Resin composition and molded article

Abstract

A resin composition and a molded article thereof, the resin composition containing a rubber (I), a block copolymer (II), and a crosslinking agent (III), the mass ratio [(I) / (II)] of the aforementioned rubber (I) to the aforementioned block copolymer (II) being from 99 / 1 to 55 / 45, the aforementioned block copolymer (II) being a block copolymer containing a polymer block (A) and a polymer block (B), the polymer block (A) containing a structural unit derived from an aromatic vinyl compound, and the polymer block (B) containing a structural unit (b1) derived from farnesene.

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded article thereof, the resin composition containing at least a rubber, a block copolymer having a structural unit derived from farnesene, and a crosslinking agent. Background Art

[0002] Rubber compositions obtained by mixing thermoplastic elastomers such as styrene-based elastomers and olefin-based elastomers with various rubbers are used in a wide range of fields such as shoe soles, various tires, building materials such as fillers, and mechanical parts due to their excellent mechanical properties and flexibility. However, rubber compositions containing thermoplastic elastomers are likely to slip due to water adhesion, especially in applications such as shoe soles and various tires, which is accompanied by high risks and thus becomes a problem.

[0003] Therefore, research has been conducted to improve the wet grip of rubber compositions containing thermoplastic elastomers and rubber components.

[0004] For example, a resin composition having a number average molecular weight of a thermoplastic elastomer, a glass transition temperature of a rubber component, or containing a tackifying resin and a hydrogenated block copolymer has been proposed (for example, Patent Documents 1 to 8). In addition, a resin composition containing a hydrogenated block copolymer containing a polymer block having a structural unit derived from farnesene has been proposed (for example, Patent Document 9).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: U.S. Patent Application Publication No. 2013 / 0086822

[0008] Patent Document 2: International Publication No. 2006 / 121069

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 2017-39819

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 2016-210937

[0011] Patent Document 5: Japanese Patent Application Laid-Open No. 2014-189697

[0012] Patent Document 6: Japanese Patent Application Laid-Open No. 2014-520017

[0013] Patent Document 7: Japanese Patent Application Laid-Open No. 2004-75882

[0014] Patent Document 8: Japanese Patent Application Laid-Open No. 2003-292672

[0015] Patent Document 9: Japanese Unexamined Patent Application Publication No. 2019-26826. Summary of the Invention

[0016] Problems to be Solved by the Invention

[0017] However, with the technologies disclosed in Patent Documents 1 to 8, it is impossible to produce a resin composition having an excellent balance among flexibility, tear strength, tensile properties, dry grip, and wet grip, and further improvement is sought. Furthermore, Patent Documents 1 to 8 do not disclose a block copolymer and its hydride as described below, which block copolymer comprises a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from farnesene.

[0018] In addition, although the resin composition disclosed in Patent Document 9 has an excellent balance among flexibility, tear strength, tensile properties, dry grip, and wet grip, further improvement is sought in terms of the performance of the non-slip degree of a molded article such as grip in various environments. Also, in applications such as shoe soles and various tires, excellent abrasion resistance is required.

[0019] Therefore, an object of the present invention is to provide a resin composition capable of producing a molded article that is not easily slippery and has excellent abrasion resistance, and a molded article of the resin composition.

[0020] Means for Solving the Problems

[0021] As a result of intensive studies to solve the above problems, the present inventors conceived the following present invention and found that it can solve the problems.

[0022] That is, the present invention is as follows.

[0023] [1] A resin composition containing rubber (I), a block copolymer (II), and a crosslinking agent (III),

[0024] The mass ratio [(I) / (II)] of the rubber (I) to the block copolymer (II) is 99 / 1 to 55 / 45,

[0025] The block copolymer (II) is a block copolymer comprising a polymer block (A) and a polymer block (B), the polymer block (A) containing a structural unit derived from an aromatic vinyl compound, and the polymer block (B) containing a structural unit (b1) derived from farnesene.

[0026] [2] A molded article which is a molded article of the resin composition according to the above [1].

[0027] [3] A sole which uses the resin composition according to the above [1] in at least a part thereof.

[0028] Advantages of the Invention

[0029] According to the present invention, there can be provided a resin composition capable of forming a shaped body that is not prone to slipping and has excellent abrasion resistance, and a shaped body of the resin composition. Detailed Embodiments

[0030] Hereinafter, an example of an embodiment of the present invention (hereinafter sometimes referred to as "the present embodiment") will be described. Among them, the embodiments shown below are examples for specifically implementing the technical idea of the present invention, and the present invention is not limited to the following description.

[0031] In addition, in this specification, preferred forms of the embodiment are shown, and forms obtained by combining two or more of the respective preferred forms are also preferred forms. Regarding matters represented by numerical ranges, in the case where there are several numerical ranges, their lower limit values and upper limit values can be selectively combined as preferred forms.

[0032] It should be noted that in this specification, when there is a description of a numerical range of "XX to YY", it means "XX or more and YY or less".

[0033] <Resin Composition>

[0034] The resin composition of the present embodiment is characterized in that it contains a rubber (I), a block copolymer (II), and a crosslinking agent (III).

[0035] The mass ratio [(I) / (II)] of the aforementioned rubber (I) to the aforementioned block copolymer (II) is 99 / 1 to 55 / 45.

[0036] The aforementioned block copolymer (II) is a block copolymer containing a polymer block (A) and a polymer block (B), and the polymer block (A) contains a structural unit derived from an aromatic vinyl compound, and the polymer block (B) contains a structural unit (b1) derived from farnesene.

[0037] By using the block copolymer (II) containing the structural unit (b1) derived from farnesene, the resin composition is imparted with softness and has road surface followability as described later, and thus has high repellency (water repellency performance). Furthermore, the block copolymer (II) has excellent water repellency performance, and therefore, it can be expected that the non-slip property (hereinafter sometimes referred to as "grip") of the shaped body is excellent under any of dry conditions (dry surface), wet conditions (wet surface), and freezing conditions (snow surface or ice surface).

[0038] Moreover, by setting the above mass ratio [(I) / (II)] within the above specific numerical range, both excellent non-slip property and abrasion resistance can be achieved.

[0039] In addition, based on the above properties, the resin composition of this embodiment has an excellent balance between tear strength and tensile properties. Furthermore, since the content of rubber (I) is higher than that of block copolymer (II), cost reduction is also expected to be facilitated.

[0040] [Rubber (I)]

[0041] Examples of rubber (I) contained in the resin composition of this embodiment include natural rubber and various synthetic rubbers used as rubber raw materials for rubber soles such as shoe soles.

[0042] It should be noted that rubber (I) does not include the aforementioned block copolymer (II).

[0043] Examples of natural rubber (NR) include TSR (Technically Specified Rubber) such as SMR (TSR produced in Malaysia), SIR (TSR produced in Indonesia), and STR (TSR produced in Thailand), RSS (Ribbed Smoked Sheet), and other natural rubbers commonly used in various fields such as the tire industry and shoe soles, high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, grafted natural rubber, and other modified natural rubbers.

[0044] Examples of synthetic rubbers include styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), ethylene-propylene-diene copolymer (EP, EPM), ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), butyl rubber (isobutene-isoprene rubber (IIR)), and halogenated butyl rubber obtained by modifying butyl rubber.

[0045] Among the above rubbers, from the viewpoints of physical properties such as strength, abrasion resistance, elasticity, and flexibility required in various applications, and compatibility with various components such as block copolymer (II), at least one selected from styrene-butadiene copolymer rubber, natural rubber, polyisoprene rubber, polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene-diene copolymer, butyl rubber, and halogenated butyl rubber obtained by modifying butyl rubber is preferred.

[0046] Rubber (I) can be used alone or in combination of two or more.

[0047] Specific combinations when using rubber (I) in combination include, for example, two or more selected from NR, SBR, and BR. From the viewpoint of the balance of grip, abrasion resistance, and mechanical properties, it is preferable to use two or more of these rubbers as rubber (I).

[0048] In addition, when at least NR is used as the rubber (I), it is preferable to use the softening agent described below in combination. Among the softening agents, liquid polybutadiene, its hydride, or its modified product (sometimes simply referred to as "liquid polybutadiene") is suitable. It is considered that by using liquid polybutadiene in combination, the viscosity of NR decreases and the dispersibility in the composition improves. Therefore, it is easier to obtain a molded body with excellent grip. One type of liquid polybutadiene can be used alone, or two or more types can be used in combination.

[0049] The weight-average molecular weight (Mw) of the above-mentioned liquid polybutadiene is preferably 100 to 200,000, more preferably 1,000 to 130,000, further preferably 2,000 to 60,000, and even more preferably 5,000 to 50,000. If the weight-average molecular weight is within the above range, the processability is improved, and the bleeding of the resin composition can be suppressed.

[0050] The number-average molecular weight (Mn) of the above-mentioned liquid polybutadiene is preferably 2,000 to 180,000, more preferably 3,000 to 130,000, further preferably 4,000 to 50,000, and even more preferably 5,000 to 35,000. If the number-average molecular weight is within the above range, the processability is improved, and the bleeding of the resin composition can be suppressed.

[0051] The molecular weight distribution (Mw / Mn) of the above-mentioned liquid polybutadiene is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and even more preferably 1 to 2. If the molecular weight distribution is within the above range, the viscosity deviation of the liquid polybutadiene is small and it is easy to handle.

[0052] The Mw and Mn of the liquid polybutadiene are values obtained by measuring gel permeation chromatography (GPC), and refer to the values measured by the method described in the following examples.

[0053] As a preferred embodiment, for example, the combination of NR, SBR, and BR can further contain liquid polybutadiene. In particular, when the content ratio of NR in the above combination is 50% by mass or more, the advantages brought about by using liquid polybutadiene in combination can be better exerted.

[0054] In addition, as an example of a preferred embodiment when at least NR is used as the rubber (I), the content of the above-mentioned liquid polybutadiene as a softening agent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 9 parts by mass, further preferably 1 to 8 parts by mass, and even more preferably 1.5 to 7 parts by mass with respect to the total 100 parts by mass of the rubber (I), block copolymer (II), and liquid polybutadiene.

[0055] It should be noted that the rubber (I) does not include the above-mentioned liquid polybutadiene.

[0056] As SBR, for example, emulsion-polymerized styrene-butadiene rubber (E-SBR), solution-polymerized styrene-butadiene rubber (S-SBR), modified styrene-butadiene rubber (modified SBR), etc. can all be used.

[0057] In addition, commercially available SBR can be used, and the styrene content is preferably 0.1 to 70% by mass, more preferably 5 to 50% by mass, further preferably 15 to 35% by mass, and even more preferably 15 to 25% by mass.

[0058] SBR has a good balance of physical properties such as elasticity and strength, and is also good for mixing, molding, and processing. It is also suitable from the perspective of easy availability.

[0059] As IR, commercially available IR can be used, preferably IR obtained by polymerization using a Ziegler catalyst with a high content of cis-form, and IR with an ultra-high cis-form content obtained by using a lanthanide-based rare earth metal catalyst.

[0060] The weight-average molecular weight (Mw) of IR is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When Mw is within the above range, the formability, tear strength, and tensile properties become good. It should be noted that the weight-average molecular weight of IR refers to the weight-average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).

[0061] The vinyl content of IR is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

[0062] IR is also suitable from the perspective of good balance of physical properties such as mechanical strength and easy availability.

[0063] As BR, commercially available BR can be used, preferably BR obtained by polymerization using a Ziegler catalyst with a high content of cis-form, and BR with an ultra-high cis-form content obtained by using a lanthanide-based rare earth metal catalyst.

