm in width and 40 mm in length to obtain a sample for measurement.
Next, this measurement sample was set in the twist type geometry of the device ARES (manufactured by TA Instruments Co., Ltd., trade name), and the tan δ peak temperature was determined under the conditions of an effective measurement length of 25 mm, a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3 ° C./min.
The tan δ peak temperature was a value determined from the peak detected by automatic measurement with an RSI Orchestrator (trade name, manufactured by TA Instruments Co., Ltd.).

(I-9) Block Structure of Copolymer The block structure was estimated from the production method.
a represents a polymer block (a) composed of vinyl aromatic units, b represents a polymer block (b) composed of conjugated diene monomer units, and c represents a random copolymer block (c) composed of conjugated diene monomer units and vinyl aromatic monomer units.

(I-10) Blocking Resistance of Hydrogenated Copolymer Blocking resistance was measured by the following method.
A total of 60 g of a plurality of hydrogenated copolymer sample pellets of the same shape (cylindrical with a diameter of about 3 mm×3 mm) was placed in a metal cylinder with a diameter of 5 cm, and a weight of 1160 g was placed thereon.
In this state, after heating for 20 hours in a gear oven heated to 42° C., the state of adhesion of pellets in the cylinder was observed.
Specifically, the mass of pellets taken out from the cylinder crumbles (however, pellets with poor blocking resistance do not crumble as clumps), so the mass of a clump consisting of three or more pellets was measured, and the ratio (%) of the weight of the pellet clump to the total mass of the pellets (60 g) was determined.
The quality of blocking resistance was evaluated based on the following criteria.
Each sample pellet was evaluated after adding calcium stearate equivalent to 1500 ppm.
◎ indicates no sticking.
〇 is partially adhered, but it can be easily loosened when touched.
△ indicates that it adheres and partly comes loose when touched.
X is adhered and hardly unraveled.

(I-11) 100% modulus 100% modulus was used as an index of flexibility.
According to JIS K 6251, the tensile properties of a compression test piece of the hydrogenated 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 7.0 MPa or less is preferable.
The tensile speed was 500 mm/min, and the measurement temperature was 23°C.

(I-12) Tensile strength (Tb), elongation at break (Eb)
Measured according to JIS K 6251 with a No. 3 dumbbell and a crosshead speed of 500 mm/min.
A tensile strength of 20 MPa or more was judged to be good for practical use.
A breaking elongation of 400% or more was judged to be good for practical use.

(I-13) Damping property Measured by the cantilever method according to JIS 7391.
A test piece for this measurement was prepared by attaching a SUS plate to a compression test piece of the hydrogenated copolymer.
The measurement test temperature was 23° C., and the loss factor was calculated from the envelope curve of the attenuation curve. The evaluation is shown in Table 2.
◎: loss factor 0.05 or more ○: loss factor less than 0.05 0.03 or more △: loss factor less than 0.03 0.01 or more ×: loss factor less than 0.01

[II. Hydrogenated block copolymer composition]
In Examples 13 to 25 and Comparative Examples 8 to 13 and 15 described later, hydrogenated block copolymer compositions were produced using the polymers 1 to 18 produced as described above.
Properties relating to the hydrogenated block copolymer composition were measured by the following methods.

[Method for evaluating properties of hydrogenated block copolymer composition]
(II-1) Hardness, 100% Stress, Tensile Strength, Elongation at Break Tensile properties were measured according to JIS K6251.
The stress at 100% stretching (hereinafter referred to as 100% Mo) was used as an index of flexibility. The smaller the 100% Mo, the better the flexibility, and 100 kg/cm2 or less was judged to be practically excellent.
The tensile speed was 500 mm/min, and the measurement temperature was 23°C.
Tensile strength was measured, and elongation at break was measured.
The hardness was measured as Shore A hardness after 10 seconds according to JIS K6253.

