JP7073857B2 - Resin composition and molded product - Google Patents

Description

The present invention relates to a resin composition containing at least a hydrogenated block copolymer of a block copolymer having a structural unit derived from farnesene and a cross-linking agent, and a molded product of the resin composition.

Rubber compositions in which thermoplastic elastomers such as styrene-based elastomers and olefin-based elastomers are mixed with various rubbers have excellent mechanical properties and flexibility, so that they are used for shoe soles for footwear, various tires, building materials such as packing, mechanical parts, etc. It is used in a wide range of fields. However, the rubber composition containing the thermoplastic elastomer becomes slippery due to the adhesion of moisture, which poses a problem especially in applications such as soles for footwear and various tires.

Therefore, studies have been conducted to improve the wet grip performance of a rubber composition containing a thermoplastic elastomer and a rubber component.
For example, resin compositions have been proposed in which the number average molecular weight of the thermoplastic elastomer and the glass transition temperature of the rubber component are specified, or a tackifier resin or a hydrogenated block copolymer is contained (for example, Patent Documents 1 to 1). 8).

U.S. Patent Application Publication No. 2013/0086822 International Publication No. 2006/121069 Japanese Unexamined Patent Publication No. 2017-39819 Japanese Unexamined Patent Publication No. 2016-210937 Japanese Unexamined Patent Publication No. 2014-189697 Japanese Unexamined Patent Publication No. 2014-5200017 Japanese Unexamined Patent Publication No. 2004-75882 Japanese Patent Application Laid-Open No. 2003-292672

However, the techniques disclosed in Patent Documents 1 to 8 cannot produce a resin composition having an excellent balance of flexibility, tear strength, tensile properties, dry grip performance and wet grip performance, and also the vulcanization rate. Since it is not sufficient, further improvement is required for these. Further, Patent Documents 1 to 8 describe block copolymers containing a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from farnesene, and hydrogenated products thereof. There is no.

Therefore, the present invention provides a resin composition having an excellent vulcanization rate (Tc90) and an excellent balance of flexibility, tear strength, tensile properties, dry grip performance and wet grip performance, and a molded product of the resin composition. Is the subject.

As a result of diligent studies to solve the above problems, the present inventors have found that a resin composition containing a specific hydrogenated block copolymer and a cross-linking agent can solve the problems.
That is, the present invention is as follows.

[1] Containing a hydrogenated block copolymer (I) and a cross-linking agent (II),
A resin composition which does not contain a polyolefin resin or has a polyolefin resin content of less than 10 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I).
The hydrogenated block copolymer (I) contains a polymer block (A) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing a structural unit (b1) derived from farnesene. The resin composition is a hydrogenated block copolymer (P) containing 50 mol% or more of carbon-carbon double bonds in the structural unit derived from the conjugated diene in the block copolymer (P). ..
[2] A molded product of the resin composition according to the above [1].
[3] A sole using the resin composition according to the above [1] at least in part.

According to the present invention, there is provided a resin composition having an excellent vulcanization rate (Tc90) and an excellent balance of flexibility, tear strength, tensile properties, dry grip performance and wet grip performance, and a molded product of the resin composition. be able to.

<Resin composition>
The resin composition of the present invention is
Contains hydrogenated block copolymer (I) and cross-linking agent (II),
A resin composition that does not contain a polyolefin resin or has a polyolefin resin content of less than 10 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I).
The hydrogenated block copolymer (I) includes a polymer block (A) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing a structural unit (b1) derived from farnesene. The block copolymer (P) is a hydrogenated product obtained by hydrogenating 50 mol% or more of carbon-carbon double bonds in the structural unit derived from the conjugated diene in the block copolymer (P).

[Hydrogenated block copolymer (I)]
By containing the hydrogenated block copolymer (I), the resin composition of the present invention has good flexibility, and has excellent tensile properties, dry grip performance and wet grip performance (hereinafter, simply referred to as "grip performance"). May be abbreviated.) Can be expressed.
(Polymer block (A))
The polymer block (A) contains a structural unit derived from an aromatic vinyl compound. Examples of such aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, and 4-. Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Examples thereof include vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene and divinylbenzene. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, styrene, α-methylstyrene and 4-methylstyrene are preferable, and styrene is more preferable.

The polymer block (A) contains a monomer other than the aromatic vinyl compound, for example, a structural unit derived from other monomers such as the monomer constituting the polymer block (B) described later. May be good. However, the content of the structural unit derived from the aromatic vinyl compound in the polymer block (A) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more. Is even more preferable, and 100% by mass is particularly preferable.

The content of the polymer block (A) in the hydrogenated block copolymer (I) is preferably 10 to 45% by mass, more preferably 10 to 40% by mass, and further preferably 10 to 10 to 40% by mass. It is 30% by mass, more preferably 15 to 25% by mass. When the content is 10% by mass or more, the molding processability of the resin composition is good, and the tear strength, tensile properties, and grip performance can be made suitable. Further, when the content is 45% by mass or less, sufficient flexibility can be obtained, and good molding processability, tensile properties, and grip performance can be exhibited.

(Polymer block (B))
The polymer block (B) contains a structural unit (b1) derived from farnesene (hereinafter, also simply referred to as “structural unit (b1)”).
The farnesene may be either α-farnesene or β-farnesene represented by the following formula (1), but β-farnesene is preferable from the viewpoint of ease of production of the block copolymer (P). In addition, α-farnesene and β-farnesene may be used in combination.

The content of the farnesene-derived structural unit (b1) in the polymer block (B) is preferably 1 to 100% by mass. Since the polymer block (B) contains the structural unit (b1) derived from farnesene, the flexibility is improved and the grip performance is excellent. From this point of view, the content of the farnesene-derived structural unit (b1) in the polymer block (B) is the content of the farnesene-derived structural unit (b1) in the polymer block (B). 10 to 100% by mass is more preferable, 20 to 100% by mass is further preferable, 30 to 100% by mass is further preferable, 50 to 100% by mass is particularly preferable, and 100% by mass, that is, the polymer block (B). ) Is most preferably composed of the structural unit (b1).
Further, when farnesene is bio-derived, the amount of conjugated diene other than farnesene such as butadiene and isoprene derived from petroleum can be suppressed, and the dependence on petroleum can be reduced. From this point of view, the content of the farnesene-derived structural unit (b1) in the polymer block (B) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 70 to 100% by mass. It is preferable, and even more preferably 80 to 100% by mass.
When the polymer block (B) contains the structural unit (b2) described later, the content of the farnesene-derived structural unit (b1) in the polymer block (B) is preferably 1% by mass or more, 10 By mass or more is more preferable, 20% by mass or more is further preferable, 30% by mass or more is further preferable, and 50% by mass or more is particularly preferable.

The polymer block (B) may contain a structural unit (b2) derived from a conjugated diene other than farnesene (hereinafter, also simply referred to as “structural unit (b2)”), and the structure in the polymer block (B) may be contained. The content of the unit (b2) is preferably 0 to 99% by mass.
Examples of such conjugated diene include isoprene, butadiene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3. -Octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, milsen, chloroprene and the like can be mentioned. These may be used alone or in combination of two or more. Among these, isoprene, butadiene and myrcene are preferable, and isoprene and butadiene are more preferable.
When the structural unit (b2) is contained in the polymer block (B), the content of the structural unit (b2) is more preferably 90% by mass or less, further preferably 80% by mass or less, and more preferably 70% by mass or less. More preferably, 50% by mass or less is particularly preferable.

The polymer block (B) may contain other structural units other than the structural unit (b1) and the structural unit (b2). The total content of the structural unit (b1) and the structural unit (b2) in the polymer block (B) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 100% by mass.

(Polymer block (C))
The block copolymer (P) is a polymer block (C) containing a structural unit (c2) derived from a conjugated diene other than farnesene in addition to the above-mentioned polymer block (A) and polymer block (B). It is preferable to include.
The polymer block (C) has a content of the structural unit (c1) derived from farnesene of 0% by mass or more and less than 1% by mass, and the content of the structural unit (c2) derived from a conjugated diene other than farnesene is 1 to 1. It is more preferable that the polymer block is 100% by mass.

Farnesene, which constitutes a structural unit (c1) derived from farnesene (hereinafter, also simply referred to as “structural unit (c1)”), and a structural unit (c2) derived from a conjugated diene other than farnesene (hereinafter, simply “structural unit (c2)). As the conjugated diene constituting (also referred to as), examples thereof include farnesene constituting the structural unit (b1) derived from farnesene and the same conjugated diene constituting the structural unit (b2) derived from the conjugated diene other than farnesene. ..
As the conjugated diene constituting the structural unit (c2) derived from the conjugated diene other than farnesene, isoprene, butadiene and myrcene are preferable, and isoprene and butadiene are more preferable.