[0064] The weight-average molecular weight (Mw) of BR 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 even more preferably 350,000 to 700,000. When Mw is within the above range, the formability, tear strength, and tensile properties become good.

[0065] The vinyl content of BR is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

[0066] In particular, from the viewpoint of being able to impart excellent abrasion resistance to the molded article of the resin composition, it is also suitable as BR.

[0067] As NBR, commercially available NBR can be used. The acrylonitrile content in NBR is preferably 20 to 41% by mass, more preferably 25 to 41% by mass. When the acrylonitrile content is within the above range, it is expected to impart more excellent grip and abrasion resistance to the molded article of the resin composition in various environments.

[0068] As ethylene-propylene-diene copolymer (EP, EPM), ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), commercially available EP and EPDM can be used. Examples of the non-conjugated diene constituting EPDM include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, 5-isopropylidene-2-norbornene, 5-vinyl-norbornene, dicyclooctadiene, methylene norbornene, etc. Among these, from the viewpoint of vulcanization rate, 5-ethylidene-2-norbornene (ENB) is preferred. In addition, among ethylene-propylene-diene copolymer (EP, EPM) and ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), from the viewpoint of being able to obtain a larger vulcanization rate, ethylene-propylene-non-conjugated diene copolymer rubber (EPDM) is preferred.

[0069] As IIR, it can be non-halogenated butyl rubber, recycled butyl rubber, etc., and examples of IIR used in the fields of tire industry or shoe soles include those. In addition, halogenated butyl rubber is a rubber obtained by introducing halogen into the molecule of IIR and modifying it, and examples include brominated butyl rubber (Br-IIR) and chlorinated butyl rubber (Cl-IIR). In addition, brominated isobutene-p-methylstyrene copolymer, etc. can also be used.

[0070] [Block copolymer (II)]

[0071] The resin composition of the present embodiment contains the block copolymer (II), so that its flexibility becomes good, it is not easy to slip, and it can exhibit abrasion resistance. Furthermore, it is also expected to exhibit tensile properties and tear strength.

[0072] The block copolymer (II) can be an unhydrogenated block copolymer (hereinafter sometimes referred to as "block copolymer (P)"), or a hydrogenated block copolymer (hereinafter sometimes referred to as "hydrogenated block copolymer (Q)") obtained by hydrogenating the block copolymer (P) at a specific hydrogenation rate as described later.

[0073] (Polymer block (A))

[0074] The polymer block (A) contains a structural unit derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. These aromatic vinyl compounds can be used alone or in combination of two or more. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferred, and styrene is more preferred.

[0075] The polymer block (A) may contain a structural unit derived from a monomer other than the aromatic vinyl compound, such as a monomer constituting the polymer block (B) described later. Among them, 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, still more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0076] In addition, the content of the polymer block (A) in the block copolymer (II) is preferably 10 to 45% by mass, more preferably 10 to 40% by mass, further preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass. If the above content is 10% by mass or more, the moldability of the resin composition becomes good, it is easy to exhibit more excellent abrasion resistance, and the tear strength and tensile properties can also be made suitable. In addition, if the above content is 45% by mass or less, sufficient flexibility can be obtained, it is easy to exhibit anti-slip properties, and it is easy to exhibit good moldability, tear strength, and tensile properties.

[0077] (Polymer block (B))

[0078] The polymer block (B) contains a structural unit (b1) derived from farnesene (hereinafter also simply referred to as "structural unit (b1)").

[0079] As the above-mentioned farnesene, it can be either α-farnesene or β-farnesene represented by the following formula (1). From the viewpoint of the ease of manufacturing the block copolymer (II), β-farnesene is preferred. It should be noted that α-farnesene and β-farnesene can be used in combination.

[0080] [Chemical formula 1]

[0081]

[0082] The content of the structural unit (b1) derived from farnesene in the polymer block (B) is preferably 1 to 100% by mass. By making the polymer block (B) contain the structural unit (b1) derived from farnesene, the flexibility becomes good and the grip is excellent. From this viewpoint, the content of the structural unit (b1) derived from farnesene in the polymer block (B) is more preferably 10 to 100% by mass, further preferably 20 to 100% by mass, still further preferably 30 to 100% by mass, particularly preferably 50 to 100% by mass, and most preferably 100% by mass, that is, the polymer block (B) is composed of the structural unit (b1).

[0083] In addition, when farnesene is of biological origin, the use amount of conjugated dienes other than farnesene such as butadiene and isoprene derived from petroleum can be inhibited, and the petroleum dependence can be reduced. From this viewpoint, the content of the structural unit (b1) derived from farnesene in the polymer block (B) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, further preferably 70 to 100% by mass, still further preferably 80 to 100% by mass.

[0084] In addition, when the polymer block (B) contains the following structural unit (b2), the content of the structural unit (b1) derived from farnesene in the polymer block (B) is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, still further preferably 30% by mass or more, and particularly preferably 50% by mass or more.

[0085] The polymer block (B) may contain a structural unit (b2) other than the conjugated diene-derived structural unit other than farnesene (hereinafter also simply referred to as "structural unit (b2)"), and the content of the structural unit (b2) in the polymer block (B) is preferably 0 to 99% by mass.

[0086] Examples of the 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, myrcene, and chloroprene. These may be used alone or in combination of two or more. Among these, isoprene, butadiene, and myrcene are preferred, and isoprene and butadiene are more preferred.

[0087] When the polymer block (B) contains the structural unit (b2), the content of the structural unit (b2) is more preferably 90% by mass or less, further preferably 80% by mass or less, still further preferably 70% by mass or less, and particularly preferably 50% by mass or less.

[0088] The polymer block (B) may contain other structural units in addition to 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, and further preferably 100% by mass.

[0089] (Polymer block (C))

[0090] The block copolymer (II) may further contain a polymer block (C) containing a structural unit (c2) derived from a conjugated diene other than farnesene, in addition to the aforementioned polymer block (A) and polymer block (B).

[0091] The polymer block (C) is preferably a polymer block in which the content of the structural unit (c1) derived from farnesene is 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 100% by mass.

[0092] Examples of the farnesene constituting the structural unit (c1) derived from farnesene (hereinafter also simply referred to as "structural unit (c1)") and the conjugated diene constituting the structural unit (c2) derived from a conjugated diene other than farnesene (hereinafter also simply referred to as "structural unit (c2)") are the same as those of the farnesene constituting the structural unit (b1) derived from farnesene and the conjugated diene constituting the structural unit (b2) derived from a conjugated diene other than farnesene described above.

[0093] Among these, as the conjugated diene constituting the structural unit (c2) derived from a conjugated diene other than farnesene, isoprene, butadiene, and myrcene are preferred, and isoprene and butadiene are more preferred. These may be used alone or in combination of two or more.

[0094] The content of the farnesene-derived structural unit (c1) in the polymer block (C) is preferably 0% by mass.

[0095] The content of the structural unit (c2) derived from a conjugated diene other than farnesene in the polymer block (C) is more preferably 60 to 100% by mass, still more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 100% by mass. By using the polymer block (C) containing the structural unit (c2), the block copolymer (P) has conjugated dienes with different structural units (b1) and structural unit (c2) as described above. Even when the hydrogenated block copolymer (Q) of the block copolymer (P) is crosslinked with the crosslinking agent (III) described later, the abrasion resistance is excellent, and it can exhibit tear strength while maintaining the tensile properties, and the coexistence of tensile properties and tear strength can be achieved.

[0096] In addition, the polymer block (C) may contain other structural units in addition to the farnesene-derived structural unit (c1) and the structural unit (c2) derived from a conjugated diene other than farnesene.

[0097] 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, and further preferably 100%.

[0098] (Bonding form)

[0099] The block copolymer (II) is a block copolymer (P) or a hydrogenated block copolymer (Q) each containing at least one polymer block (A) and a polymer block (B).

[0100] 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 each block is linearly bonded is preferred.

[0101] As a linear bonding form, when the polymer block (A) is denoted as A and the polymer block (B) is denoted as B, examples include (A-B) l , A-(B-A) m or B-(A-B) n The bonding forms shown, etc. It should be noted that l, m, and n each independently represent an integer of 1 or more.

[0102] When the block copolymer (II) contains at least one polymer block (A) and a polymer block (B) respectively, it preferably has a block bonding form in the order of the polymer block (A), the polymer block (B), and the polymer block (A), and is a triblock copolymer represented by A-B-A.

[0103] That is, the block copolymer (II) is preferably a triblock copolymer represented by A-B-A, and this triblock copolymer may be an unhydrogenated product or a hydrogenated product.

[0104] When the block copolymer (II) contains a polymer block (A), a polymer block (B), and a polymer block (C), the block copolymer (II) is preferably a block copolymer having at least one polymer block (B) at the end, and this block copolymer may be an unhydrogenated product or a hydrogenated product. By having at least one polymer block (B) present at the end of the polymer chain, the moldability is improved. From this viewpoint, when the block copolymer (II) is linear, it is more preferably to have polymer blocks (B) at both of its ends. In addition, when the block copolymer (II) is branched or radial, the number of polymer blocks (B) present at the end is preferably 2 or more, and more preferably 3 or more.

[0105] In addition, the block copolymer (II) is preferably a block copolymer containing at least two polymer blocks (A), at least one polymer block (B), and at least one polymer block (C), and more preferably contains at least two polymer blocks (A), at least one polymer block (B), and at least one polymer block (C), and has more than one of at least one polymer block (B) at the end.

[0106] When the block copolymer (II) contains a polymer block (A), a polymer block (B), and a polymer block (C), the bonding form of the plurality of polymer blocks is not particularly limited, and may be linear, branched, radial, or a combination of two or more of them. Among these, the form obtained by bonding each block linearly is preferred.

[0107] The block copolymer (II) preferably has a block structure in the order of polymer block (B), polymer block (A), and polymer block (C) (that is, a B-A-C structure).

[0108] Specifically, the block copolymer (II) is preferably a tetrablock copolymer represented by B-A-C-A, a pentablock copolymer represented by B-A-C-A-B, B-A-(C-A) p -B, B-A-(C-A-B) q 、B-(A-C-A-B) r (p, q, r each independently represent an integer of 2 or more), and among them, the pentablock copolymer represented by B-A-C-A-B is more preferred.

[0109] That is, the block copolymer (II) is preferably a pentablock copolymer represented by B-A-C-A-B, and this pentablock copolymer may be an unhydrogenated product or a hydrogenated product.

[0110] Here, in this specification, when polymer blocks of the same type are bonded linearly by a divalent coupling agent or the like, the entire polymer blocks being bonded are regarded as one polymer block. Thus, a polymer block that should strictly speaking be expressed as A-X-A (where X represents a coupling agent residue) is shown as A as a whole. In this specification, such polymer blocks containing coupling agent residues are treated as described above. Therefore, for example, a block copolymer that contains a coupling agent residue and should strictly speaking be expressed as B-A-C-X-C-A-B is expressed as B-A-C-A-B and regarded as an example of a pentablock copolymer.

[0111] In addition, two or more polymer blocks (A) in the above block copolymer (II) may be polymer blocks containing the same structural units or may be polymer blocks containing different structural units. Similarly, when the block copolymer (II) has two or more polymer blocks (B) or two or more polymer blocks (C), each polymer block may be a polymer block containing the same structural units or may be a polymer block containing different structural units. For example, in the two polymer blocks (A) of a triblock copolymer represented by A-B-A, the types of each aromatic vinyl compound may be the same or different.

[0112] When the block copolymer (II) contains the polymer block (A) and the polymer block (B) but does not contain the polymer block (C), the mass ratio [(A) / (B)] of the polymer block (A) to the polymer block (B) is 1 / 99 to 70 / 30, preferably 5 / 95 to 60 / 40, more preferably 10 / 90 to 50 / 50, further preferably 15 / 85 to 40 / 60, and even more preferably 15 / 85 to 35 / 65. If within this range, a resin composition with excellent flexibility and excellent grip properties can be obtained.