(II-2) Abrasion resistance Gakushin type friction tester (manufactured by Tester Sangyo Co., Ltd., AB-301 type) was used to measure the grain depth (Ry value) before and after rubbing the molded sheet surface (skin grain processed surface) prepared by the method described in Examples and Comparative Examples below with Kanakin No. 3 cotton and a load of 500 g, and the grain depth residual rate was calculated by the following formula 1, and the wear resistance was determined 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)
<Abrasion resistance evaluation criteria>
◎: After 10,000 times of rubbing, the grain depth residual rate is 50% or more ○: After 10,000 times of rubbing, the grain depth residual rate is less than 50%, 30% or more

(II-3) Oil Resistance According to JIS K6258, a test piece was immersed in IRM902 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, it is 0%, but the larger the swelling, the larger the number.
A swelling rate of less than 70% was judged to be practically good, and a swelling rate of less than 50% was judged to be excellent.
◎: 30% or less swelling rate ○: 30% or more and less than 50% swelling rate △: 50% or more and less than 70% swelling rate ×: 70% or more swelling rate

(II-4) Compression Set According to JIS K6262, the compression set was measured at 25% compression at 70° C. for 22 hours.
A compression set of 80% or less was judged to be good for practical use.

[Method for producing hydrogenated block copolymer]
<Preparation of hydrogenation catalyst>
The hydrogenation catalyst used for the hydrogenation reaction 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, followed by reaction at room temperature for about 3 days.

<Example 1>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added.
Next, 0.085 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium were added and polymerized at 70°C for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 29 parts by mass of butadiene and 50 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 63.3% by mass and a vinyl bond content of 19% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain a hydrogenated copolymer 1 (polymer 1).
The hydrogenation rate of the obtained hydrogenated copolymer 1 (polymer 1) was 99%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 91°C and 23°C. Table 1 shows the physical properties and characteristics of the polymer.

<Example 2>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 28 parts by mass of butadiene and 46 parts by mass of styrene (concentration of 20% by mass) was added. Although the temperature was not adjusted at this time, the internal temperature of the reactor reached 82°C at the end of the reaction.
Next, a cyclohexane solution containing 3 parts by mass of butadiene was added and polymerized at 80° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane per 1 mol of n-butyllithium was added and reacted at 80° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 63.0% by mass and a vinyl bond content of 20% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain a hydrogenated copolymer 2 (polymer 2).
The hydrogenation rate of the obtained hydrogenated copolymer 2 (polymer 2) was 97%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 104°C and 22°C.

<Example 3>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 27 parts by mass of butadiene and 47 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 63.4% by mass and a vinyl bond content of 20% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain hydrogenated copolymer 3 (polymer 3).
The hydrogenation rate of the obtained hydrogenated copolymer 3 (polymer 3) was 99%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 104°C and 23°C.

<Example 4>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 29 parts by mass of butadiene and 43 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 4 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 63.5% by mass and a vinyl bond content of 23% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 4 (polymer 4) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the obtained hydrogenated copolymer 4 (polymer 4) was 97%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 107°C and 23°C.

<Example 5>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 39 parts by mass of butadiene and 35 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 47.3% by mass and a vinyl bond content of 23% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 5 (polymer 5) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the resulting hydrogenated copolymer 5 (polymer 5) was 98%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 103°C and -8°C.

<Example 6>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 22 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 27 parts by mass of butadiene and 45 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 62.5% by mass and a vinyl bond content of 20% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain a hydrogenated copolymer 6 (polymer 6).
The hydrogenation rate of the resulting hydrogenated copolymer 6 (Polymer-6) was 92%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 105°C and 21°C.

<Example 7>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 30 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.04 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 10 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, a cyclohexane solution containing 27 parts by mass of butadiene and 40 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 59.7% by weight and a vinyl bond content of 22% by weight in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain a hydrogenated copolymer 7 (polymer 7).
The hydrogenation rate of the obtained hydrogenated copolymer 7 (polymer 7) was 98%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 108°C and 16°C.