The content of the farnesene-derived structural unit (c1) in the polymer block (C) is preferably 0% by mass.
The content of the structural unit (c2) derived from the conjugated diene other than farnesene in the polymer block (C) is more preferably 60 to 100% by mass, further preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. It is more preferably 100% by mass, and particularly preferably 100% by mass. By using the polymer block (C) containing the structural unit (c2), the block copolymer (P) will have different conjugated dienes of the above-mentioned structural unit (b1) and structural unit (c2). Even if the hydrogenated block copolymer of the block copolymer is crosslinked with a cross-linking agent (II) described later, it is possible to develop tear strength while maintaining excellent tensile properties, achieving both tensile properties and tear strength. Can be planned.

Further, the polymer block (C) may contain a structural unit (c1) derived from farnesene and a structural unit other than the structural unit (c2) derived from a conjugated diene other than farnesene.
The total content of the structural unit (c1) and the structural unit (c2) in the polymer block (C) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 100% by mass.

(Combination form)
The hydrogenated block copolymer (I) is a hydrogenated additive of the block copolymer (P) containing at least one polymer block (A) and one polymer block (B).
The bonding form of the polymer block (A) and the polymer block (B) is not particularly limited, and may be linear, branched, radial, or a combination of two or more thereof. Among these, a form in which the blocks are linearly connected is preferable.
As the linear bonding form, when the polymer block (A) is represented by A and the polymer block (B) is represented by B, (AB) _l , A- (BA) _m , or B- (AB) The binding form represented by _n can be exemplified. In addition, the above l, m and n each independently represent an integer of 1 or more.
When the block copolymer (P) contains at least one polymer block (A) and one polymer block (B), the polymer block (A), the polymer block (B), and the polymer block (A) It is preferable that it is a binding form having blocks in the order of ABA and is a triblock copolymer represented by ABA.
That is, the hydrogenated block copolymer (I) is preferably a hydrogenated additive of the triblock copolymer represented by ABA.

When the block copolymer (P) contains the polymer block (A), the polymer block (B) and the polymer block (C), the hydrogenated block copolymer (I) is at least one polymer. It is preferably a hydrogenated additive of the block copolymer (P) having the block (B) at the end. The molding processability is improved by having at least one polymer block (B) at the end of the polymer chain. From this point of view, when the hydrogenated block copolymer (I) is linear, it is more preferable to have the polymer blocks (B) at both ends thereof. When the hydrogenated block copolymer (I) is branched or radial, the number of the polymer blocks (B) present at the ends is preferably 2 or more, and more preferably 3 or more.

Further, the block copolymer (P) is a block copolymer containing at least two polymer blocks (A), at least one polymer block (B), and at least one polymer block (C). It contains at least two polymer blocks (A), at least one polymer block (B), and at least one polymer block (C), and at least one polymer. It is more preferable to have the block (B) at the end.

When the block copolymer (P) contains the polymer block (A), the polymer block (B) and the polymer block (C), the bonding form of the plurality of polymer blocks is not particularly limited, and is linear. It may be branched, radial or a combination of two or more thereof. Among these, a form in which the blocks are linearly connected is preferable.
The block copolymer (P) has a structure having blocks in the order of the polymer block (B), the polymer block (A), and the polymer block (C) (that is, the structure of BAC). Is preferable.
Specifically, the block copolymer (P) is a tetrablock copolymer represented by BACA, a pentablock copolymer represented by BACABA, and the like. BA- (CA) _p -B, B-A- (C-AB) _q , B- (ACAB) _r (p, q, r are 2 independently. It is preferably a copolymer represented by (representing the above integer), and more preferably a pentablock copolymer represented by BACAB.
That is, the hydrogenated block copolymer (I) is preferably a hydrogenated additive of the pentablock copolymer represented by BACAB.

Here, in the present specification, when the same type of polymer block is linearly bonded via a divalent coupling agent or the like, the entire bonded polymer block is treated as one polymer block. Is done. According to this, the polymer block which should be strictly described as AXA (X represents a coupling agent residue) is displayed as A as a whole. In the present specification, since this kind of polymer block containing a coupling agent residue is treated as described above, for example, it contains a coupling agent residue and is strictly BACXC-. The block copolymer to be described as AB is described as BACAB and is treated as an example of the pentablock copolymer.

Further, the two or more polymer blocks (A) in the above-mentioned block copolymer (P) may be a polymer block having the same structural unit or a polymer block having different structural units. good. Similarly, when the block copolymer (P) has two or more polymer blocks (B) or two or more polymer blocks (C), each polymer block is composed of the same structural unit. It may be a polymer block or a polymer block composed of different structural units. For example, in the two polymer blocks (A) in the triblock copolymer represented by ABA, the aromatic vinyl compounds may be the same or different in the same kind.

When the block copolymer (P) contains the polymer block (A) and the polymer block (B) and does not contain the polymer block (C), the polymer block (A) and the polymer block (B) The mass ratio [(A) / (B)] is 1/99 to 70/30, preferably 5/95 to 60/40, more preferably 10/90 to 50/50, and 15/85 to 40. / 60 is even more preferred, and 15/85 to 35/65 is even more preferred. Within the range, a resin composition having excellent flexibility and excellent grip performance can be obtained.
When the block copolymer (P) contains the polymer block (A), the polymer block (B) and the polymer block (C), the mass ratio of the polymer block (A) to the polymer block (B). [(A) / (B)] is 1/99 to 70/30, preferably 5/95 to 60/40, more preferably 10/90 to 50/50, and 20/80 to 40/60. More preferably, 25/75 to 35/65 is even more preferable. Within the range, a resin composition having excellent flexibility and excellent grip performance can be obtained.

In the block copolymer (P), the mass ratio of the polymer block (A), the total amount of the polymer block (B) and the polymer block (C) [(A) / ((B) + (C) ))] Is preferably 1/99 to 70/30. Within the above range, a resin composition having excellent tensile properties, molding processability and grip performance can be obtained. From this point of view, the mass ratio [(A) / ((B) + (C))] is more preferably 1/99 to 60/40, further preferably 10/90 to 40/60, and 10/90 to 10/90. 30/70 is even more preferred, and 15/85 to 25/75 is even more preferred.

When the block copolymer (P) contains the polymer block (A), the polymer block (B) and the polymer block (C), the polymer block (B) and the weight in the block copolymer (P). The total content of the structural unit (b1) and the structural unit (c1) with respect to the total amount of the combined block (C) [((b1) + (c1)) / ((B) + (C))] is flexible. From the viewpoint of excellent tensile properties and grip performance, 40 to 90% by mass is preferable, 50 to 80% by mass is more preferable, and 60 to 70% by mass is further preferable.

When the block copolymer (P) contains the polymer block (A) and the polymer block (B) and does not contain the polymer block (C), the polymer block in the block copolymer (P) ( The total content of A) and the polymer block (B) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 100% by mass.
Further, when the block copolymer (P) contains the polymer block (A), the polymer block (B) and the polymer block (C), these polymer blocks (in the block copolymer (P)) The total content of A) to (C) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 100% by mass.

As an example of a more preferable embodiment of the hydrogenated block copolymer (I), from the viewpoints of flexibility, tear strength, tensile properties and grip performance,
A hydrogenated additive of a block copolymer (P) containing a polymer block (A), a polymer block (B) and a polymer block (C).
-The polymer block (C) has a content of the structural unit (c1) derived from farnesene of 0% by mass or more and less than 1% by mass, and the content of the structural unit (c2) derived from a conjugated diene other than farnesene is 1. It is a polymer block having a mass content of ~ 100% by mass.
-The mass ratio [(A) / ((B) + (C))] of the polymer block (A) and the total amount of the polymer block (B) and the polymer block (C) is 10/90 to 30. / 70,
-The block copolymer (P) comprises at least two of the polymer blocks (A), at least one of the polymer blocks (B), and at least one polymer block (C), and at least. It has one polymer block (B) at the end and
-The hydrogenation rate of the carbon-carbon double bond in the constituent unit derived from the conjugated diene in the block copolymer (P) is 50 mol% or more.

(Polymer block composed of other monomers)
The hydrogenated block copolymer (I) is composed of the polymer block (A), the polymer block (B), the polymer block (C), and other monomers as long as the effects of the present invention are not impaired. It may contain a polymer block to be used.

Examples of such other monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene and 1-. Unsaturated hydrocarbon compounds such as tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene; acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate , Acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2 -Functional group-containing unsaturated compounds such as methylpropanesulfonic acid, vinylsulfonic acid, vinyl acetate, and methylvinyl ether; and the like. These may be used alone or in combination of two or more.
When the hydrogenated block copolymer (I) has another polymer block, the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less.