[0113] When the block copolymer (II) contains the polymer block (A), the polymer block (B), and the polymer block (C), the mass ratio [(A) / (B)] of the polymer block (A) to the polymer block (B) is 1 / 99 to 70 / 30, preferably 5 / 95 to 60 / 40, more preferably 10 / 90 to 50 / 50, further preferably 20 / 80 to 40 / 60, and even more preferably 25 / 75 to 35 / 65. If within this range, a resin composition with excellent flexibility and excellent grip properties can be obtained.

[0114] In the block copolymer (II), the mass ratio [(A) / ((B)+(C))] of the total amount of the polymer block (A), the polymer block (B), and the polymer block (C) is preferably 1 / 99 to 70 / 30. If it is within this range, a resin composition having excellent tensile properties, moldability, and grip properties can be obtained. From this viewpoint, the mass ratio [(A) / ((B)+(C))] is more preferably 1 / 99 to 60 / 40, further preferably 10 / 90 to 40 / 60, still further preferably 10 / 90 to 30 / 70, and still further preferably 15 / 85 to 25 / 75.

[0115] When the block copolymer (II) contains the polymer block (A), the polymer block (B), and the polymer block (C), from the viewpoint of excellent flexibility, tensile properties, and grip properties, the total content of the structural unit (b1) and the structural unit (c1) in the block copolymer relative to the total amount of the polymer block (B) and the polymer block (C) [((b1)+(c1)) / ((B)+(C))] is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and further preferably 60 to 70% by mass.

[0116] When the block copolymer (II) contains the polymer block (A) and the polymer block (B) but does not contain the polymer block (C), the total content of the polymer block (A) and the polymer block (B) in the block copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and still further preferably 100% by mass.

[0117] In addition, when the block copolymer (II) contains the polymer block (A), the polymer block (B), and the polymer block (C), the total content of these polymer blocks (A) to (C) in the block copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and still further preferably 100% by mass.

[0118] As an example of a more preferred form of the block copolymer (II), from the viewpoints of anti-slip properties, abrasion resistance, flexibility, tear strength, and tensile properties,

[0119] ・ It is a hydrogenated block copolymer (Q) obtained by hydrogenating a block copolymer (P) containing the polymer block (A), the polymer block (B), and the polymer block (C),

[0120] ・ The polymer block (C) is a polymer block in which the content of the structural unit (c1) derived from farnesene is 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 100% by mass.

[0121] - The mass ratio [(A) / ((B)+(C))] of the polymer block (A) to the total amount of the polymer block (B) and the polymer block (C) is 10 / 90 to 30 / 70.

[0122] - It contains at least 2 of the aforementioned polymer blocks (A), at least 1 of the aforementioned polymer blocks (B), and at least 1 polymer block (C), and has at least 1 polymer block (B) at the end.

[0123] - The hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated dienes in the hydrogenated block copolymer (Q) is 70 mol% or more.

[0124] (Polymer block composed of other monomers)

[0125] In addition to containing the polymer block (A), the polymer block (B), and the polymer block (C), the block copolymer (II) may contain a polymer block composed of other monomers as long as the effects of the present invention are not impaired.

[0126] Examples of such other monomers include unsaturated hydrocarbon compounds such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene; unsaturated compounds containing functional groups such as 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-methylpropanesulfonic acid, vinylsulfonic acid, vinyl acetate, methyl vinyl ether, etc. They can be used alone or in combination of two or more.

[0127] When the block copolymer (II) has other polymer blocks, its content is preferably 10% by mass or less, more preferably 5% by mass or less.

[0128] (Method for producing the block copolymer (II))

[0129] When the block copolymer (II) is, for example, a block copolymer (P) containing a polymer block (A) and a polymer block (B), or a block copolymer (P) containing a polymer block (A), a polymer block (B), and a polymer block (C) when containing a polymer block (C), it can be suitably produced by a polymerization process based on anionic polymerization. Further, when the block copolymer (II) is a hydrogenated block copolymer (Q), it can be suitably produced by a process of hydrogenating the carbon-carbon double bonds in the structural units derived from conjugated dienes in the aforementioned block copolymer (P).

[0130] 〈Polymerization process〉

[0131] The block copolymer (P) can be produced by a solution polymerization method or the methods described in Japanese Patent Application Laid-Open No. 2012-502135 and Japanese Patent Application Laid-Open No. 2012-502136. Among these, the solution polymerization method is preferred, and known methods such as ionic polymerization methods such as anionic polymerization and cationic polymerization, and radical polymerization methods can be applied. Among these, anionic polymerization is preferred. As the anionic polymerization method, in the presence of a solvent, an anionic polymerization initiator, and a Lewis base as needed, an aromatic vinyl compound, farnesene, and / or a conjugated diene other than farnesene are successively added to obtain the block copolymer (P).

[0132] Examples of the anionic polymerization initiator include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; rare earth metals of the lanthanide series such as lanthanum and neodymium; and compounds containing the aforementioned alkali metals, alkaline earth metals, and rare earth metals of the lanthanide series. Among these, compounds containing alkali metals and alkaline earth metals are preferred, and organoalkali metal compounds are more preferred.

[0133] Examples of the aforementioned organoalkali metal compounds include organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dilithium methane, dilithium naphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene, etc. Among these, organolithium compounds are preferred, n-butyllithium and sec-butyllithium are more preferred, and sec-butyllithium is further preferred. It should be noted that the organoalkali metal compound can be reacted with a secondary amine such as diisopropylamine, dibutylamine, dihexylamine, and dibenzylamine to be used as an organoalkali metal amide.

[0134] The amount of the organoalkali metal compound used in the polymerization also varies depending on the molecular weight of the block copolymer (P). Generally, it is in the range of 0.01 to 3% by mass based on the total amount of the aromatic vinyl compound, farnesene, and the conjugated diene other than farnesene.

[0135] As the solvent, so long as it does not have an adverse effect on the anionic polymerization reaction, there is no particular limitation, and examples thereof include saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, and isooctane; saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene, etc. They can be used alone in one kind, or two or more kinds can be used in combination. The amount of the solvent is not particularly limited.

[0136] The Lewis base has the effect of controlling the microstructure in the structural unit derived from farnesene and the structural unit derived from conjugated dienes 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; alkali metal alcoholates such as potassium tert-butoxide; phosphine compounds, etc. When using a Lewis base, its amount is usually preferably in the range of 0.01 to 1000 molar equivalents relative to 1 mole of the anionic polymerization initiator.

[0137] The temperature of the polymerization reaction is usually in the range of about -80 to 150 °C, preferably 0 to 100 °C, more preferably 10 to 90 °C. The form of the polymerization reaction can be batchwise or continuous. By continuously supplying or intermittently supplying each monomer to the polymerization reaction solution in such a way that the amounts of the aromatic vinyl compound, farnesene, and / or conjugated dienes other than farnesene in the polymerization reaction system reach a specific range, or by polymerizing them in sequence in such a way that each monomer reaches a specific ratio in the polymerization reaction solution, a block copolymer (P) can be produced.

[0138] The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator. The block copolymer (P) can be precipitated by injecting the obtained polymerization reaction solution into a poor solvent such as methanol, or after washing and separating the polymerization reaction solution with water and then drying, the block copolymer (P) can be separated.

[0139] As described above, the block copolymer (II) preferably has a structure having a polymer block (B), a polymer block (A), and a polymer block (C) in this order. Therefore, it is more preferable to produce the hydrogenated block copolymer (Q) by a method including the following steps: a step of obtaining the block copolymer (P) by successively producing the polymer block (B), the polymer block (A), and the polymer block (C); or, in the case of a hydride, a step of further hydrogenating the obtained block copolymer (P).

[0140] It should be noted that in the case where the aforementioned block copolymer (II) has a polymer block (B) only at a single end of the polymer chain, it can be obtained by a method in which after polymerizing the other polymer blocks in a linearly bonded manner, the polymer block (B) is finally produced.

[0141] When the block copolymer (II) is a block copolymer (P) containing at least two polymer blocks (A), at least one polymer block (B), and at least one polymer block (C) and having at least one polymer block (B) at the terminal, or a hydrogenated block copolymer (Q) obtained by hydrogenating the same, as a method for producing the block copolymer (P), the following can be mentioned:

[0142] 〔i〕A method of polymerizing the polymer block (B), the polymer block (A), the polymer block (C), and the polymer block (A) in this order; and

[0143] 〔ii〕A method of producing by polymerizing the polymer block (B), the polymer block (A), and the polymer block (C) in this order and coupling the terminals of the polymer block (C) to each other using a coupling agent, etc.

[0144] In the present embodiment, from the viewpoint of efficient production, the latter method 〔ii〕 using a coupling agent is preferred.

[0145] Examples of the aforementioned coupling agent include divinylbenzene; polyvalent epoxides such as epoxidized 1,2-polybutadiene, epoxidized soybean oil, and tetraglycidyl-1,3-bis(aminomethyl)cyclohexane; halides such as tin tetrachloride, tetrachlorosilane, trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, and dibromodimethylsilane; ester compounds such as methyl benzoate, ethyl benzoate, phenyl benzoate, diethyl oxalate, diethyl malonate, diethyl adipate, dimethyl phthalate, and dimethyl terephthalate; carbonate compounds such as dimethyl carbonate, diethyl carbonate, and diphenyl carbonate; alkoxysilane compounds such as diethoxydimethylsilane, trimethoxymethylsilane, triethoxymethylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra(2-ethylhexyl)oxysilane, bis(triethoxysilyl)ethane, and 3-aminopropyltriethoxysilane; 2,4-toluene diisocyanate, etc.

[0146] In this polymerization step, an unmodified block copolymer can be obtained as described above, or a modified block copolymer can be obtained as follows.

[0147] In the case of the modified block copolymer, the aforementioned block copolymer (P) can be modified before the subsequent hydrogenation step. Examples of the functional groups that can be introduced include, for example, amino, alkoxysilyl, hydroxyl, epoxy, carboxyl, carbonyl, mercapto, isocyanate, acid anhydride, etc.

[0148] Examples of methods for modifying the block copolymer (P) include adding a coupling agent capable of reacting with the active polymerization terminals, such as tin tetrachloride, tetrachlorosilane, dichlorodimethylsilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, or 2,4-toluene diisocyanate, a polymerization terminal modifier such as 4,4'-bis(diethylamino)benzophenone or N-vinylpyrrolidone, or other modifiers described in JP-A-2011-132298, before adding a polymerization terminator. Furthermore, the separated copolymer may be grafted with maleic anhydride and reused.

[0149] The position where the functional group is to be introduced can be the polymerization end of the block copolymer (P) or a side chain. In addition, the functional group can be one or a combination of two or more. The modifier is preferably in the range of 0.01 to 10 molar equivalents relative to 1 mole of the anionic polymerization initiator.

[0150] Hydrogenation process

[0151] The block copolymer (II) is subjected to a step of hydrogenating the block copolymer (P) or the modified block copolymer obtained by the above-mentioned method to obtain a hydrogenated block copolymer (Q).

[0152] The hydrogenation method may be a known method. For example, a block copolymer (P) is dissolved in a solvent that does not affect the hydrogenation reaction, and a Ziegler catalyst; a nickel, platinum, palladium, ruthenium, or rhodium metal catalyst supported on carbon, silica, diatomaceous earth, or the like; or an organic metal complex containing cobalt, nickel, palladium, rhodium, or ruthenium metal is used as a hydrogenation catalyst to carry out the hydrogenation reaction.