< Reference example 8>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 22 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.05 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and N, N
, N′,N′-tetramethylethylenediamine (hereinafter referred to as “TMEDA”) was added in an amount of 0.8 mol per 1 mol of n-butyllithium, and polymerized at 70° C. for 10 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added to 70% by mass.
°C for 5 minutes.
Finally, a cyclohexane solution containing 29 parts by mass of butadiene and 46 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 61.3% by mass and a vinyl bond content of 21% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain hydrogenated copolymer 8 (polymer 8).
The hydrogenation rate of the obtained hydrogenated copolymer 8 (polymer 8) was 99%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 97°C and 19°C.

<Example 9>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium were added and polymerized at 70°C for 10 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 29 parts by mass of butadiene and 46 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes. The block copolymer obtained as described above was a polymer having a styrene content of 63.4% by mass and a vinyl bond content of 22% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 9 (polymer 9) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the resulting hydrogenated copolymer 9 (polymer 9) was 84%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at 102°C and 23°C.

<Example 10>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 26 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 10 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 2 parts by mass of butadiene was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 47 parts by mass of butadiene and 25 parts by mass of styrene (concentration of 20% by mass) was added. Although the temperature was not adjusted at this time, the internal temperature of the reactor reached 89°C at the end of the reaction.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium and reacted at 70° C. for 30 minutes. The block copolymer obtained as described above was a polymer having a styrene content of 34.7% by mass and a vinyl bond content of 31% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 10 (polymer 10) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the resulting hydrogenated copolymer 10 (polymer 10) was 99%. Further, when the viscoelastic spectrum of the hydrogenated copolymer 10 was measured, tan δ peak temperatures existed at 105°C and -29°C.

< Reference Example 11>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 21 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 10 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 6 parts by mass of butadiene was added to 70% by mass.
°C for 15 minutes.
Next, a cyclohexane solution containing 23 parts by mass of butadiene and 44 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 6 parts by mass of butadiene was added to 70% by mass.
°C for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium, and reacted at 70° C. for 30 minutes. The block copolymer obtained as described above was a polymer having a styrene content of 65.7% by mass and a vinyl bond content of 25% by mass in the random block (c).
Further, a hydrogenation catalyst was added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain hydrogenated copolymer 11 (polymer 11).
The hydrogenation rate of the obtained hydrogenated copolymer 11 (polymer 11) was 99%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, the tan δ peak temperatures were 104 ° C. and 27 ° C.
existed in

<Comparative Example 1>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added and the temperature was adjusted to 60°C.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution containing 33 parts by mass of butadiene and 52 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Finally, 0.3 mol of dimethoxydimethylsilane per 1 mol of n-butyllithium was added and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 61.2% by mass and a vinyl bond content of 22% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 12 (polymer 12) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the obtained hydrogenated copolymer 12 (polymer 12) was 97%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, the tan δ peak temperature existed only at 19°C.

<Comparative Example 2>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 34 parts by mass of styrene was added and the temperature was adjusted to 60°C.
Next, 0.16 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium were added and polymerized at 70°C for 25 minutes.
Next, a cyclohexane solution containing 32 parts by mass of butadiene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 45 minutes.
Finally, a cyclohexane solution (concentration: 20% by mass) containing 34 parts by mass of styrene was added and polymerized at 70° C. for 25 minutes.
The block copolymer obtained as described above had no styrene in the random block (c) and had a vinyl bond content of 36% by mass.
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 13 (polymer 13) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the resulting hydrogenated copolymer 13 (polymer 13) was 98%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed at -44°C and 108°C.