(Method for producing hydrogenated block copolymer (I))
The hydrogenated block copolymer (I) is, for example, a block copolymer (P) containing a polymer block (A) and a polymer block (B), or a polymer when the polymer block (C) is contained. A polymerization step of obtaining a block copolymer (P) containing a block (A), a polymer block (B) and a polymer block (C) by anion polymerization, and a conjugated diene in the block copolymer (P). It can be suitably produced by the step of hydrogenating the carbon-carbon double bond in the derived structural unit.

<Polymerization process>
The block copolymer (P) can be produced by a solution polymerization method or the method described in JP-A-2012-502135 and JP-A-2012-502136. Among these, the solution polymerization method is preferable, and for example, known methods such as an ionic polymerization method such as anionic polymerization and cationic polymerization, and a radical polymerization method can be applied. Among these, the anion polymerization method is preferable. As an anionic polymerization method, a block copolymer (P) is obtained by sequentially adding an aromatic vinyl compound, farnesene and / or a conjugated diene other than farnesene in the presence of a solvent, an anionic polymerization initiator, and if necessary, a Lewis base. ).
Examples of the anion polymerization initiator include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodym; the alkali metals and alkalis. Examples thereof include earth metals and compounds containing lanthanoid-based rare earth metals. Of these, compounds containing alkali metals and alkaline earth metals are preferable, and organic alkali metal compounds are more preferable.

Examples of the organic alkali metal compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stelvenelithium, dilithiomethane, dilithionaphthalene, and 1,4-dilithiobtan. , 1,4-Dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other organic lithium compounds; sodium naphthalene, potassium naphthalene and the like. Of these, organolithium compounds are preferable, n-butyllithium and sec-butyllithium are more preferable, and sec-butyllithium is even more preferable. The organic alkali metal compound may be used as an organic alkali metal amide by reacting with a secondary amine such as diisopropylamine, dibutylamine, dihexylamine, or dibenzylamine.
The amount of the organic alkali metal compound used for the polymerization varies depending on the molecular weight of the block copolymer (P), but is usually 0.01 to 3 with respect to the total amount of the aromatic vinyl compound, farnesene and conjugated diene other than farnesene. It is in the range of% by mass.

The solvent is not particularly limited as long as it does not adversely affect the anion polymerization reaction. For example, saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, and methylcyclopentane. Saturated alicyclic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene and the like. These may be used alone or in combination of two or more. There is no particular limitation on the amount of solvent used.

Lewis bases play a role in controlling the microstructure in structural units derived from farnesene and structural units derived from conjugated diene other than farnesene. Examples of such Lewis bases include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol diethyl ether; pyridine; tertiary amines such as N, N, N', N'-tetramethylethylenediamine, and trimethylamine; potassium. Alkali metal alkoxides such as t-butoxide; phosphine compounds and the like can be mentioned. When a Lewis base is used, the amount is usually preferably in the range of 0.01 to 1000 mol equivalents per 1 mol of anionic polymerization initiator.

The temperature of the polymerization reaction is usually in the range of about −80 to 150 ° C., preferably 0 to 100 ° C., and more preferably 10 to 90 ° C. The type of the polymerization reaction may be a batch type or a continuous type. Whether each monomer is continuously or intermittently supplied into the polymerization reaction solution so that the abundance of the aromatic vinyl compound, farnesene and / or conjugated diene other than farnesene in the polymerization reaction system is within a specific range. Alternatively, the block copolymer (P) can be produced by sequentially polymerizing each monomer in the polymerization reaction solution so as to have a specific ratio.
The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator. The obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate the block copolymer (P), or the polymerization reaction solution is washed with water, separated, and then dried to obtain the block copolymer (P). Can be isolated.

As described above, the hydrogenated block copolymer (I) preferably contains a structure having a polymer block (B), a polymer block (A), and a polymer block (C) in this order. Therefore, the step of obtaining the block copolymer (P) by producing the polymer block (B), the polymer block (A), and the polymer block (C) in this order, and the obtained block copolymer ( It is more preferable to produce by a method including a step of hydrogenating P).
When the hydrogenated block copolymer (I) has the polymer block (B) only at one end of the polymer chain, each of the other polymer blocks is polymerized so as to bond linearly. Later, it may be obtained by a method for finally producing the polymer block (B).

The hydrogenated block copolymer (I) comprises at least two polymer blocks (A), at least one polymer block (B), and at least one polymer block (C), and at least one. In the case of a hydrogenated product of the block copolymer (P) having the individual polymer blocks (B) at the ends, the method for producing the block copolymer (P) is as follows.
[I] A method for polymerizing a polymer block (B), a polymer block (A), a polymer block (C), and a polymer block (A) in this order, and [ii] a polymer block (B), weight. Examples thereof include a method of polymerizing the combined block (A) and the polymer block (C) in this order, and coupling the ends of the polymer block (C) with each other using a coupling agent.
In the present invention, the latter method [ii] using a coupling agent is preferable from the viewpoint of efficient production.

Examples of the coupling agent include divinylbenzene; polyvalent epoxy compounds such as epoxidized 1,2-polybutadiene, epoxidized soybean oil, and tetraglycidyl-1,3-bisaminomethylcyclohexane; tin tetrachloride, tetrachlorosilane, and the like. Halogens such as trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, dibromodimethylsilane; methyl benzoate, ethyl benzoate, phenyl benzoate, diethyl oxalate, diethyl malonate, diethyl adipate, dimethyl phthalate, dimethyl terephthalate. Ester compounds such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like; diethoxydimethylsilane, trimethoxymethylsilane, triethoxymethylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrakis (2- Alkoxysilane compounds such as ethylhexyloxy) silane, bis (triethoxysilyl) ethane, and 3-aminopropyltriethoxysilane; 2,4-tolylene diisocyanate and the like can be mentioned.

In this polymerization step, an unmodified block copolymer may be obtained as described above, but a blocked block copolymer modified as described below may be obtained.
In the case of a modified block copolymer, the block copolymer may be modified before the hydrogenation step described later. Examples of the functional group that can be introduced include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl group, a mercapto group, an isocyanate group, an acid anhydride group and the like.
As a method for modifying the block copolymer, for example, tin tetrachloride, tetrachlorosilane, dichlorodimethylsilane, dimethyldiethoxysilane, tetramethoxysilane, and tetraethoxy that can react with the polymerization active terminal before the addition of the polymerization terminator is used. Coupling agents such as silane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylenediisocyanate, 4,4'-bis (diethylamino) benzophenone, N-vinyl. Examples thereof include a method of adding a polymerization terminal modifier such as pyrrolidone or another modifier described in JP-A-2011-132298. Further, maleic anhydride or the like can be grafted onto the isolated copolymer and used.
The position where the functional group is introduced may be the polymerization terminal of the block copolymer or the side chain. Further, the functional group may be used alone or in combination of two or more. The modifier is preferably in the range of 0.01 to 10 molar equivalents with respect to 1 mol of the anionic polymerization initiator.

<Hydrogenation process>
The hydrogenated block copolymer (I) can be obtained by subjecting the block copolymer (P) obtained by the above method or the modified block copolymer to the step of hydrogenating.
A known method can be used as the method of hydrogenating. For example, in a solution in which the block copolymer (P) is dissolved in a solvent that does not affect the hydrogenation reaction, a Cheegler-based catalyst; nickel, platinum, palladium, ruthenium or nickel, platinum, palladium, ruthenium or the like supported on carbon, silica, silica soil, etc. A rhodium metal catalyst; an organic metal complex having cobalt, nickel, palladium, rhodium or ruthenium metal is present as a hydrogenation catalyst to carry out a hydrogenation reaction.
In the hydrogenation step, a hydrogenation catalyst may be added to a polymerization reaction solution containing the block copolymer (P) obtained by the above-mentioned method for producing a block copolymer (P) to carry out a hydrogenation reaction. .. In the present invention, the hydrogenation catalyst is preferably palladium carbon in which palladium is supported on carbon.
In the hydrogenation reaction, the hydrogen pressure is preferably 0.1 to 20 MPa, the reaction temperature is preferably 100 to 200 ° C., and the reaction time is preferably 1 to 20 hours.

The hydrogenated block copolymer (I) is a hydrogenated product obtained by hydrogenating 50 mol% or more of carbon-carbon double bonds in the structural unit derived from the conjugated diene in the block copolymer (P). The hydrogenation rate is preferably 50 to 98 mol%, more preferably 70 to 97 mol%, further preferably 80 to 96 mol%, from the viewpoint of heat resistance, weather resistance, and exhibiting excellent tear strength by crosslinking. Preferably, 85-96 mol% is even more preferable, and 90-96 mol% is particularly preferable.
The hydrogenation rate is the hydrogenation rate of carbon-carbon double bonds in all the conjugated diene-derived structural units present in the block copolymer (P).