[0153] In the hydrogenation step, a hydrogenation reaction can be carried out by adding a hydrogenation catalyst to a polymerization reaction solution containing a block copolymer obtained by the method for producing the block copolymer (P). In the present invention, the hydrogenation catalyst is preferably palladium-carbon obtained by supporting palladium on carbon.

[0154] 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.

[0155] One of the preferred embodiments of the block copolymer (II) is a hydrogenated block copolymer (Q) obtained by hydrogenating 70 mol% or more of the carbon-carbon double bonds in the structural units derived from conjugated dienes. From the viewpoints of heat resistance, weather resistance, and excellent tear strength exhibited by crosslinking, the hydrogenation ratio of the carbon-carbon double bonds in the structural units derived from conjugated dienes is preferably 70 to 98 mol%, more preferably 70 to 97 mol%, further preferably 80 to 96 mol%, still further preferably 85 to 96 mol%, and particularly preferably 87 to 96 mol%.

[0156] It should be noted that the above hydrogenation ratio is the hydrogenation ratio of the carbon-carbon double bonds in all the structural units derived from conjugated dienes present in the block copolymer (P).

[0157] Examples of the carbon-carbon double bonds in the structural units derived from conjugated dienes present in the block copolymer (P) include, for example, the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (B). In addition, when the block copolymer (P) further contains a polymer block (C), examples include the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (B) and the polymer block (C).

[0158] When the hydrogenated block copolymer (Q) contains a polymer block (B) and a polymer block (C), the hydrogenation ratios of the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (B) and the polymer block (C) are preferably different. The difference in the hydrogenation ratios of the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (B) and the polymer block (C) can be, for example, 1 to 20 mol%, 3 to 15 mol%, or 5 to 10 mol%. It is considered that by making the above hydrogenation ratios different, the degree of crosslinking based on the crosslinking agent (III) described below varies depending on the polymer blocks (B) and (C), and thus, different soft and hard parts are present in the hydrogenated block copolymer (Q), and excellent effects such as tear strength and tensile properties can be exhibited. In addition, from the viewpoint of exhibiting significantly excellent tensile properties, it is more preferable that the above hydrogenation ratio of the polymer block (C) is higher than that of the polymer block (B).

[0159] It should be noted that in this specification, the polymer block (B) and the polymer block (C) in the hydrogenated block copolymer (Q) are hydrogenated, but they are expressed as "polymer block (B)" and "polymer block (C)" in the same manner as before hydrogenation.

[0160] The hydrogenation ratio of the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (B) in the hydrogenated block copolymer (Q) is preferably 70 to 98 mol%, more preferably 70 to 95 mol%, further preferably 70 to 95 mol%, still further preferably 70 to 95 mol%, and particularly preferably 80 to 95 mol%.

[0161] When the block copolymer (P) contains the polymer block (C), the hydrogenation rate of the carbon-carbon double bond in the conjugated diene-derived structural unit of the polymer block (C) in the hydrogenated block copolymer (Q) is preferably 95 to 99.9 mol%, more preferably 96 to 99.5 mol%, and still more preferably 97 to 99.5 mol%.

[0162] It should be noted that the hydrogenation rate can be calculated by measuring the 1 1H-NMR of the block copolymer (P) and the hydrogenated block copolymer (Q) after hydrogenation.

[0163] From the viewpoint of moldability, the peak molecular weight (Mp) of the block copolymer (P) is preferably 4,000 to 1,500,000, more preferably 9,000 to 1,000,000, still more preferably 30,000 to 800,000, and even more preferably 50,000 to 500,000.

[0164] The molecular weight distribution (Mw / Mn) of the block copolymer (P) is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and even more preferably 1 to 2. If the molecular weight distribution is within the above range, the viscosity deviation of the block copolymer (P) is small and it is easy to handle.

[0165] From the viewpoint of moldability, the peak molecular weight (Mp) of the hydrogenated block copolymer (Q) is preferably 4,000 to 1,500,000, more preferably 9,000 to 1,000,000, still more preferably 30,000 to 800,000, and even more preferably 50,000 to 500,000.

[0166] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (Q) is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and even more preferably 1 to 2. If the molecular weight distribution is within the above range, the viscosity deviation of the hydrogenated block copolymer (Q) is small and it is easy to handle.

[0167] It should be noted that the peak molecular weight (Mp) and the molecular weight distribution (Mw / Mn) in this specification refer to the values measured by the methods described in the following examples.

[0168] From the viewpoint of moldability, the peak 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 50,00, and even more preferably 6,000 to 30,000.

[0169] From the viewpoint of moldability, the peak molecular weight of the polymer block (B) is preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 4,000 to 100,000.

[0170] Furthermore, from the viewpoint of moldability, the peak molecular weight of the polymer block (C) is preferably 4,000 to 200,000, more preferably 4,500 to 150,000, and still more preferably 5,000 to 100,000.

[0171] In addition, the block copolymer (II) has a characteristic of being easily water-repellent. Specifically, the above-mentioned "ease of water repellency" can be evaluated by dropping water on a quartz plate, placing a molded body containing the block copolymer (II) thereon, and observing the state of the water when pressure is applied to the molded body from above from the side of the quartz plate. If it is a molded body containing the block copolymer (II), substantially all of the water present between the molded body and the quartz plate can be repelled.

[0172] More specifically, the ease of water repellency can be evaluated by the method described in the examples below.

[0173] [Crosslinking agent (III)]

[0174] The resin composition of the present embodiment contains a crosslinking agent (III).

[0175] As the crosslinking agent (III), it is preferable to carry out a crosslinking reaction only through the carbon-carbon double bond or its α-methylene group in the structural unit derived from a conjugated diene. Here, the α-methylene group means a methylene group adjacent to the carbon-carbon double bond. By containing such a crosslinking agent (III), only the above-mentioned carbon-carbon double bond or the α-methylene group of the carbon-carbon double bond (in the case of a hydrogenated block copolymer, the one remaining in the copolymer) in the block copolymer (II) undergoes crosslinking, and excellent flexibility can be maintained, it is not easily slippery, has excellent abrasion resistance, and good tensile properties and tear strength can also be expected.

[0176] Examples of the crosslinking agent (III) include, for example, radical generators, sulfur, and sulfur-containing compounds. From the viewpoints of tear strength and tensile properties, etc., sulfur and / or sulfur-containing compounds are more preferable, and sulfur is still more preferable.

[0177] As the radical generator, examples thereof include organic peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, 1,3-bis(tert-butylperoxyisopropyl)benzene, α,α'-bis(tert-butylperoxy)diisopropylbenzene, 3,3,5-trimethylcyclohexane, n-butyl 4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like. They may be used alone or in combination of two or more.

[0178] As sulfur, it can be used without particular limitation and can be any one of, for example, fine sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur and the like.

[0179] Examples of the sulfur-containing compound include sulfur monochloride, sulfur dichloride, disulfide compounds, triazine mercaptans and the like.

[0180] As the crosslinking agent (III), in addition, phenolic resins such as alkylphenol resins and brominated alkylphenol resins can also be used; combinations such as p-quinone dioxime and lead dioxide, and p,p'-dibenzoylquinone dioxime and lead tetraoxide can also be used.

[0181] [Content]

[0182] The mass ratio [(I) / (II)] of the aforementioned rubber (I) to the aforementioned block copolymer (II) is 99 / 1 to 55 / 45. If the mass ratio [(I) / (II)] is outside the above range, excellent abrasion resistance cannot be obtained. In addition, if the mass ratio is within the above range, the anti-slip property is more significantly exhibited. That is, if it is the above mass ratio, a resin composition capable of forming a molded body that is less likely to slip and has excellent abrasion resistance can be formed. Furthermore, in order to significantly improve the anti-slip property such as dry grip and wet grip and make the abrasion resistance more excellent, the above mass ratio is preferably 99 / 1 to 60 / 40, preferably 99 / 1 to 65 / 35, preferably 99 / 1 to 70 / 30, preferably 95 / 5 to 70 / 30.

[0183] By containing the block copolymer (II), flexibility is imparted to the resin composition. Therefore, there is a tendency that the higher the content ratio of the block copolymer (II), the higher the grip performance. However, it is known that within a specific range as shown by the above mass ratio [(I) / (II)], as the content ratio of the rubber (I) becomes higher than that of the block copolymer (II), the grip performance unexpectedly improves. Moreover, since excellent abrasion resistance is also exhibited, the resin composition of the present embodiment can be formed into a molded article excellent in both anti-slip properties and abrasion resistance.

[0184] From the viewpoint of easily making the anti-slip properties and abrasion resistance more excellent and also being able to exhibit a balance among flexibility, tear strength, and tensile properties, the content of the crosslinking agent (III) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6.0 parts by mass, further preferably 1.0 to 4.0 parts by mass, and still further preferably 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the total content of the rubber (I) and the block copolymer (II).

[0185] From the viewpoint of easily making the anti-slip properties and abrasion resistance more excellent and also being able to exhibit a balance among flexibility, tear strength, and tensile properties, the total content of the rubber (I), the block copolymer (II), and the crosslinking agent (III) in the resin composition of the present embodiment is preferably 60 to 80% by mass, more preferably 65 to 80% by mass.

[0186] [Other]

[0187] (Silica)

[0188] The resin composition of the present embodiment preferably contains silica.

[0189] Examples of the silica include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among these silicas, from the viewpoint of further improving the moldability, mechanical strength, and abrasion resistance of the obtained molded article and further improving the anti-slip properties such as dry grip performance and wet grip performance, wet silica is preferred. These silicas can be used alone or in combination of two or more.

[0190] From the viewpoint of making the grip performance more excellent, the specific surface area of the silica is preferably 20 m 2 / g or more, more preferably 50 m 2 / g or more, further preferably 100 m 2 / g or more, and still further preferably 150 m 2 / g or more. The upper limit value of the specific surface area of the silica is only required to be within a range that does not impair the effects of the present invention. Silicas having different specific surface areas as described above may also be used in combination. In particular, in order to make the anti-slip properties such as dry grip, wet grip, and ice grip more significantly excellent, it is preferable to contain the silica having a specific surface area of 150 m 2 / g or more. If a part of the silica contained in the resin composition (for example, 50% by mass or more of the total amount of the silica) has a specific surface area of 150 m 2 / g or more, even when used in combination with silica having a specific surface area of less than 150 m 2 / g, it is possible to expect to exhibit the above-mentioned significantly excellent grip properties.

[0191] The specific surface area of the above-mentioned silica can be measured by, for example, the BET method.

[0192] The content of the silica is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and further preferably 20 to 40 parts by mass based on 100 parts by mass in total of the rubber (I) and the block copolymer (II). If the content of the silica is within the above range, excellent mechanical strengths such as tear strength are exhibited, and the grip properties and abrasion resistance are further improved.

[0193] (Silane Coupling Agent)

[0194] The resin composition of the present embodiment preferably contains a silane coupling agent.

[0195] Examples of the silane coupling agent include, for example, thioether compounds, mercapto compounds, vinyl compounds, amino compounds, glycidyloxy compounds, nitro compounds, chlorine compounds, and the like.

[0196] In addition, from the viewpoint of reactivity with silica, the silane coupling agent preferably has an alkoxysilyl group, and among them, methoxysilane and ethoxysilane are preferable. These silane coupling agents can be used alone or in combination of two or more.

[0197] Examples of the thioether compounds include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, and 3-trimethoxysilylpropyl methacrylate monosulfide, etc.

[0198] Examples of the mercapto compounds include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl-bis(tridecane-1-oxy-13-penta(ethylene oxide))ethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane, etc.