< Reference Example 12>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 21 parts by mass of styrene was added and the temperature was adjusted to 60°C.
Next, 0.04 parts by mass of n-butyl lithium with respect to 100 parts by mass of all monomers and N, N
, N′,N′-tetramethylethylenediamine (hereinafter referred to as “TMEDA”) was added in an amount of 0.8 mol per 1 mol of n-butyllithium, and polymerized at 70° C. for 15 minutes.
Next, a cyclohexane solution containing 22 parts by mass of butadiene and 33 parts by mass of styrene (concentration of 20% by mass) was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 50 minutes.
Finally, a cyclohexane solution (concentration: 20% by mass) containing 21 parts by mass of styrene was added and polymerized at 70° C. for 15 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 40% by mass and a vinyl bond content of 29% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 14 (polymer 14) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the resulting hydrogenated copolymer 14 (polymer 14) was 99%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, the tan δ peak temperature was -22 ° C. and 109
°C.

<Comparative Example 4>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of styrene was added and the temperature was adjusted to 60°C.
Next, 0.16 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium were added and polymerized at 70°C for 5 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene (concentration of 20% by mass) was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration of 20% by mass) containing 26 parts by mass of butadiene and 65 parts by mass of styrene was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 35 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene (concentration of 20% by mass) was added and polymerized at 70° C. for 5 minutes.
Finally, 0.3 mol of dimethoxydimethylsilane per 1 mol of n-butyllithium was added and reacted at 70° C. for 30 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 72% by mass and a vinyl bond content of 17% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain hydrogenated copolymer 15 (polymer 15).
The hydrogenation rate of the resulting hydrogenated copolymer 15 (polymer 15) was 97%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, the tan δ peak temperature existed only at 38°C.

<Comparative Example 5>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.16 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium were added and polymerized at 70°C for 10 minutes.
Next, a cyclohexane solution containing 2 parts by mass of butadiene (concentration of 20% by mass) was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration of 20% by mass) containing 29 parts by mass of butadiene and 47 parts by mass of styrene was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 25 minutes.
Next, a cyclohexane solution containing 2 parts by mass of butadiene (concentration of 20% by mass) was added and polymerized at 70° C. for 5 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added and polymerized at 70° C. for 10 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 62% by mass and a vinyl bond content of 24% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 16 (polymer 16) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the obtained hydrogenated copolymer 16 (polymer 16) was 81%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed only at 20°C and 74°C.

<Comparative Example 6>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 8.5 parts by mass of styrene was added and the temperature was adjusted to 60°C.
Next, 0.16 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and N,
N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") is n-
0.8 mol was added to 1 mol of butyllithium, and polymerized at 70° C. for 10 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 12 parts by mass of butadiene and 62 parts by mass of styrene was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 60 minutes.
Finally, a cyclohexane solution (concentration: 20% by mass) containing 8.5 parts by mass of styrene was added and polymerized at 70° C. for 10 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 84% by mass and a vinyl bond content of 14% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the block copolymer to obtain hydrogenated copolymer 17 (polymer 17).
The hydrogenation rate of the resulting hydrogenated copolymer 17 (polymer 17) was 97%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, tan δ peak temperatures existed only at 62°C and 96°C.

<Comparative Example 7>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was added, and the temperature was adjusted to 60°C.
Next, 0.16 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.8 mol of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") per 1 mol of n-butyllithium were added and polymerized at 70°C for 10 minutes.
Next, a cyclohexane solution (concentration of 20% by mass) containing 58 parts by mass of butadiene and 24 parts by mass of styrene was supplied so as to keep the reaction temperature constant, and polymerization was carried out at 70° C. for 60 minutes.
Finally, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was added and polymerized at 70° C. for 10 minutes.
The block copolymer obtained as described above was a polymer having a styrene content of 62% by mass and a vinyl bond content of 14% by mass in the random block (c).
Furthermore, 100 ppm of a hydrogenation catalyst based on Ti per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Hydrogenated copolymer 18 (polymer 18) was obtained by adding 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to 100 parts by mass of the block copolymer.
The hydrogenation rate of the obtained hydrogenated copolymer 18 (polymer 18) was 97%. Further, when the viscoelastic spectrum of the hydrogenated copolymer was measured, the tan δ peak temperature existed only at -42°C.