As the carbon-carbon double bond in the structural unit derived from the conjugated diene present in the block copolymer (P), for example, the carbon-carbon double bond in the structural unit derived from the conjugated diene in the polymer block (B). And when the block copolymer (P) further contains the polymer block (C), carbon in the polymer block (B) and in the structural unit derived from the conjugated diene in the polymer block (C). -Carbon double bond can be mentioned.
When the block copolymer (P) contains the polymer block (B) and the polymer block (C), carbon in the structural unit derived from the conjugated diene of the polymer block (B) and the polymer block (C)-. It is preferable that the hydrogenation rate of the carbon double bond is different. Due to the difference in the hydrogenation rate, the degree of cross-linking by the cross-linking agent (II) described later differs for each of the polymerization blocks (B) and (C), whereby the hydrogenated block copolymer (I) is hard and soft. It is considered that different portions of the above can be present to exhibit excellent effects such as tear strength and tensile properties. Further, from the viewpoint of exhibiting remarkably excellent tensile properties, it is more preferable that the hydrogenation rate of the polymer block (C) is higher than that of the polymer block (B).

The hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene of the polymer block (B) in the hydrogenated block copolymer (I) is preferably 50 to 98 mol%, more preferably. It is 50 to 95 mol%, more preferably 60 to 95 mol%, even more preferably 70 to 95 mol%, and particularly preferably 80 to 95 mol%.
When the block copolymer (P) contains the polymer block (C), the carbon-carbon double bond in the structural unit derived from the conjugated diene of the polymer block (C) in the hydrogenated block copolymer (I). The hydrogenation rate of the above is preferably 95 to 99.9 mol%, more preferably 96 to 99.5 mol%, and further preferably 97 to 99.5 mol%.
The hydrogenation rate can be calculated by measuring ¹ H-NMR of the block copolymer (P) and the hydrogenated block copolymer (I) after hydrogenation.

The peak top molecular weight (Mp) of the hydrogenated block copolymer (I) is preferably 4,000 to 1,500,000, more preferably 9,000 to 1,000,000, and 30 000 to 800,000 is even more preferable, and 50,000 to 500,000 is even more preferable.
The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (I) is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and even more preferably 1 to 2. When the molecular weight distribution is within the above range, the variation in the viscosity of the hydrogenated block copolymer (I) is small and the handling is easy.
The peak top molecular weight (Mp) and the molecular weight distribution (Mw / Mn) in the present specification mean the values measured by the method described in Examples described later.

The peak top molecular weight of the polymer block (A) is preferably 2,000 to 100,000, more preferably 4,000 to 80,000, still more preferably 5,000 to 50,000, from the viewpoint of molding processability. , 6,000 to 30,000 are even more preferred.

The peak top molecular weight of the polymer block (B) is preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 4,000 to 100,000 from the viewpoint of molding processability. ..

Further, the peak top molecular weight of the polymer block (C) is preferably 4,000 to 200,000, more preferably 4,500 to 150,000, and 5,000 to 100,000 from the viewpoint of molding processability. More preferred.

[Crosslinking agent (II)]
The resin composition of the present invention contains a cross-linking agent (II). The cross-linking agent (II) is preferably one that undergoes a cross-linking reaction only with a carbon-carbon double bond or α-methylene thereof in a structural unit derived from a conjugated diene. Here, α-methylene indicates methylene adjacent to a carbon-carbon double bond. By containing such a cross-linking agent (II), only the carbon-carbon double bond or the carbon-carbon double bond α-methylene remaining in the hydrogenated block copolymer (I) is cross-linked. It is possible to have excellent tear strength while maintaining excellent flexibility, tensile properties and grip properties.

Examples of the cross-linking agent (II) include a radical generator, sulfur and a sulfur-containing compound, and more preferably sulfur or a sulfur-containing compound, and further preferably sulfur, from the viewpoint of tear strength and tensile properties. be.
Examples of the radical generator include dicumyl peroxide, dit-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t). -Butylperoxy) Hexin-3,1,3-bis (t-butylperoxyisopropyl) benzene, α, α'-bis (t-butylperoxy) diisopropylbenzene, 3,3,5-trimethylcyclohexane, n-butyl- 4,4-Bis (t-butylperoxy) peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetylperoxide, lauroyl peroxide, t -Organic peroxides such as butylcumyl peroxides may be mentioned, which may be used alone or in combination of two or more.

The sulfur can be used without particular limitation, and may be, for example, fine powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, or the like.
Examples of the sulfur-containing compound include sulfur monochloride, sulfur dichloride, disulfide compounds, triazinethiols and the like.
Other examples of the cross-linking agent (II) include phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations of p-quinonedioxime and lead dioxide, p, p'-dibenzoylquinonedioxime and trilead tetroxide, etc. Can also be used.

[Rubber (III)]
The resin composition of the present invention may further contain rubber (III).
As the rubber (III), natural rubber (NR), various synthetic rubbers and the like, which have been conventionally used as a rubber raw material for rubber soles such as shoe soles, are used without particular limitation.
The rubber (III) does not contain the above-mentioned hydrogenated block copolymer (I).

Specific examples of synthetic rubber include styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), acrylic nitrile butadiene copolymer rubber (NBR), and ethylene-propylene-diene rubber (EPDM). , Butyl rubber (isobutylene-isoprene rubber (IIR)) and modified halogenated butyl rubber thereof (for example, Br-IIR and Cl-IIR) and the like. These may be used alone or in combination of two or more. Among these, styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), butyl rubber (IIR) and halogenated butyl rubber modified thereof are preferable.

As the styrene-butadiene copolymer rubber, for example, emulsified polymerized styrene-butadiene rubber (E-SBR), solution-polymerized styrene-butadiene rubber (S-SBR), modified styrene-butadiene rubber (modified SBR) and the like can be used. It is preferably E-SBR.
Further, a commercially available styrene-butadiene copolymer rubber can be used, and a rubber having a styrene content of 0.1 to 70% by mass is preferable, a rubber having a styrene content of 5 to 50% by mass is more preferable, and a rubber having a styrene content of 15 to 35% by mass is further preferable. It is preferable that the content is 15 to 25% by mass, more preferably 15 to 25% by mass.
Styrene-butadiene copolymer rubber has a good balance of physical properties such as elasticity and strength, is also good for kneading and molding, and is suitable from the viewpoint of easy availability.

As the polyisoprene rubber, a commercially available polyisoprene rubber can be used, but an ultra-high cis isomer obtained by using a polyisoprene rubber polymerized by a Cheegler-based catalyst having a high cis-form content or a lanthanoid-based rare earth metal catalyst. It is preferably a polyisoprene rubber having a content.
The weight average molecular weight (Mw) of the polyisoprene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When Mw is in the above range, moldability, tear strength, and tensile properties are good. The vinyl content of the polyisoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
Polyisoprene rubber has a good balance of physical properties such as mechanical strength and is suitable from the viewpoint of easy availability.

As the polybutadiene rubber, a commercially available polybutadiene rubber can be used, but a polybutadiene rubber polymerized by a Cheegler-based catalyst having a high cis-form content or a polybutadiene having an ultra-high cis-form content obtained by using a lanthanoid-based rare earth metal catalyst. It is preferably rubber.
The weight average molecular weight (Mw) of the polybutadiene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000, further preferably 250,000 to 1,000,000, and 350,000 to 70. It is even more preferable that it is 10,000. When Mw is in the above range, moldability, tear strength, and tensile properties are good. The vinyl content of the polybutadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
Polybutadiene rubber is particularly suitable from the viewpoint that it can be expected to impart excellent wear resistance to the molded product of the resin composition.