[0199] Examples of the vinyl compounds include vinyltriethoxysilane and vinyltrimethoxysilane, etc.

[0200] Examples of the amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane, etc.

[0201] Examples of the glycidoxy compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane, etc.

[0202] Examples of the nitro compounds include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane, etc.

[0203] Examples of the chloro compounds include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane, etc.

[0204] Among these silane coupling agents, from the viewpoint of abrasion resistance, bis(3-triethoxysilylpropyl) disulfide, bis(3-triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane are preferred.

[0205] The content of the silane coupling agent is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, further preferably 1 to 20 parts by mass, and still more preferably 3 to 15 parts by mass with respect to 100 parts by mass of silica. If the content of the silane coupling agent is within the above range, the dispersibility and abrasion resistance in the composition are further improved.

[0206] (Polyolefin resin)

[0207] The resin composition of the present embodiment preferably does not contain a polyolefin resin or the content of the polyolefin resin is less than 10 parts by mass with respect to 100 parts by mass of the block copolymer (II). If the content is less than 10 parts by mass, melt kneading can be suitably performed. The resin composition of the present embodiment more preferably does not contain a polyolefin resin.

[0208] Examples of the polyolefin resin that can be contained include polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and the like.

[0209] (Crosslinking accelerator)

[0210] The resin composition of the present embodiment may contain a crosslinking accelerator.

[0211] Examples of the crosslinking accelerator include thiazoles such as N,N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, bis-2-benzothiazolyl disulfide, 2-(4-morpholinodithio)benzothiazole; guanidines such as diphenylguanidine, triphenylguanidine; aldehyde-amine reactants or aldehyde-ammonia reactants such as butyraldehyde-aniline reactant, hexamethylenetetramine-acetaldehyde reactant; imidazolines such as 2-mercaptoimidazoline; thioureas such as thiocarbanilide, diethylurea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea; thiuram mono- or polysulfides such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, pentamethylenetetramine tetrasulfide; thiocarbamates such as zinc dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate; xanthates such as zinc dibutylxanthate; salicylic acid, etc. These crosslinking accelerators can be used alone or in combination of two or more.

[0212] The content of the crosslinking promoter is preferably 0.05 to 15.0 parts by mass, more preferably 0.1 to 5.0 parts by mass, and further preferably 0.5 to 4.0 parts by mass, relative to a total of 100 parts by mass of the rubber (I) and the block copolymer (II).

[0213] (Filler)

[0214] The resin composition of the present embodiment may contain a filler other than the above-mentioned silica. As the aforementioned filler, an inorganic filler and / or an organic filler can be used. As a preferable inorganic filler, silicate compounds and metal oxides etc. can be preferably exemplified. The silicate compound is preferably at least one silicate compound selected from kaolin, talc, clay, pyrophyllite, mica, montmorillonite, bentonite, wollastonite, sepiolite, xonotlite, zeolite, diatomaceous earth, and halloysite. In addition, the metal oxide is at least one metal oxide selected from titanium oxide, iron oxide, magnesium oxide, aluminum oxide, cerium oxide, antimony oxide, tin oxide, lead oxide, chromium oxide, cobalt oxide, tungsten oxide, and copper oxide.

[0215] In addition, as a preferable organic filler, a particulate organic filler and / or a fibrous organic filler can be exemplified. As a preferable example of the aforementioned particulate organic filler, at least one organic filler selected from urethane fine particles, acrylic fine particles, styrene fine particles, acrylic / styrene-based fine particles, styrene olefin fine particles, fluorine-based fine particles, polyethylene-based fine particles, and silicone fine particles can be cited. From the viewpoint of the moldability of the composition, the preferable average particle diameter of the aforementioned particulate organic filler is 2 to 50 μm. It should be noted that the average particle diameter can be measured by the laser diffraction method based on JIS Z 8825-1.

[0216] As the aforementioned fibrous organic filler, various organic fibers can be used, and for example, 6-nylon fiber, 6,6-nylon fiber, 4,6-nylon fiber, aromatic polyamide fiber, para-aramid fiber, meta-aramid fiber, polyethylene terephthalate (PET) fiber, polyethylene naphthalate (PEN) fiber, poly(p-phenylene benzoxazole) (PBO) fiber, PVA-based fiber (vinylon), polyarylene sulfide-based fiber, 2,6-hydroxynaphthoic acid·p-hydroxybenzoic acid fiber (Vectran), polyethylene (PE) fiber, polypropylene (PP) fiber, polylactic acid (PLA) fiber, polybutylene succinate (PBS) fiber, polyethylene succinate fiber, syndiotactic-1,2-polybutadiene (SPB) fiber, polyvinyl chloride (PVC) fiber and other synthetic fibers, cotton, hemp, rayon, cellulose fiber and other natural (regenerated) fibers etc. can be preferably exemplified.

[0217] The aforementioned organic fibers can be roughly classified into organic microfibers and organic nanofibers according to their average fiber diameter. Organic microfibers are organic fibers with an average fiber diameter in the micron order. The average fiber diameter is preferably in the range of 1 to 200 μm, more preferably in the range of 10 to 100 μm, and further preferably in the range of 15 to 90 μm. In addition, the average fiber length of the organic microfibers is not particularly limited, and is preferably in the range of 0.1 to 20 mm, more preferably in the range of 0.5 to 15 mm, and further preferably in the range of 1 to 10 mm. By having this average fiber diameter and average length, the balance between the processability of the resin composition and the improvement effect of the obtained wet grip performance is excellent.

[0218] In addition, organic nanofibers are organic fibers with an average fiber diameter in the nanometer order. Regarding its average fiber diameter, the average fiber diameter is preferably in the range of 1 to 900 nm, more preferably in the range of 1 to 700 nm, and further preferably in the range of 1 to 500 nm. The average fiber length of the organic nanofibers is preferably in the range of 0.1 to 1000 μm, more preferably in the range of 1 to 750 μm, and further preferably in the range of 5 to 600 μm.

[0219] The types of the aforementioned organic microfibers and the aforementioned organic nanofibers are not particularly limited, and are preferably polyethylene terephthalate (PET) fibers, PVA-based fibers (vinylon), 2,6-hydroxynaphthoic acid / p-hydroxybenzoic acid fibers (Vectran), polylactic acid (PLA) fibers, and cellulose fibers. From the viewpoint of the effect of improving the grip performance, PVA-based fibers (vinylon) and cellulose fibers are more preferable, and cellulose fibers are further preferable. As the organic microfibers containing cellulose fibers, for example, cellulose-based microfibers sold under the product name "ARBOCEL" manufactured by Rettenmaier can be preferably exemplified. In addition, as the organic nanofibers containing cellulose fibers, for example, cellulose-based nanofibers such as Celish KY-100G (average fiber length: 500 μm, average fiber diameter: 20 nm, solid content: 10% by mass) manufactured by Daicel Finechem can be preferably exemplified.

[0220] The content of the above-mentioned filler is preferably 0 to 120 parts by mass, can be 0.5 to 80 parts by mass, can also be 1 to 50 parts by mass, and can further be 1 to 30 parts by mass relative to 100 parts by mass of the total content of the rubber (I) and the block copolymer (II).

[0221] (Softening agent)

[0222] The resin composition of the present embodiment may contain a softening agent within a range that does not impair the effects of the invention. However, since the resin composition has sufficient fluidity for molding processing due to the aforementioned constitution, it may not contain a softening agent. In particular, oil-based softening agents such as process oils, mineral oils, and white oils of the alkane series, naphthene series, and aromatic series among softening agents may exude oil over time when forming a molded body, so it is preferred not to contain them in the resin composition.

[0223] Examples of the softening agent that can be contained include phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; liquid copolymers of ethylene and α-olefins; liquid paraffin; polybutene; low molecular weight polyisobutylene; liquid polybutadiene, liquid polyisoprene, liquid β-farnesene, liquid polyisoprene / butadiene copolymer, liquid isoprene / β-farnesene, liquid butadiene / β-farnesene, liquid styrene / butadiene copolymer, liquid styrene / isoprene copolymer, etc., and hydrogenated products or modified products of liquid polyolefins.

[0224] When containing a softening agent, the content in the above resin composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 1.0 to 15% by mass.

[0225] (Other additives)

[0226] In the resin composition of the present embodiment, other additives other than the above additives can be added within a range that does not impair the effects of the present invention. Examples of other additives include heat aging resistant agents, antioxidants, light stabilizers, antistatic agents, mold release agents, flame retardants, foaming agents, pigments, dyes, brightening agents, etc. These additives can be used alone or in combination of two or more.

[0227] [Manufacturing method of resin composition]

[0228] In the manufacturing method of the resin composition of the present embodiment, it can be manufactured by, for example, melt-kneading each component except for the aforementioned crosslinking agent (III) and the crosslinking accelerator added as needed, and then crosslinking using the crosslinking method described later.

[0229] The method of melt-kneading the components except for the crosslinking agent (III) and the crosslinking accelerator added as required is not particularly limited, and examples include: a method of simultaneously supplying the rubber (I), block copolymer (II), and other optional components to a kneading device such as a single-screw extruder, multi-screw extruder, Banbury mixer, Brabender mixer, open mill, heating roll, various kneaders, etc., and performing melt-kneading. In addition, it may be a method of supplying the rubber (I), block copolymer (II), and other optional components from their respective feed ports and performing melt-kneading; or a method of pre-melt-kneading the block copolymer (II) with some optional components such as silica and silane coupling agent, and then melt-kneading the melt-kneaded product with other optional components, etc.

[0230] The temperature during melt-kneading can generally be arbitrarily selected within the range of 20 to 270 °C.

[0231] As the crosslinking method, examples include: after the above melt-kneading, adding the crosslinking agent (III) and the crosslinking accelerator added as required, using a vulcanization mold, and under the conditions that the vulcanization temperature is generally about 120 to 200 °C, preferably 140 to 200 °C, and the vulcanization pressure is generally about 0.5 to 10 MPa, usually maintaining for about 1 minute to 2 hours, thereby performing crosslinking, etc.

[0232] [Physical properties]

[0233] (Slip resistance)

[0234] The resin composition of this embodiment can evaluate the slip resistance by the static friction coefficient measured based on ASTM D-1894. The preferred numerical range of the static friction coefficient varies depending on the type of rubber (I) used and cannot be generalized. The larger the value of the static friction coefficient, the more difficult it is to slip. For example, when using SBR as the rubber (I), the static friction coefficient is preferably 4.5 or more, more preferably 5.0 or more under dry conditions. In addition, under wet conditions, it is preferably 1.5 or more, more preferably 2.0 or more.

[0235] Regarding the dry condition and wet condition, it refers to the measurement conditions described in the following examples.

[0236] (Abrasion resistance)

[0237] The resin composition of this embodiment can evaluate the abrasion resistance by the abrasion amount measured based on JIS K 6264-2:2005 using a DIN abrasion test (rotating cylinder type abrasion testing machine). The abrasion amount is preferably 200 mm 3 Hereinafter, more preferably 190 mm 3 Hereinafter, it can also be set to 180 mm 3 Hereinafter, 170 mm3 as follows

[0238] (Vulcanization rate)

[0239] When the resin composition of the present embodiment uses sulfur and / or a sulfur-containing compound as the crosslinking agent (III), excellent vulcanization rate, that is, a short time required for vulcanization (90% vulcanization time) can be expected.

[0240] If the vulcanization rate is fast, the viscosity of the resin composition during vulcanization increases rapidly, and plasticizers such as vulcanizing agents, crosslinking accelerators, crosslinking aids, antioxidants, anti-aging agents, and softeners, which are sulfur and / or sulfur-containing compounds in the resin composition, are not easily exuded to the surfaces of the rubber (I) and the block copolymer (II). Therefore, contamination of the processing mold can be suppressed.