[Method for producing hydrogenated copolymer composition]
A hydrogenated block copolymer composition was produced using the hydrogenated copolymer produced as described above and the materials of Components 1 to 3 below.
<Component 1>
PM801A (PP/manufactured by Sun Allomer; MFR=15) was used as the olefin resin. It is written as "PP" in the following table.
<Component 2>
As a thermoplastic resin other than the hydrogenated copolymer related to the present invention, a styrene-based thermoplastic elastomer, N504 (manufactured by Nippon Elastomer Co., Ltd.) was used. It is written as "SEBS" in the following table.
<Component 3>
Paraffin oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) was used as a softening agent. It is described as "Oil" in the following table.

(Examples 13-16, Reference Example 17, Examples 18-19, Reference Example 20, Examples 21-24, Reference Example 25), (Comparative Examples 8-13, 15)
Hydrogenated copolymers 1, 2, 3, 4, 6, 7, 8, 9, 10, 11 produced as described above
, 12, 13, 14, 15, 17, and 18, and the components 1 to 3, as shown in Table 3 below.
, were blended in the ratio shown in Table 4, kneaded with a twin-screw extruder (TEX-30, manufactured by Japan Steel Works, Ltd.), and pelletized to obtain a hydrogenated 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 obtained hydrogenated copolymer composition.
The physical properties of the test piece were measured, and the results are shown in Tables 3 and 4 below.

The hydrogenated copolymer and hydrogenated copolymer composition of the present invention have industrial applicability in the fields of reinforcing filler formulations, crosslinked products, foams, molded articles such as multilayer films and multilayer sheets, building materials, vibration damping/soundproofing materials, wire coating materials, high frequency fusible compositions, slush molding materials, adhesive compositions, asphalt compositions, automobile interior materials, automobile exterior materials, medical device materials, various containers such as food packaging containers, household appliances, industrial parts, and toys.

Claims (8)

A hydrogenated copolymer comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit,
at least one polymer block (a) consisting of vinyl aromatic monomer units;
at least one polymer block (b) consisting of conjugated diene monomer units;
a random copolymer block (c) consisting of conjugated diene monomer units and vinyl aromatic monomer units;
have
The content of the vinyl aromatic monomer unit is 50% by mass to 80% by mass,
In the dynamic viscoelastic spectrum, it has tan δ peak temperatures at −30 to 50 ° C. and 80 ° C. or higher,
Measurement by gel permeation chromatography using standard polystyrene as calibration curve
has one or more peaks in the molecular weight range of 250,000 or more,
The polymer block (b) composed of the conjugated diene monomer unit is the vinyl aromatic monomer
A polymer block (a) consisting of units, the conjugated diene monomer unit and the vinyl aromatic monomer
present between the random copolymer block (c) consisting of a unit and
The content of the polymer block (b) composed of the conjugated diene monomer unit is 1 to 8% by mass.
Hydrogenated copolymer. The content of the polymer block (a) composed of the vinyl aromatic monomer unit is 5% by mass to 4%
The hydrogenated copolymer according to claim 1, which is 0% by mass. 3. The hydrogenated copolymer according to claim 1, wherein the content of vinyl aromatic monomer units in the random copolymer block (c) is 35% by mass to 80% by mass. 4. The hydrogenated copolymer according to any one of claims 1 to 3, wherein the hydrogenation rate of conjugated diene monomer units is 85% or more. 1 to 99 parts by mass of the hydrogenated copolymer according to any one of claims 1 to 4 ,
99 to 1 part by mass of a thermoplastic resin other than the hydrogenated copolymer and/or a rubber-like polymer other than the hydrogenated copolymer;
A hydrogenated copolymer composition containing. A foam containing the hydrogenated copolymer composition according to claim 5 . A molded article of the hydrogenated copolymer composition according to claim 5 . The molded body is
The molded article according to claim 7 , which is selected from the group consisting of an extruded article, an injection molded article, a hollow molded article, a pressure molded article, a vacuum molded article, a foam molded article, a multilayer extruded article, a multilayer injection molded article, a high frequency fusion molded article, and a slush molded article.