[Content]
The contents of the hydrogenated block copolymer (I), the cross-linking agent (II) and the rubber (III) are preferably satisfied with the following requirements.
The mass ratio of the content ratio [(I) / (III)] of the hydrogenated block copolymer (I) and the rubber (III) is a balance between flexibility, tear strength, tensile properties, dry grip performance and wet grip performance. From the viewpoint of expressing the above, it is preferably 1/99 to 100/0, more preferably 10/90 to 100/0, still more preferably 15/85 to 100/0, and even more preferably 20 /. It is 80 to 100/0.
On the other hand, from the viewpoint of wet grip performance and tensile properties, the higher the content ratio of the hydrogenated block copolymer (I) to the rubber (III), the more the physical properties tend to improve, and from the above viewpoint, [(I) / ( The mass ratio of III)] is preferably 40/60 to 100/0, more preferably 55/45 to 100/0, still more preferably 70/30 to 100/0, and even more preferably. It is 90/10 to 100/0.
Further, from the viewpoint of raw material cost, it may be advantageous to increase the content ratio of the rubber (III) to the hydrogenated block copolymer (I), and from the above viewpoint, the hydrogenated block is within the range that does not impair the effect of the present invention. The content ratio of the copolymer (I) and the rubber (III) may be freely set. As described above, when the hydrogenated block copolymer (I) and the rubber (III) are used in combination in the resin composition of the present invention, the content ratio of both may be set as a reason, but the effect of the present invention is good. From the viewpoint of easy exertion, the mass ratio of [(I) / (III)] is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and further preferably 40 /. It is 60 to 60/40.

When the resin composition of the present invention does not contain rubber (III), the content of the cross-linking agent (II) is flexibility, tear strength, with respect to 100 parts by mass of the content of the hydrogenated block copolymer (I). From the viewpoint of exhibiting a balance between tensile properties, dry grip performance and wet grip performance, it is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6.0 parts by mass, and further preferably 1.0 to 1.0 parts by mass. It is 4.0 parts by mass, more preferably 1.5 to 2.5 parts by mass.
When the resin composition of the present invention contains rubber (III), the content of the cross-linking agent (II) is based on 100 parts by mass of the total content of the hydrogenated block copolymer (I) and rubber (III). From the viewpoint of exhibiting a balance between flexibility, tear strength, tensile properties, dry grip performance and wet grip performance, it is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6.0 parts by mass, and further. It is preferably 1.0 to 4.0 parts by mass, and even more preferably 1.5 to 2.5 parts by mass.

[Other optional ingredients]
(Polyolefin resin)
The resin composition of the present invention does not contain a polyolefin-based resin, or the content of the polyolefin-based resin with respect to 100 parts by mass of the hydrogenated block copolymer (I) is less than 10 parts by mass. If the content exceeds 10 parts by mass, melt-kneading may not be possible and the effect of the resin composition of the present invention may be impaired. Therefore, it is preferable that the polyolefin-based resin is not contained.
Examples of the polyolefin-based resin that can be contained include polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, and ethylene-vinyl acetate co-weight. Examples thereof include a coalescence, an ethylene-acrylic acid copolymer and the like.

(Crosslink accelerator)
The resin composition of the present invention may contain a cross-linking accelerator. Examples of the cross-linking accelerator include N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, di-2-benzothiazolyldisulfide, 2- (4-morpholinodithio) benzothiazole and the like. Thiazols; guanidines such as diphenylguanidine and triphenylguanidine; aldehyde-amine-based reactants such as butylaldehyde-aniline reactants, hexamethylenetetramine-acetaldehyde reactants or aldehyde-ammonia-based reactants; 2-mercaptoimidazoline and the like. Imidazolines; thioureas such as thiocarbanilide, diethylurea, dibutylthiourea, trimethylthiourea, diorsotrilthiourea; thiurammono or polysulfides such as tetramethylthium monosulfide, tetramethylthium disulfide, pentamethylene thiuram tetrasulfide; dimethyldithiocarbamine Thiocarbamates such as zinc acid, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, telluryl diethyldithiocarbamate; xanthogenates such as zinc dibutylxanthogenate and the like can be mentioned. These cross-linking accelerators may be used alone or in combination of two or more.
When the resin composition of the present invention does not contain rubber (III), the content of the cross-linking accelerator is 100 parts by mass of the hydrogenated block copolymer (I), and also contains rubber (III). In this case, the amount is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 5 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of the hydrogenated block copolymer (I) and the rubber (III). It is 1.0 to 4.0 parts by mass.

(Inorganic filler)
The resin composition of the present invention may contain an inorganic filler.
Examples of the inorganic filler include talc, calcium carbonate, silica, glass fiber, carbon fiber, carbon black, mica, kaolin, titanium oxide and the like. Among these, talc, calcium carbonate and silica are preferable, and tear strength, tear strength, etc. In particular, silica is more preferable from the viewpoint of improving the static friction property in a wet state.
When the resin composition of the present invention does not contain rubber (III), the content of the inorganic filler is 100 parts by mass of the hydrogenated block copolymer (I), and also contains rubber (III). In this case, the total content of the hydrogenated block copolymer (I) and the rubber (III) is preferably 0 to 120 parts by mass with respect to 100 parts by mass.
If the molded body of the resin composition is, for example, a sole for footwear, the weight of the footwear can be reduced and the flexibility is good without the hardness and the specific gravity becoming too high while imparting excellent tear strength. From the viewpoint of maintaining properties, tensile properties and grip, the upper limit of the content of the inorganic filler is more preferably 100 parts by mass or less, further preferably 80 parts by mass or less, still more preferably 60 parts by mass. It is less than the mass part.
Further, the lower limit of the content is 0, that is, the inorganic filler may not be contained. Even if it does not contain an inorganic filler, it is possible to obtain a resin composition having a good balance between flexibility, tear strength, tensile properties and grip performance. Therefore, the inorganic filler may be appropriately determined in the above-mentioned content range according to the performance required for the use of the resin composition.

(Softener)
The resin composition of the present invention may contain a softening agent as long as the effects of the present invention are not impaired. However, the resin composition of the present invention does not have to contain a softening agent because it has sufficient fluidity for molding due to the above-mentioned constitution. In particular, among the softeners, paraffin-based, naphthen-based and aromatic process oils, mineral oils, white oils and other oil-based softeners may exude oil over time when formed into a molded product. Therefore, it is preferable not to include it in the resin composition.
Examples of the softening agent that can be contained include phthalic acid derivatives such as dioctylphthalate and dibutylphthalate; liquid co-oligomers of ethylene and α-olefin; liquid paraffin; polybutene; low molecular weight polyisobutylene; liquid polybutadiene, liquid polyisobutylene, and the like. Examples thereof include liquid polydiene such as liquid polyisobutylene / butadiene copolymer, liquid styrene / butadiene copolymer, liquid styrene / isoprene copolymer, and hydrogenated products thereof.
When the softening agent is contained, the content is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 0% by mass, that is, not contained in the resin composition of the present invention.

(Other additives)
The resin composition of the present invention contains other additives such as a cross-linking aid, a silane coupling agent, a heat antiaging agent, an antioxidant, a light stabilizer, and an antistatic agent as long as the effects of the present invention are not impaired. Agents, mold release agents, flame retardants, foaming agents, pigments, dyes, whitening agents and the like can be added. These additives may be used alone or in combination of two or more.

[Manufacturing method of resin composition]
The method for producing a resin composition of the present invention is produced by, for example, melt-kneading each component excluding the crosslinking agent (II) and the crosslinking accelerator added as necessary, and then crosslinking by the crosslinking method described later. can do.
There is no particular limitation on the method of melt-kneading each component except the cross-linking agent (II) and the cross-linking accelerator added as necessary, and the hydrogenated block copolymer (I), rubber (III) and other optional components are not particularly limited. Is simultaneously supplied to a kneading device, for example, a uniaxial extruder, a multi-screw extruder, a rubbery mixer, a brabender mixer, a heating roll, various kneaders, or the like, and melt-kneaded. Further, a method in which the hydrogenated block copolymer (I), rubber (III) and other optional components are supplied from separate charging ports and melt-kneaded, or the hydrogenated block copolymer (I) and an inorganic filler ( For example, a method may be used in which some optional components such as silica) are melt-kneaded in advance and then melt-kneaded with the melt-kneaded product and other optional components.
The temperature at the time of melt-kneading can be arbitrarily selected in the range of usually 45 ° C to 270 ° C.

As a crosslinking method, a vulcanization mold is used and the vulcanization temperature is usually about 120 to 200 ° C., preferably 140 to 200 ° C., the vulcanization pressure is usually about 0.5 to 10 MPa, and usually about 1 minute to 2 hours. By maintaining it, a method of cross-linking and the like can be mentioned.

[Physical characteristics]
(Vulcanization rate)
The resin composition of the present invention is crosslinked using a crosslinking agent (II) under the conditions of the examples described later. Above all, when sulfur or a sulfur-containing compound is used as the cross-linking agent, the resin composition of the present invention has an excellent vulcanization rate, that is, the time required for vulcanization (90% vulcanization time) is short.
When the vulcanization rate of the resin composition of the present invention is high, the viscosity of the resin composition increases rapidly at the time of vulcanization, and a vulcanizing agent which is sulfur or a sulfur-containing compound in the resin composition, a crosslinking accelerator, or a crosslinking agent. Plastics such as auxiliaries, antioxidants, antioxidants, and softeners are less likely to bleed to the surface of the vulcanized block copolymer (I) and rubber (III), thus contaminating the processing mold. It can be suppressed.
In the present specification, the vulcanization rate of the resin composition is 90 by measuring the torque of the rubber composition at 160 ° C. using a vibration type vulcanization tester (curast meter) according to JIS K 6300-2: 2001. % The time required to reach the vulcanization amount (90% vulcanization time). The vulcanization rate Tc (90) of the resin composition is preferably 13 minutes or less, more preferably 11 minutes or less, still more preferably 10 minutes or less. The lower limit is not particularly limited, but is usually 1 minute or more.