[0241] In this specification, the vulcanization rate of the resin composition is set to the following time: According to JIS K 6300-2:2001, using a vibration vulcanization tester (CURELASTOMETER), the torque of the resin composition at 160 °C is measured, and the time required until the vulcanization amount reaches 90% (90% vulcanization time). As the vulcanization rate Tc(90) of the resin composition, it is preferably 13 minutes or less, more preferably 12 minutes or less. The lower limit is not particularly limited and is usually 1 minute or more.

[0242] (Specific gravity)

[0243] The specific gravity of the resin composition of the present embodiment measured based on ISO 1183:1987 is preferably 0.88 to 1.30, more preferably 0.90 to 1.20. If it is within the above range, the molded article containing the resin composition will not lack practicality. For example, when the resin composition is used for shoe soles, it will not become too heavy, and weight reduction of the shoes can be expected.

[0244] (Hardness)

[0245] The hardness of the resin composition of the present embodiment based on the type A durometer method of JIS K 6253-2:2012 (hereinafter also referred to as "A hardness") is preferably 90 or less, more preferably 85 or less. In addition, the A hardness is preferably 25 or more, more preferably 30 or more, and further preferably 35 or more. If the A hardness is within the above range, the molding processability becomes good and the flexibility is good. Therefore, the frictional force becomes high, and the grip and abrasion resistance also become excellent.

[0246] (Tensile fracture strength)

[0247] The tensile strength at break (tensile fracture strength) of the resin composition of the present embodiment measured based on JIS K 6251:2010 is preferably 5.0 MPa or more, more preferably 10.0 MPa or more, and further preferably 13.0 MPa or more. When the tensile fracture strength is 5.0 MPa or more, the tensile properties become good.

[0248] (Elongation at break)

[0249] The elongation at break (tensile fracture elongation) of the resin composition of the present embodiment measured based on JIS K 6251:2010 is preferably 100% or more, more preferably 150% or more, further preferably 200% or more, and even more preferably 370% or more. When the tensile fracture elongation is 100% or more, the tensile properties become good.

[0250] (Tear strength)

[0251] The tear strength (split strength) of the resin composition of the present embodiment measured based on JIS K 6252-1:2015 is preferably 2.0 kN / m or more, more preferably 2.5 kN / m or more, and further preferably 3.0 kN / m or more.

[0252] <Formed body>

[0253] The formed body in the present embodiment is obtained by using the above resin composition.

[0254] Regarding the shape of the formed body, as long as it is a formed body that can be manufactured using the above resin composition, it can be any shape, and can be formed into various shapes such as pellets, films, sheets, plates, pipes, tubes, rod-like bodies, granular bodies, etc. The manufacturing method of the formed body is not particularly limited, and it can be formed by various conventional forming methods such as injection molding, blow molding, compression molding, extrusion molding, calendering molding, etc. The above resin composition can particularly suitably obtain a compression molded body.

[0255] It is also expected that the above formed body is not prone to slipping, has excellent abrasion resistance, and has an excellent balance between tear strength and tensile properties. Therefore, it can be used for formed products that require these properties. In particular, it can be suitably used as formed products such as soles obtained by using the resin composition of the present embodiment at least in part.

[0256] Specifically, it can be suitably used for shoe soles for mountaineering shoes, slippers, safety boots, hiking boots, marathon running shoes, gum-soled socks, boots, etc.; sports goods such as goggles, snorkels, ski boots and snowboards; note-taking utensils such as pens and scissors, tools and electrical tools such as screwdrivers, pliers and wrenches, water-related supplies such as toothbrushes and kitchen utensils (such as kitchen knives and shovels), various handles such as golf clubs, the stock of skis, bicycles, motorcycles and other sports and fitness appliances, and knives, etc.; components of household appliances such as refrigerators, vacuum cleaners and waterproof bodies (such as mobile phones); automotive supplies such as side moldings, rack and pinion covers, spring seat covers, constant velocity joint covers, weather strips, fenders, floor mats, elbow rests, waistlines, ceiling lights and interior and exterior automotive decorations (such as gears and knobs); tread components of tires, especially winter tires, tubeless tires, all-weather tires, low fuel consumption tires and heavy load tires, etc.; office equipment such as feed rollers and take-up rollers of copiers; components used in furniture such as sofas and chairs; rubber components such as switch covers, brakes, rolling wheels and floor mat rubbers; building materials such as plywood covers and steel plate covers; industrial components such as industrial belts and industrial rubber hoses, etc. Examples

[0257] Hereinafter, the present invention will be described more specifically in Examples and Comparative Examples, but the present invention is not limited thereto. It should be noted that β-farnesene (purity 97.6 mass%, manufactured by Amylis, Incorporated) was refined using 3 Å molecular sieves and distilled under a nitrogen atmosphere to remove hydrocarbon impurities such as zingiberene, bisabolene, farnesene epoxide, farnesol isomers, E,E-farnesol, squalene, ergosterol and several dimers of farnesene, and used for the following polymerization.

[0258] <Rubber (I)>

[0259] ・ Rubber (I): SBR

[0260] Product name: JSR 1502, manufactured by JSR Corporation, styrene-butadiene copolymer rubber (E-SBR), manufactured by emulsion polymerization method, styrene content = 23.5 mass%.

[0261] <Block copolymer (II)>

[0262] ・ Hydrogenated block copolymer (II-1)

[0263] The hydrogenated block copolymer (II-1) of Production Example 1 described later

[0264] ・ Hydrogenated block copolymer (II-2)

[0265] The hydrogenated block copolymer (II-2) of Production Example 2 described later

[0266] ・Unhydrogenated block copolymer (II’-1)

[0267] The unhydrogenated block copolymer (II’-1) of Production Example 3 described below.

[0268] <Crosslinking agent (III)>

[0269] ・Sulfur: Micronized sulfur 200 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.

[0270] <Crosslinking accelerator>

[0271] ・Crosslinking accelerator (1): Product name Nocceler CZ, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., N-cyclohexyl-2-benzothiazolesulfenamide

[0272] ・Crosslinking accelerator (2): Product name Nocceler TT, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., tetramethylthiuram disulfide).

[0273] <Silica>

[0274] ・Silica (1): Product name ULTRASIL 7000GR, manufactured by Evonik Degussa Japan Co., Ltd., wet silica, BET specific surface area is 175 m 2 / g

[0275] ・Silica (2): Product name Nipsil VN3, manufactured by Tosoh Silica Corporation, wet silica, BET specific surface area is 200 m 2 / g

[0276] ・Silica (3): Product name Nipsil ER, manufactured by Tosoh Silica Corporation, wet silica, BET specific surface area is 70 - 100 m 2 / g.

[0277] <Silane coupling agent>

[0278] ・Silane coupling agent (1): Product name Si75, manufactured by Evonik Degussa Japan Co., Ltd., bis(3-triethoxysilylpropyl) disulfide

[0279] ・Silane coupling agent (2): Product name Si69, manufactured by Evonik Degussa Japan Co., Ltd., bis(3-triethoxysilylpropyl) tetrasulfide

[0280] ・Silane coupling agent (3): Product name Silquest A189, manufactured by Momentive, 3-mercaptopropyltrimethoxysilane.

[0281] <Other additives>

[0282] ・ Zinc oxide: 1 type of zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.

[0283] ・ Stearic acid: Product name is Lunaic S-20, manufactured by Kao Corporation.

[0284] [Measurement method]

[0285] Details of the measurement methods for each of the polymers obtained in the production examples are as follows.

[0286] (1) Measurement of peak molecular weight and molecular weight distribution

[0287] The peak molecular weight (Mp) and molecular weight distribution (Mw / Mn) of the styrene block and the polymer are determined in terms of the molecular weight converted to standard polystyrene by GPC (gel permeation chromatography), and the peak molecular weight (Mp) is determined from the position of the peak apex of the molecular weight distribution. The measurement apparatus and conditions are as follows.

[0288] ・ Apparatus: GPC apparatus “HLC-8320GPC” manufactured by Tosoh Corporation

[0289] ・ Separation column: Column “TSKgel SuperHZ4000” manufactured by Tosoh Corporation

[0290] ・ Eluent: Tetrahydrofuran

[0291] ・ Eluent flow rate: 0.7 mL / min

[0292] ・ Sample concentration: 5 mg / 10 mL

[0293] ・ Column temperature: 40 °C.

[0294] (2) Measurement method of hydrogenation rate

[0295] (2-1) The block copolymer (P) and the hydrogenated block copolymer (II) (referred to as “hydrogenated block copolymer (II)”) are separately dissolved in a deuterated chloroform solvent, and measured at 50 °C using “Lambda-500” manufactured by JEOL Ltd. 1 The 1H-NMR.

[0296] The hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene in the hydrogenated block copolymer (II) is calculated based on the peak of the proton possessed by the carbon-carbon double bond appearing at 4.5 to 6.0 ppm in the obtained spectrum and using the following formula.

[0297] Hydrogenation rate (mol%) = {1 - (number of moles of carbon-carbon double bonds contained in each 1 mole of hydrogenated block copolymer (II)) / (number of moles of carbon-carbon double bonds contained in each 1 mole of block copolymer (P))} × 100

[0298] (2-2) Further, regarding the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (B) and the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated dienes in the polymer block (C), based on the proton peaks appearing in each of the spectra obtained above, the calculation is carried out in the same manner as above.

[0299] (3) Contact area of water (ease of water repellency)

[0300] On a colorless and transparent quartz plate (5 cm × 5 cm) with a smooth surface, 1 mL of water added with food red is dropped, and a molded body containing the polymer produced in the production example (a circular planar sheet with a diameter of 25 mm and a thickness of 2 mm) is placed thereon, and a load of 2 kg is applied to this molded body using a tensile testing machine. It should be noted that food red is added to the water from the perspective of easy observation, which does not affect the ease of water repellency.

[0301] From the side of the quartz plate, visually observe the state of the water on the grounding surface of the molded body and the quartz plate, and evaluate according to the following evaluation criteria A to C.

[0302] A: Food red is not visible on the above-mentioned grounding surface

[0303] B: Food red is slightly visible on the above-mentioned grounding surface

[0304] C: A large amount of food red is visible on the above-mentioned grounding surface.

[0305] In addition, regarding the proportion of the grounding surface of the molded body and the quartz plate covered by water (coverage rate %), using image analysis software (manufactured by Mitani Corporation, product name "WinROOF ver.5.7.2"), perform image analysis on the observation image taken from the side of the quartz plate, and quantify it by the following formula.

[0306] Coverage rate % = [(area of the red region in the grounding surface of the molded body and the quartz plate) / (area of the grounding surface of the molded body and the quartz plate)] × 100.

[0307] [Production Example 1]

[0308] Hydrogenated block copolymer (II-1):

[0309] Into a pressure-resistant container purged 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 heating to 50 °C, 6.34 kg of β-farnesene was added and polymerization was carried out for 2 hours. Then, 2.50 kg of styrene (1) was added and polymerized for 1 hour. Further, 3.66 kg of butadiene was added and polymerized for 1 hour. Then, 0.02 kg of dichlorodimethylsilane as a coupling agent was added to the polymerization reaction solution and reacted for 1 hour, whereby a reaction solution containing a poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer (P1) was obtained.

[0310] To this reaction solution, 5 mass% of palladium carbon (palladium loading: 5 mass%) as a hydrogenation catalyst with respect to the aforementioned block copolymer (P1) was added, and the reaction was carried out at a hydrogen pressure of 2 MPa and 150 °C for 10 hours. After natural cooling and pressure release, the palladium carbon was removed by filtration, the filtrate was concentrated, and further dried under vacuum, whereby a hydride (II-1) of poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer (hereinafter referred to as "hydrogenated block copolymer (II-1)") was obtained.