(specific gravity)
The resin composition of the present invention has a specific gravity measured according to ISO 1183: 1987, preferably 0.88 to 1.30, and more preferably 0.90 to 1.20. Within the above range, the molded product made of the resin composition does not lack practicality.

(hardness)
The resin composition of the present invention has a hardness (hereinafter, also referred to as “A hardness”) according to the type A durometer method of JIS K 6253-: 2012, preferably 90 or less, more preferably 85 or less. Further, the A hardness is preferably 25 or more, more preferably 30 or more, and further preferably 35 or more. When the A hardness is in the above range, the molding processability is good, and the frictional force is high due to the good flexibility, and the grip performance is also excellent.

(Tear strength)
The resin composition of the present invention has a tear strength (tear strength) measured according to JIS K 6252-1: 2015, preferably 2.0 kN / m or more, more preferably 2.5 kN / m or more, and further. It is preferably 3.0 kN / m or more, and even more preferably 3.5 kN / m or more.

(Stiction coefficient)
The resin composition of the present invention has a static friction coefficient measured according to ASTM D-1894 under dry conditions, preferably 1.5 or more, more preferably 1.8 or more. Further, in the case of wet matter, it is preferably 0.8 or more, more preferably 1.0 or more, still more preferably 1.2 or more, still more preferably 1.3 or more.
The dry condition and the wet condition mean the measurement conditions described in Examples described later.

(Tensile breaking strength)
The resin composition of the present invention has a tensile strength at cutting (tensile breaking strength) measured according to JIS K 6251: 2010, preferably 2.0 MPa or more, more preferably 3.0 MPa or more, still more preferable. Is 4.0 MPa or more, particularly preferably 6.5 MPa or more. When the tensile breaking strength is 2.0 MPa or more, the tensile characteristics are good.

(Tension breaking elongation)
In the resin composition of the present invention, the elongation at cutting (tensile fracture elongation) measured according to JIS K 6251: 2010 is preferably 100% or more, more preferably 110% or more, still more preferably 120. % Or more, and even more preferably 130% or more. When the tensile elongation at break is 100% or more, the tensile characteristics are good.

<Molded body>
The molded product of the present invention is made of the resin composition of the present invention.
The shape of the molded body may be any molded body that can be produced using the resin composition of the present invention, and is formed into various shapes such as pellets, films, sheets, plates, pipes, tubes, rods, and granules. can do. The manufacturing method of this molded product is not particularly limited, and can be molded by various conventional molding methods such as injection molding, blow molding, press molding, extrusion molding, and calendar molding. The resin composition of the present invention can particularly preferably obtain a press-molded product.

The molded product obtained by molding the resin composition of the present invention has an excellent balance of tear strength, tensile properties, dry grip performance and wet grip performance, and can be used for molded products requiring these properties. In particular, it can be suitably used as a molded product such as a shoe sole using at least a part of the resin composition of the present invention.
Specifically, shoe soles for footwear such as hiking boots, sandals, safety shoes, mountain climbing shoes, marathon shoes, underground socks and boots; sports equipment such as underwater glasses, snorkels, ski boots and skis / snowboards; pens and scissors, etc. Used for writing tools, drivers, tools such as pliers and wrench, electric tools, water accessories such as toothbrushes and kitchen utensils (kitchens and spatula), golf clubs, ski stock, bicycles, motorcycles and other sports and fitness, etc. Equipment to be used, and various grips such as knives; Home appliance parts such as refrigerators, vacuum cleaners and waterproof bodies (mobile phones, etc.); Side moldings, rack opinion boots, suspension boots, constant velocity joint boots, weather strips, mat guards, etc. Floor mats, armrests, belt line moldings, flash mounts and automobile supplies for interior and exterior of automobiles (gears, knobs, etc.); Office equipment such as copy machine feed rollers and take-up rollers; Parts used for furniture such as sofas and chair seats; Rubber parts such as switch covers, stoppers, casters and foot rubber; can be suitably used for building materials such as coated plywood and coated steel plates.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Β-Farnesene (purity 97.6% by mass, manufactured by Amyris, Incorporated) is purified by a 3Å molecular sieve and distilled in a nitrogen atmosphere to produce gingiberene, bisabolen, farnesene epoxide, farnesol. Hydrocarbon impurities such as isomers, E, E-farnesol, squalene, ergosterol and several dimers of farnesene were removed and used for the following polymerizations.

<Hydrogenated block copolymer (I)>
Hydrogenated block copolymers (I-1) and (I-2) of Production Examples 1 and 2 described later.
<Hydrogenated block copolymer (I')>
Hydrogenated block copolymer (I'-1) of Production Example 3 described later.
<1,4-Polyfarnesen>
1,4-Polyfarnesene (1), (2) of Production Examples 4 and 5 described later.
<Polystyrene-3,4-polyfarnesene-polystyrene>
Polystyrene-3,4-polyfarnesene-polystyrene of Production Example 6 described later

<Crosslinking agent (II)>
-Sulfur (II): Fine sulfur 200 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd. <Rubber (III)>
-Rubber (III-1): Product name JSR 1502, manufactured by JSR Corporation, styrene-butadiene rubber (E-SBR), manufactured by emulsification polymerization method, styrene content = 23.5% by mass
-Rubber (III-2): Product name JSR BR01, manufactured by JSR Corporation, polybutadiene rubber (BR), cis form content = 95% by mass, vinyl content = 2.5% by mass, weight average molecular weight (Mw) = 550,000 <Crosslink accelerator>
-Crosslink accelerator (1): Product name Noxeller DM, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., (di-2-benzothiazolyl disulfide)
-Crosslink accelerator (2): Product name Noxeller TT, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., tetramethylthiuram disulfide)
<Inorganic filler>
・ Silica: Product name ULTRASIL7000GR, made by Evonik Degussa Japan

<Other additives>
・ Stearic acid: Product name Lunac S-20, manufactured by Kao Co., Ltd. ・ Zinc oxide: Zinc oxide type 1, manufactured by Sakai Chemical Industry Co., Ltd. ・ Silane coupling agent: Product name Si69, manufactured by Evonik Degussa Japan ・ Polyethylene glycol: Product name PEG4000, manufactured by Toho Chemical Industry Co., Ltd.

The details of each measuring method for the polymer obtained in the production example are as follows.
(1) Measurement of peak top molecular weight and molecular weight distribution Polymer (hydrogenated block copolymer (I) or (I'), 1,4 polyfarnesene (1) or (2), polystyrene-3,4-polyfarnesene-polystyrene ) And the peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn) of the styrene block are obtained by standard polystyrene equivalent molecular weight by GPC (gel permeation chromatography), and the peak top molecular weight is obtained from the position of the peak of the molecular weight distribution. (Mp) was calculated. The measuring device and conditions are as follows.
・ Equipment: GPC equipment "HLC-8320GPC" manufactured by Tosoh Corporation
-Separation column: Column "TSKgelSuperHZ4000" manufactured by Tosoh Corporation
・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 0.7 mL / min
-Sample concentration: 5 mg / 10 mL
-Column temperature: 40 ° C

(2) Method for measuring the hydrogenation rate (2-1) Block copolymer (P) or (P') and hydrogenated block copolymer (I) or (I') after hydrogenation are used as heavy chloroform solvents, respectively. ¹ H-NMR was measured at 50 ° C. using "Lambda-500" manufactured by JEOL Ltd.
The hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene in the block copolymer (P) or (P') of the hydrogenated block copolymer (I) or (I') is obtained. It was calculated by the following formula from the peak of the proton having a carbon-carbon double bond appearing at 4.5 to 6.0 ppm of the spectrum.
Hydrogenation rate (mol%) = {1- (Mole number of carbon-carbon double bonds contained in 1 mol of hydrogenated block copolymer (I) or (I')) / (block copolymer (P) ) Or (P') Number of moles of carbon-carbon double bond contained per mole)} × 100
(2-2) Further, the hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene in the polymer block (B), and the carbon in the structural unit derived from the conjugated diene in the polymer block (C). -The hydrogenation rate of the carbon double bond was calculated in the same manner as above from the proton peaks appearing in the respective spectra obtained above.