[0311] For the obtained hydrogenated block copolymer (II-1), the above physical properties were measured. The results are shown in Table 1.

[0312] [Production Example 2]

[0313] Hydrogenated block copolymer (II-2):

[0314] Into a pressure-resistant container purged 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 anionic polymerization initiator were charged. After heating 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. Further, 1.12 kg of styrene (2) was added and polymerized for 1 hour, whereby a reaction solution containing a polystyrene-poly(β-farnesene)-polystyrene triblock copolymer (P2) was obtained.

[0315] To the reaction solution, 5% by mass of palladium-carbon (palladium loading: 5% by mass) as a hydrogenation catalyst relative to the aforementioned block copolymer (P2) was added, and the reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 °C. After natural cooling and pressure release, the palladium-carbon was removed by filtration, the filtrate was concentrated, and further dried under vacuum to obtain a hydrogenated product of polystyrene-poly(β-farnesene)-polystyrene triblock copolymer (hereinafter also referred to as "hydrogenated block copolymer (II-2)").

[0316] For the hydrogenated block copolymer (II-2), the above physical properties were measured. The results are shown in Table 1.

[0317] [Production Example 3]

[0318] Unhydrogenated block copolymer (II'-1):

[0319] 50.0 kg of cyclohexane as a solvent and 0.1010 kg of sec-butyllithium (10.5% by mass cyclohexane solution) as an anionic polymerization initiator were introduced into a nitrogen-purged and dried pressure-resistant container. After heating to 50 °C, 1.70 kg of styrene (1) was added and polymerized for 1 hour, 0.065 kg of N,N,N',N'-tetramethylethylenediamine (TMEDA) as a Lewis base was added, then 13.30 kg of isoprene was added and polymerized for 2 hours, and further 1.70 kg of styrene (2) was added and polymerized for 1 hour to obtain a reaction solution containing a styrene-isoprene-styrene triblock copolymer (P'1).

[0320] The polymerization reaction was terminated by adding 200 mL of methanol to the reaction solution. The resulting mixture was washed with water and then reprecipitated in a large amount of methanol to obtain a styrene-isoprene-styrene triblock copolymer (hereinafter also referred to as "unhydrogenated block copolymer (II'-1)").

[0321] For the unhydrogenated block copolymer (II'-1), the above physical properties were measured. The results are shown in Table 1.

[0322] [Table 1]

[0323] .

[0324] It should be noted that each expression in Table 1 is as follows.

[0325] *1: (A) / (B) represents the mass ratio of the content of polymer block (A) to the content of polymer block (B).

[0326] *2: (A) / ((B)+(C)) represents the mass ratio of the content of polymer block (A) to the total content of the respective contents of polymer block (B) and polymer block (C).

[0327] *3: (b1) / (B) represents the content (mass %) of the structural unit (b1) derived from farnesene in polymer block (B).

[0328] *4: ((b1)+(c1)) / ((B)+(C)) represents the total content (mass %) of structural unit (b1) and structural unit (c1) relative to the total amount of polymer block (B) and polymer block (C).

[0329] *5: F-St-Bd-St-F represents poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer.

[0330] St-F-St represents polystyrene-poly(β-farnesene)-polystyrene triblock copolymer.

[0331] St-Ip-St represents polystyrene-polyisoprene-polystyrene triblock copolymer.

[0332] *6: The hydrogenation rate of (II) represents the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated dienes in block copolymer (P).

[0333] *7: The hydrogenation rate of polymer block (B) represents the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated dienes in polymer block (B). Here, it only represents the case where there is polymer block (B).

[0334] *8: The hydrogenation rate of polymer block (C) represents the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated dienes in polymer block (C). Here, it only represents the case where there is polymer block (C).

[0335] [Examples 1 to 9][Comparative Examples 1 to 5]

[0336] (1) Melt kneading (manufacture of resin composition)

[0337] According to the compounding ratio (parts by mass) described in Table 3, each component except for the crosslinking agent (III) and the crosslinking accelerator was charged into a kneading roll (14-inch roll, manufactured by Kansai Roll Co., Ltd.) under the conditions shown in Table 2, and melt kneading was carried out (Steps 1 and 2). Thereafter, the melt kneaded product was taken out from the open mill roll (Step 3).

[0338] Next, the melt-kneaded mixture is put into a kneading roll (Step 4), a crosslinking agent (III) and a crosslinking accelerator are added (Step 5), and re-kneading is carried out and then taken out (Step 6), thereby obtaining a resin composition.

[0339] (2) Molding (manufacture of a molded article)

[0340] In addition, the resin composition obtained above is compression-molded (at 160 °C for 7 to 40 minutes) to be crosslinked, and a rubber sheet (thickness: 0.5 mm) is obtained.

[0341] Using the obtained resin composition or rubber sheet, physical properties are evaluated according to the following evaluation method. The results are shown in Table 3.

[0342] [Table 2]

[0343] .

[0344] [Evaluation method]

[0345] (Coefficient of static friction)

[0346] (1) Dry

[0347] According to ASTM D-1894, the coefficient of static friction on the surface of the rubber sheet of the resin composition obtained in the examples and comparative examples is measured.

[0348] A test piece with a length of 110 mm, a width of 63.5 mm, and a thickness of 0.5 mm is cut out from the above rubber sheet, wound around a box (weight: 200 g, 63.5 mm × 63.5 mm), and fixed to the head of an automatic plotter in such a way that the test piece stage of the friction coefficient measuring device is horizontal. The material of the friction table is set to aluminum, and the coefficient of static friction is measured at a tensile speed of 150 mm / min. The larger the value of the coefficient of static friction, the greater the frictional force, the less likely to slip, and the excellent dry grip performance.

[0349] (2) Wet

[0350] Except that 1 cc of distilled water is dripped onto the friction table, the coefficient of static friction is measured by the same method as in the above (1) dry method. The larger the value of the coefficient of static friction, the greater the frictional force, the less likely to slip, and the excellent wet grip performance.

[0351] (Abrasion resistance)

[0352] According to JIS K 6264-2:2005, the DIN abrasion amount is measured using a DIN abrasion test. The smaller the value, the more excellent the abrasion resistance.

[0353] (Vulcanization rate)

[0354] In the measurement of the vulcanization rate (Tc90), in accordance with JIS K 6300-2, using a vibration vulcanization testing machine (curastometer), the torque of the above resin compositions obtained in the examples and comparative examples at 160 °C was measured, and the vulcanization time when the vulcanization amount reached 90% was defined as the vulcanization rate (Tc90). The smaller the value, the more excellent the vulcanization rate.

[0355] (Specific gravity)

[0356] The measurement was carried out in accordance with ISO 1183:1987. In all the examples and comparative examples, the specific gravity was 1.1 g / cm 3 .

[0357] (Hardness)

[0358] Using a punching edge based on JIS K 6251:2010, dumbbell No. 3 test pieces (thickness 0.5 mm) were obtained from the rubber sheets of the resin compositions obtained in the examples and comparative examples.

[0359] Twelve of the obtained test pieces were overlapped to a thickness of 6 mm, and using the indenter of type A durometer, the hardness was measured in accordance with JIS K 6253-3:2012. It should be noted that the smaller the value of the hardness, the more excellent the softness.

[0360] (Tensile fracture strength and tensile fracture elongation)

[0361] Using dumbbell No. 3 test pieces (0.5 mm) prepared by the same method as the above (hardness) measurement, the tensile fracture strength and tensile fracture elongation were measured in accordance with JIS K 6251:2010. The larger the values of the tensile fracture strength and tensile fracture elongation, the more excellent the tensile properties.

[0362] (Tear strength)

[0363] In accordance with JIS K 6252-1:2015, using a punching edge, angular test pieces (thickness 0.5 mm) were obtained without cuts from the rubber sheets of the resin compositions obtained in the examples and comparative examples. Using the obtained test pieces, the tear strength was measured under the conditions of a tensile speed of 500 mm / min and a temperature of 23 °C. The larger the value, the more excellent the tear strength.

[0364] [Table 3]

[0365] .

[0366] From the comparisons between Examples 1 to 4 and Comparative Example 1, Examples 5 and 6 and Comparative Examples 3 and 4, and Example 9 and Comparative Example 5 respectively, it can be seen that by containing the block copolymer (II), the static friction coefficient becomes larger and the anti-slip property is excellent under any of dry and wet conditions.

[0367] In addition, from the comparison between Examples 1 and 4 and Comparative Example 2, it can be seen that by setting the mass ratio of the rubber (I) to the block copolymer (II) within a specific numerical range, excellent anti-slip property is maintained and the abrasion resistance is also excellent.

[0368] Furthermore, from all the examples shown in Table 3, it can be seen that if it is the resin composition of the present embodiment, a molded article with excellent anti-slip property, excellent abrasion resistance, and excellent balance of tear strength and tensile properties can be obtained.

[0369] [Examples 10 to 13][Comparative Examples 6, 7]

[0370] According to the compounding ratio (parts by mass) described in Table 4, the same procedure as in Example 1 was carried out to obtain a resin composition and a rubber sheet, and the physical properties were evaluated.

[0371] In addition, the rubber (I) and crosslinking accelerators (3) to (5) in Table 4 are as follows, and other materials are as described above.

[0372] <Rubber (I)>

[0373] ・ Rubber (I): BR

[0374] Product name: BR-01, manufactured by JSR Corporation, polybutadiene rubber (BR), weight average molecular weight (Mw) = 550,000, cis content = 95% by mass, vinyl content = 2.5% by mass.

[0375] <Crosslinking accelerator>

[0376] ・ Crosslinking accelerator (3): Product name: Nocceler DM, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., 2,2'-dibenzothiazolyl disulfide

[0377] ・ Crosslinking accelerator (4): Product name: Nocceler TBT, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., tetrabutylthiuram disulfide

[0378] ・ Crosslinking accelerator (5): Salicylic acid.

[0379] [Table 4]

[0380] 。

[0381] From the comparison between Examples 10 to 13 and Comparative Example 6, it can be seen that by containing the block copolymer (II), the static friction coefficient becomes larger and the anti-slip property is excellent under any of dry and wet conditions.

[0382] In addition, from the comparison between Examples 10 and 11 and Comparative Example 7, it can be seen that by setting the mass ratio of the rubber (I) to the block copolymer (II) within a specific numerical range, excellent anti-slip property is maintained and the abrasion resistance is also excellent.

[0383] Furthermore, from all the Examples shown in Table 4, it can be seen that if it is the resin composition of the present embodiment, a molded article with excellent anti-slip property, excellent abrasion resistance, and excellent balance of tear strength and tensile properties can be obtained.

[0384] [Example 14][Comparative Examples 8, 9]

[0385] According to the compounding ratio (parts by mass) described in Table 5, the same procedure as in Example 1 was carried out to obtain a resin composition and a rubber sheet, and the physical properties were evaluated.

[0386] In addition, the rubber (I) in Table 5 is as follows, and the other materials are as above.

[0387] <Rubber (I)>

[0388] ・ Rubber (I): NR

[0389] Natural rubber, produced in Indonesia, RSS No. 1.

[0390] [Table 5]

[0391] 。

[0392] From the comparison between Example 14 and Comparative Example 8, it can be seen that by containing the block copolymer (II), the static friction coefficient becomes larger and the anti-slip property is excellent under any of dry and wet conditions.

[0393] In addition, from the comparison between Example 14 and Comparative Example 9, it can be seen that by setting the mass ratio of the rubber (I) to the block copolymer (II) within a specific numerical range, excellent anti-slip property is maintained and the abrasion resistance is also excellent.