[Manufacturing Example 1]
Hydrogenated block copolymer (I-1):
In a pressure-resistant container substituted with nitrogen and dried, 50.0 kg of cyclohexane as a solvent, 0.1905 kg of sec-butyl lithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator, and 0.40 kg of tetrahydrofuran as a Lewis base were charged. After the temperature is raised to 50 ° C., 6.34 kg of β-farnesene is added and polymerization is carried out for 2 hours, then 2.50 kg of styrene (1) is added and polymerized for 1 hour, and 3.66 kg of butadiene is further added for 1 hour. Polymerization was performed. Subsequently, 0.02 kg of dichlorodimethylsilane as a coupling agent was added to this polymerization reaction solution and reacted for 1 hour to obtain a poly (β-farnesene) -polystyrene-polybutadiene-polystyrene-poly (β-farnesene) pentablock copolymer. A reaction solution containing (P1) was obtained.
Palladium carbon (palladium carrying amount: 5% by mass) was added to this reaction solution as a hydrogen addition catalyst in an amount of 5% by mass based on the block copolymer (P1), and the reaction was carried out at a hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. Was done. After allowing to cool and pressurize, palladium carbon is removed by filtration, the filtrate is concentrated, and then vacuum dried to carry out poly (β-farnesene) -polystyrene-polybutadiene-polystyrene-poly (β-farnesene) pentablock co-weight. A coalesced hydrogen additive (I-1) (hereinafter referred to as "hydrogenated block copolymer (I-1)") was obtained.
The above physical properties of the obtained hydrogenated block copolymer (I-1) were measured. The results are shown in Table 1.

[Manufacturing Example 2]
Hydrogenated block copolymer (I-2):
In a pressure-resistant container that has been replaced with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 0.0413 kg of sec-butyl lithium (10.5 mass% cyclohexane solution) as an anion polymerization initiator are charged, and the temperature is raised to 50 ° C. 1.12 kg of styrene (1) was added and polymerized for 1 hour, then 10.25 kg of β-farnesene was added and polymerized for 2 hours, and 1.12 kg of styrene (2) was further added and polymerized for 1 hour. A reaction solution containing a polystyrene-poly (β-farnesene) -polystyrene triblock copolymer (P2) was obtained.
Palladium carbon (palladium carrying amount: 5% by mass) was added to this reaction solution as a hydrogen addition catalyst in an amount of 5% by mass based on the block copolymer (P2), and the reaction was carried out at a hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. Was done. After allowing to cool and pressurize, palladium carbon is removed by filtration, the filtrate is concentrated, and then vacuum dried to hydrogenate a polystyrene-poly (β-farnesene) -polystyrene triblock copolymer (hereinafter, "". Hydrogenated block copolymer (I-2) ”) was obtained.
The above physical properties of the hydrogenated block copolymer (I-2) were measured. The results are shown in Table 1.

[Manufacturing Example 3]
Hydrogenated block copolymer (I'-1):
62.4 kg of cyclohexane as a solvent and 0.206 kg of sec-butyl lithium (10.5 mass% cyclohexane solution) as an anion polymerization initiator were charged in a pressure-resistant container that had been replaced with nitrogen and dried, and the temperature was raised to 60 ° C. 1.65 kg of styrene (1) was added and polymerized for 1 hour, then 7.71 kg of isoprene was added and polymerized for 2 hours, and 1.65 kg of styrene (2) was further added and polymerized for 1 hour. A reaction solution containing an isoprene-styrene triblock copolymer (P'1) was obtained.
Palladium carbon (palladium carrying amount: 5% by mass) was added to this reaction solution as a hydrogen addition catalyst in an amount of 5% by mass based on the block copolymer (P'1), and the hydrogen pressure was 2 MPa and the temperature was 150 ° C. A time reaction was performed.
After allowing to cool and pressurize, palladium carbon is removed by filtration, the filtrate is concentrated, and then vacuum dried to add hydrogenated styrene-isoprene-styrene block copolymer (hereinafter, "hydrogenated block copolymer"). (I'-1) ") was obtained.
The above physical properties of the hydrogenated block copolymer (I'-1) were measured. The results are shown in Table 1.

[Manufacturing Example 4]
1,4-Polyfarnesen (1):
36.76 kg of cyclohexane as a solvent and 0.198 kg of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator are charged in a pressure-resistant container that has been replaced with nitrogen and dried, and the temperature is raised to 50 ° C. 36.56 kg of β-farnesene was added and polymerization was carried out for 2 hours to obtain a reaction solution containing 1,4-polyfarnesene (1).
A 1% by mass solution of ethanol and t-butylcatechol was added to this reaction solution to precipitate 1,4-polyfarnesene (1), which was filtered and then vacuum dried to obtain 1,4-polyfarnesene (1). ..
The above physical characteristics of 1,4-polyfarnesene (1) were measured. The results are shown in Table 1.

[Manufacturing Example 5]
1,4-Polyfarnesen (2):
1,4-Polyfarnesene (2) was obtained in the same manner as in Production Example 4 except that the blending amounts shown in Table 1 were used.
The above physical characteristics of 1,4-polyfarnesene (2) were measured. The results are shown in Table 1.

[Manufacturing Example 6]
Polystyrene-3,4-polyfarnesene-polystyrene:
62.4 kg of cyclohexane as a solvent and 0.105 kg of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator are charged in a pressure-resistant container that has been replaced with nitrogen and dried, and the temperature is raised to 50 ° C. 5.34 kg of styrene (1) was added and polymerization was carried out for 1 hour, and then 5.67 kg of β-farnesene was added and polymerization was carried out for 2 hours. Subsequently, 0.00018 kg of dichlorosilane as a coupling agent was added to this polymerization reaction solution and reacted for 1 hour to obtain a reaction solution containing polystyrene-3,4-polyfarnesene-polystyrene.
To this reaction solution, a 1% by mass solution of ethanol and t-butylcatechol was added to precipitate polystyrene-3,4-polyfarnesene-polystyrene, filtered, and then vacuum dried to obtain polystyrene-3,4-polyfarnesene-polystyrene. Obtained.
The above physical characteristics of polystyrene-3,4-polyfarnesene-polystyrene were measured. The results are shown in Table 1.

The notations in Table 1 are as follows.
* 1: (A) / (B) indicates the mass ratio between the content of the polymer block (A) and the content of the polymer block (B).
* 2: (A) / ((B) + (C)) is the sum of the content of the polymer block (A) and the contents of each of the polymer block (B) and the polymer block (C). Shows the mass ratio.
* 3: (b1) / (B) indicates the content (mass%) of the structural unit (b1) derived from farnesene in the polymer block (B).
* 4: ((b1) + (c1)) / ((B) + (C)) is a structural unit (b1) and a structural unit (b1) with respect to the total amount of the polymer block (B) and the polymer block (C). The total content (mass%) of c1) is shown.
* 5: F-St-Bd-St-F represents a poly (β-farnesene) -polystyrene-polybutadiene-polystyrene-poly (β-farnesene) pentablock copolymer.
St-F-St represents a polystyrene-poly (β-farnesene) -polystyrene triblock copolymer.
St-Ip-St represents a polystyrene-polyisoprene-polystyrene triblock copolymer.
F represents a poly (β-farnesene) homopolymer.
St-F-St represents a polystyrene-3,4-polyfarnesene-polystyrene copolymer.
* 6: The hydrogenation rate of (I) or (I') indicates the hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene in the block copolymer (P) or (P'). ..
* 7: The hydrogenation rate of the polymer block (B) indicates the hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene in the polymer block (B). However, it is shown only when it has a polymer block (B).
* 8: The hydrogenation rate of the polymer block (C) indicates the hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene in the polymer block (C). However, it is shown only when it has a polymer block (C).

[Examples 1 to 8] [Comparative Examples 1 to 18]
(1) Melt kneading (manufacturing of resin composition)
According to the blending ratios (parts by mass) shown in Tables 3 to 6, each component excluding the cross-linking agent (II) and the cross-linking accelerator was mixed with a lavender mixer (product name: Plastograph EC50cc mixer, lavender) under the conditions shown in Table 2. It was put into (manufactured by the company) and melt-kneaded (steps 1 and 2). Then, the melt-kneaded product was taken out of the lavender mixer and cooled to room temperature (step 3).
Next, this melt-kneaded product is placed in a mixing roll (manufactured by Kansai Roll Co., Ltd.) (step 4), a cross-linking agent (II) and a cross-linking accelerator are added (step 5), and the resin is re-kneaded (step 6). The composition was obtained.
(2) Molding (manufacturing of molded body)
Further, the resin composition obtained above was press-molded (160 ° C., 7 to 40 minutes) and crosslinked to obtain a rubber sheet (thickness 0.5 mm).
Using the obtained resin composition or rubber sheet, the physical properties were evaluated based on the following measurement method. The results are shown in Tables 3-6.
In Comparative Examples 1, 6 and 11, the resin composition and the rubber sheet could not be obtained because the hydrogenated block copolymer (I'-1) had poor dispersibility and could not be melt-kneaded. ..

The elastomers in Table 2 were a hydrogenated block copolymer (I), a hydrogenated block copolymer (I'), 1,4-polyfarnesene, or polystyrene-3,4-polyfarnesene-polystyrene, and blended. If the case is rubber (III).

(Vulcanization rate)
The vulcanization rate (t90) was measured according to JIS K 6300-2, using a vibration vulcanization tester (curast meter), and the above resin composition obtained in Examples and Comparative Examples at 160 ° C. The vulcanization time up to 90% vulcanization amount was defined as the vulcanization rate (t90). The smaller the value, the better the vulcanization rate.

(specific gravity)
Measured according to ISO 1183: 1987.
(hardness)
A dumbbell type 3 test piece (thickness 0.5 mm) was obtained from the rubber sheets of the resin compositions obtained in Examples and Comparative Examples using a punching blade conforming to JIS K 6251: 2010.
Twelve obtained test pieces were stacked to make a thickness of 6 mm, and the hardness was measured according to JIS K 6253-3: 2012 using an indenter of a type A durometer. The lower the hardness value, the better the flexibility, and if it is 80 or less, the flexibility is good.

(Tear strength)
According to JIS K6252-1: 2015, a non-cutting angle type test piece (thickness 0.5 mm) was obtained from the rubber sheet of the resin composition obtained in Examples and Comparative Examples using a punching blade. Using the obtained test piece, the tear strength was measured at a tensile speed of 500 mm / min and a temperature of 23 ° C. The higher the value, the better the tear strength.

(Stiction coefficient)
(1) According to Dry ASTM D-1894, the coefficient of static friction on the surface of the rubber sheet of the resin composition obtained in Examples and Comparative Examples was measured.
A test piece having a length of 110 mm, a width of 63.5 mm, and a thickness of 0.5 mm is cut out from the rubber sheet and wound around a cell (weight 200 g, 63.5 mm × 63.5 mm), and the test piece stand of the friction coefficient measuring device is horizontal. It was fixed to the autograph head so that it would be. The material of the friction table was aluminum, and the static friction coefficient was measured at a tensile speed of 150 mm / min. The higher the value of the static friction coefficient, the larger the frictional force and the less slippery, and the better the dry grip performance.
(2) The coefficient of static friction was measured by the same method as in (1) Dry above, except that 1 cc of distilled water was dropped on the wet friction table. The higher the value of the static friction coefficient, the larger the frictional force and the less slippery, and the better the wet grip performance.

(Tensile breaking strength and tensile breaking elongation)
Using a dumbbell type 3 test piece (0.5 mm) produced by the same method as the above (hardness) measurement, tensile breaking strength and tensile breaking elongation were measured according to JIS K 6251: 2010. The higher the values of tensile strength at break and elongation at break, the better the tensile properties.

From the results of Tables 3 to 6, Examples 1 and 2 which are the resin compositions of the present invention have tear strength, dry grip performance, wet grip performance, and tension as compared with Comparative Example 5 using rubber (III-2). It can be seen that both the breaking strength and the tensile breaking elongation are improved.
Further, the dry grip performance and the wet grip performance tend to be improved in Comparative Examples 2 to 4 as compared with Comparative Example 5, but in Examples 1 and 2, the dry grip performance and the wet grip performance are further maintained. It can be seen that the tear strength, tensile breaking strength, tensile breaking elongation and vulcanization rate are superior to those of Comparative Examples 2 to 4. In particular, in Example 1, it can be seen that the tensile breaking strength and the tensile breaking elongation are remarkably improved, and at the same time, the balance of other physical properties is also excellent.
Further, also in Table 4 having a structure containing 50 parts by mass of silica and Table 5 having a structure not containing silica, the resin composition of the present invention is more than the comparative examples 10 and 15 using the rubber (III-2). , It can be seen that each physical property is improved in a well-balanced manner.
Further, Example 7 using the hydrogenated block copolymer (I-1) and rubber (III-1) is particularly excellent in vulcanization speed, dry grip performance and wet grip performance as compared with Comparative Examples 16 and 17. The rubber and other physical properties were also good, and the balance of each physical property was excellent.
Further, when Example 8 and Comparative Example 5 are compared, compared to Comparative Example 5 in which only rubber (III-2) is used, in Example 8, tensile strength, dry grip performance, wet grip performance, tensile breaking strength and tensile breaking It can be seen that the growth is greatly improved.
In Comparative Examples 1, 6 and 11 in which the hydrogenated block copolymer (I'-1) was blended, melt-kneading could not be performed, whereas in Comparative Example 16, the hydrogenated block copolymer (I') was not melt-kneaded. When -1) and rubber (III-1) were used in combination, melt kneading was possible, but when the crosslinked state of the resin composition obtained in Comparative Example 16 was confirmed, the hydrogenated block copolymer (I) Crosslinking did not occur probably because the hydrogenation rate of'-1) was high. Therefore, the resin composition of Comparative Example 16 was inferior in wear resistance.

Since the resin composition of the present invention has an excellent balance of tear strength, tensile properties, dry grip performance and wet grip performance, shoe soles for footwear; sporting goods; various grips such as writing tools, tools and electric tools; It can be suitably used for office equipment such as rollers; rubber parts such as foot rubber; building materials such as coated plywood and coated steel plate.

Claims (16)

Contains hydrogenated block copolymer (I) and cross-linking agent (II),
A resin composition which does not contain a polyolefin resin or has a polyolefin resin content of less than 10 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I).
The hydrogenated block copolymer (I) comprises a polymer block (A) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing a structural unit (b1) derived from farnesene. The block copolymer (P) containing the block copolymer (P) is a hydrogenated product obtained by hydrogenating 50 mol% or more of carbon-carbon double bonds in the structural unit derived from the conjugated diene in the block copolymer (P).
A resin composition having a tear strength of 2.0 kN / m or more measured according to JIS K 6252-1: 2015 . The hydrogenation rate of a carbon-carbon double bond in the structural unit derived from the conjugated diene of the polymer block (B) in the hydrogenated block copolymer (I) is 50 to 98 mol%, according to claim 1. The resin composition described. The block copolymer (P) further contains a polymer block (C) containing a structural unit (c2) derived from a conjugated diene other than farnesene.
According to the hydrogenated block copolymer (I), the hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene between the polymer block (B) and the polymer block (C) is different. Item 2. The resin composition according to Item 1 or 2. The third aspect of the present invention, wherein the hydrogenation rate in the polymer block (B) is 50 to 95 mol%, and the hydrogenation rate in the polymer block (C) is 95 to 99.9 mol%. The resin composition described. The block copolymer (P) contains at least two of the polymer blocks (A), at least one of the polymer blocks (B), and at least one of the polymer blocks (C). The resin composition according to claim 3 or 4, further comprising at least one polymer block (B) at the end. The resin composition according to any one of claims 1 to 5, wherein the cross-linking agent (II) is a cross-linking agent that undergoes a cross-linking reaction only with a carbon-carbon double bond in the structural unit derived from the conjugated diene or α-methylene thereof. .. The resin composition according to any one of claims 1 to 6, wherein the cross-linking agent (II) is sulfur or a sulfur-containing compound. The invention according to any one of claims 1 to 7, wherein the content of the cross-linking agent (II) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I). Resin composition. The resin composition according to any one of claims 1 to 8, further comprising 0 to 120 parts by mass of an inorganic filler with respect to 100 parts by mass of the hydrogenated block copolymer (I). The resin composition according to any one of claims 1 to 9, further comprising rubber (III). Claims 1 to 10 wherein the polymer block (B) contains 1 to 100% by mass of the structural unit (b1) derived from farnesene and 99 to 0% by mass of a structural unit (b2) derived from a conjugated diene other than farnesene. The resin composition according to any one of. The resin composition according to any one of claims 1 to 11, wherein the content of the polymer block (A) in the hydrogenated block copolymer (I) is 10 to 45% by mass. The resin composition according to any one of claims 1 to 12, wherein the tensile elongation at break measured according to JIS K 6251: 2010 is 100% or more. The resin composition according to any one of claims 1 to 13 , which does not contain a softening agent. A molded product of the resin composition according to any one of claims 1 to 14 . A sole using the resin composition according to any one of claims 1 to 14 at least in part.