[0394] Furthermore, from Example 14, it can be seen that if it is the resin composition of the present embodiment, a molded article with excellent anti-slip property, excellent abrasion resistance, and excellent balance of tear strength and tensile properties can be obtained.

[0395] [Examples 15 to 20][Comparative Example 10]

[0396] According to the compounding ratio (parts by mass) described in Table 6, the same procedure as in Example 1 was carried out to obtain a resin composition and a rubber sheet, and the physical properties were evaluated.

[0397] In addition, the materials in Table 6 are as shown above.

[0398] [Table 6]

[0399] 。

[0400] From the comparison between Examples 15 to 20 and Comparative Example 10, it can be seen that: even when using a combination of multiple rubbers (I), by containing the block copolymer (II), the static friction coefficient becomes larger and the anti-slip property is excellent under any of the dry and wet conditions.

[0401] Furthermore, from all the examples shown in Table 6, it can be seen that: if it is the resin composition of the present embodiment, a molded article with excellent anti-slip property, excellent abrasion resistance, and excellent balance between tear strength and tensile properties can be obtained.

[0402] [Examples 21 to 33][Comparative Examples 11, 12]

[0403] According to the compounding ratio (parts by mass) described in Tables 8 and 9, the same procedure as in Example 1 was carried out to obtain a resin composition and a rubber sheet, and the physical properties were evaluated.

[0404] In addition, the softeners in Tables 8 and 9 are the softeners produced in Production Examples 4 to 8 below. The filler (cellulose fiber) in Table 9 is as shown below, and the other materials are as shown above.

[0405] <Softener>

[0406] [Production Example 4]

[0407] Poly-β-farnesene (IV-1):

[0408] 40 kg of hexane as a solvent and 0.55 kg of n-butyllithium (17% by mass hexane solution) as an initiator were charged into a pressure-resistant container purged with nitrogen and dried, and after heating to 50 °C, 40 kg of β-farnesene was added and polymerized for 1 hour. The obtained polymerization reaction solution was treated with methanol and washed with water. The washed polymerization reaction solution was separated from water and dried at 70 °C for 12 hours to obtain poly-β-farnesene (IV-1) having the physical properties shown in Table 7.

[0409] It should be noted that the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were measured in the same manner as in the above [Measurement Method].

[0410] [Production Example 5]

[0411] Poly-β-farnesene (IV-2):

[0412] Into a pressure-resistant container purged with nitrogen and dried, 40 kg of hexane as a solvent and 1.84 kg of n-butyllithium (17% by mass hexane solution) as an initiator were introduced. After heating to 50 °C, 40 kg of β-farnesene was added and polymerized for 1 hour. The resulting polymerization reaction solution was treated with methanol and the polymerization reaction solution was washed with water. The washed polymerization reaction solution was separated from water and dried at 70 °C for 12 hours to obtain poly-β-farnesene (IV-2) having the physical properties shown in Table 7.

[0413] It should be noted that the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were measured in the same manner as in the above [measurement method].

[0414] [Production Example 6]

[0415] Butadiene-β-farnesene copolymer (IV-3):

[0416] Into a pressure-resistant container purged with nitrogen and dried, 40 kg of hexane as a solvent and 0.72 kg of n-butyllithium (17% by mass hexane solution) as an initiator were introduced. After heating to 50 °C, a mixture of 24.0 kg of β-farnesene and 16.0 kg of butadiene prepared in advance was added and polymerized for 1 hour. The resulting polymerization reaction solution was treated with methanol and the polymerization reaction solution was washed with water. The washed polymerization reaction solution was separated from water and dried at 70 °C for 12 hours to obtain a butadiene-β-farnesene copolymer (IV-3) having the physical properties shown in Table 7.

[0417] It should be noted that the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were measured in the same manner as in the above [measurement method].

[0418] [Production Example 7]

[0419] Hydrogenated polyisoprene (IV-4):

[0420] Into a pressure-resistant container purged with nitrogen and dried, 40 kg of hexane as a solvent and 0.77 kg of n-butyllithium (17% by mass hexane solution) as an initiator were introduced. After heating to 50 °C, 40 kg of isoprene was added and polymerized for 1 hour. The resulting polymerization reaction solution was treated with methanol and the polymerization reaction solution was washed with water. The washed polymerization reaction solution was separated from water and dried at 70 °C for 12 hours to obtain polyisoprene.

[0421] 40 kg of the above polyisoprene was mixed with 50 kg of cyclohexane as a solvent in an autoclave, and the temperature was raised to 50 °C. Next, a substance obtained by mixing triisobutylaluminum and nickel 2-ethylhexanoate in a molar ratio of 3:1 was used as a hydrogenation catalyst, and 1.5×10 -3 times the molar amount of nickel metal constituting the hydrogenation catalyst was added relative to the total number of moles of unsaturated bonds contained in the above polyisoprene, and the temperature was raised to 80 °C. In order to maintain the hydrogen pressure at 1.0 MPa, hydrogen was continuously supplied while stirring at any time, and the reaction was carried out for 10 hours. After natural cooling and pressure release, triisobutylaluminum and nickel 2-ethylhexanoate were removed by filtration, and the filtrate was concentrated and dried under vacuum to obtain hydrogenated polyisoprene (IV-4) having the physical properties shown in Table 7.

[0422] It should be noted that the number average molecular weight (Mn), molecular weight distribution (Mw / Mn), and hydrogenation rate (mol%) were measured in the same manner as the above [measurement method].

[0423] [Production Example 8]

[0424] Modified liquid polyisoprene (IV-5):

[0425] 40 kg of hexane and 0.90 kg of n-butyllithium (17% by mass hexane solution) were put into a nitrogen-purged and dried pressure-resistant container, and after the temperature was raised to 70 °C, 41 kg of isoprene was added and polymerized for 1 hour. After adding methanol to the obtained polymerization reaction solution, the polymerization reaction solution was washed with water. The water was separated, and the polymerization reaction solution was dried under vacuum at 70 °C for 12 hours to obtain unmodified polyisoprene (IV-5). Next, 30 kg of unmodified polyisoprene (IV-5) and 0.45 kg of maleic anhydride were added, and the reaction was carried out at 160 °C for 20 hours to obtain maleic anhydride-modified liquid polyisoprene (IV-5) having the physical properties shown in Table 7.

[0426] It should be noted that the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured in the same manner as the above [measurement method].

[0427] The reaction rate of the modifier was 99%, and the functional groups added in the modified liquid polyisoprene (IV-5) were 1.5 parts by mass relative to 100 parts by mass of the unmodified polymer.

[0428] [Cellulose fiber]

[0429] ・Cellulose fiber: Product name ARBOCEL-BWW40, manufactured by Rettenmaier & Söhne GmbH + Co. KG, fiber length 200 μm, fiber diameter 20 μm, fiber density 110 - 145.

[0430] [Table 7]

[0431] .

[0432] [Table 8]

[0433] .

[0434] When comparing Comparative Example 11 with Example 21, the static friction coefficient under dry conditions increases. In Examples 22 to 30 to which a softening agent is added, even under wet conditions on the basis of the dry conditions, the static friction coefficient also increases. The reason is not clear yet, but it can be speculated that: if the content of NR increases, the viscosity difference between the various rubbers (I) and the block copolymer (II) increases, and by adding a softening agent, the viscosity of the rubber component decreases and the viscosity difference becomes smaller, thereby improving the dispersibility.

[0435] Furthermore, according to all the examples shown in Table 8, it can be known that: if it is the resin composition of the present embodiment, a molded article that is not prone to slipping, has excellent abrasion resistance, and has an excellent balance between tear strength and tensile properties can be obtained.

[0436] [Table 9]

[0437] .

[0438] When comparing Comparative Example 12 with Example 31, the static friction coefficient of Example 31 containing the block copolymer (II-1) is excellent. The grip of Example 32 in which a part of the silica (1) of Example 31 is replaced with cellulose fiber is further improved. In addition, Example 33 in which a part of the softening agent of Example 32 is replaced with modified liquid polyisoprene (IV-5) not only maintains the static friction coefficient of Example 32, but also the value of the DIN abrasion amount becomes smaller.

[0439] Industrial Applicability

[0440] The resin composition of the present invention can be made into a molded article that is not prone to slipping and has excellent abrasion resistance. Furthermore, an excellent balance between tear strength and tensile properties can be expected. Therefore, the resin composition of the present invention can be suitably used for shoe soles; sports goods; various handles such as writing utensils, tools, and electric tools; parts of household appliances such as refrigerators; automotive supplies such as side moldings; tread components such as tires; office equipment such as winding rollers; parts used in furniture such as sofas; rubber components such as floor mat rubbers; building materials such as plywood coverings and steel plate coverings; industrial components such as industrial belts, etc.

Claims

1. A resin composition comprising a rubber (I), a block copolymer (II), and a crosslinking agent (III), wherein the mass ratio [(I) / (II)] of the rubber (I) to the block copolymer (II) is from 99 / 1 to 55 / 45, the total content of the rubber (I), the block copolymer (II), and the crosslinking agent (III) in the resin composition is 60 to 80% by mass, the rubber (I) is at least one selected from natural rubber (NR), styrene-butadiene copolymer rubber (SBR), and polyisoprene rubber (BR), the block copolymer (II) is a block copolymer comprising a polymer block (A) and a polymer block (B), the polymer block (A) contains a structural unit derived from an aromatic vinyl compound, and the polymer block (B) contains a structural unit (b1) derived from farnesene, the crosslinking agent (III) is sulfur and / or a sulfur-containing compound, the content of the crosslinking agent (III) is 0.5 to 6.0 parts by mass with respect to 100 parts by mass of the total content of the rubber (I) and the block copolymer (II), and the composition does not contain a polyolefin resin.

2. The resin composition according to claim 1, wherein The mass ratio [(I) / (II)] of the rubber (I) to the block copolymer (II) is from 99 / 1 to 70 / 30.

3. The resin composition according to claim 1 or 2, wherein The block copolymer (II) further comprises a polymer block (C), and the polymer block (C) contains a structural unit (c2) derived from a conjugated diene other than farnesene.

4. The resin composition according to claim 3, wherein, The block copolymer (II) 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), and has at least one of the polymer blocks (B) at the terminal.

5. The resin composition according to claim 1 or 2, wherein The block copolymer (II) is a hydrogenated block copolymer (Q) in which 70 mol% or more of the carbon-carbon double bonds in the structural units derived from conjugated dienes are hydrogenated.

6. The resin composition according to claim 3, wherein, The block copolymer (II) is a hydrogenated block copolymer (Q) in which 70 mol% or more of the carbon-carbon double bonds in the structural units derived from conjugated dienes are hydrogenated. The hydrogenation rates of the carbon-carbon double bonds in the structural units derived from conjugated dienes of the polymer block (B) and the polymer block (C) are different.

7. The resin composition according to claim 1 or 2, wherein The content of the crosslinking agent (III) is 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the total content of the rubber (I) and the block copolymer (II).

8. The resin composition according to claim 1 or 2, further comprising silica.

9. The resin composition according to claim 1 or 2, further comprising a silane coupling agent.

10. The resin composition according to claim 1 or 2, wherein The rubber (I) contains at least natural rubber and also contains a softening agent.

11. The resin composition according to claim 1 or 2, having a wear amount of 200 mm or less as measured according to JIS K 6264-2:2005 by a DIN abrasion test. 3 Hereinafter.

12. A molded article which is a molded article of the resin composition according to any one of claims 1 to 11.

13. A sole which uses the resin composition according to any one of claims 1 to 11 in at least a part thereof.

Images