Rubber composition for outsole and outsole

Abstract

The present invention provides a rubber composition for an outsole, which contains a rubber, a filler, and an adhesion imparting agent.

Description

TECHNICAL FIELD

[0001] The present application relates to a rubber composition for outsoles and an outsole. BACKGROUND

[0002] As one of the important characteristics of an outsole of a shoe, the grip performance has been cited in the past, and there has been a demand for further improvement. As of now, technologies related to outsoles aimed at improving the grip performance have been disclosed.

[0003] For example, Patent Literature 1 discloses a technology related to a rubber composition and an outsole in which tan δ, which is an index of viscoelasticity, is improved by using a specific silane coupling agent on the basis of a prescribed composition ratio, and the grip performance is improved.

[0004] In addition, Patent Literature 2 discloses a technology related to a rubber composition and an outsole in which the grip performance is improved by using a cyclic olefin ring-opening polymer containing a terminal-modified group and by prescribing the glass transition temperature.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application No. 2017-549835

[0008] Patent Literature 2: Japanese Patent Application No. 2015-72532 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] However, the rubber compositions described in Patent Literature 1 and Patent Literature 2 have a problem in that there is room for improvement when they are applied to outsoles of sports shoes and the like that require more excellent grip performance.

[0011] According to the research by the present inventors on the properties of materials that contribute to the grip performance of a shoe, the adhesion of the surface that comes into contact with the ground is important. On the other hand, if the amount of a plasticizer such as oil added to a rubber composition is increased in order to improve the adhesion, there is a problem in that the wear resistance or the strength of the rubber composition significantly decreases, and the durability of the outsole deteriorates.

[0012] Therefore, in view of the problems of the related art described above, an object of the present application is to provide a rubber composition for outsoles in which the strength and the wear resistance are good in practical terms, and an outsole in which excellent grip performance is obtained.

[0013] MEANS FOR SOLVING THE PROBLEMS

[0014] In order to solve the problems of the prior art, the inventors conducted in-depth research and found that by mixing an adhesive into a rubber composition containing rubber and fillers, it is possible to provide a rubber composition for outsoles that can improve adhesion without reducing abrasion resistance and strength, thus completing the present invention.

[0015] That is, the present invention is as follows. [1]

[0017] A rubber composition for outsoles, comprising: rubber; Filler; and Adhesive. [2]

[0019] The rubber composition for outsole described above [1] contains a conjugated diene polymer as the rubber. [3]

[0021] According to the rubber composition for outsoles described above [2], wherein the conjugated diene polymer contains aromatic vinyl monomer units and conjugated diene monomer units. [4]

[0023] According to the rubber composition for outsoles described above [3], the content of aromatic vinyl monomer units in the conjugated diene polymer is 10% or more and 60% or less by mass, and the vinyl bonding content is 20% or more and 70% or less. [5]

[0025] According to the rubber composition for outsoles described in [3] or [4] above, the content of aromatic vinyl monomer blocks in the conjugated diene polymer is less than 5% by mass. [6]

[0027] According to any one of the above [1] to [5] rubber compositions for outsoles, wherein the content of the filler is 15 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the rubber. [7]

[0029] The rubber composition for outsole according to any one of [1] to [6] above contains 80% by mass or more of silica relative to the total mass of the filler. [8]

[0031] The rubber composition for outsole according to any one of [1] to [7] above, wherein the softening point of the tackifier is 40 to 170°C. [9]

[0033] The composition for outsole according to any one of [1] to [8] above, wherein the glass transition temperature of the tackifier is -20°C or higher.

[10]

[0035] The rubber composition for outsole according to any one of [1] to [9] above, wherein the tackifier is a terpene compound and / or a petroleum hydrocarbon compound.

[11]

[0037] The outsole composition according to any one of [1] to

[10] above, wherein the above-mentioned adhesive b The value is below 50.

[12]

[0039] According to the rubber composition for outsoles described in

[10] or

[11] above, wherein the petroleum hydrocarbon compound is an aromatic petroleum hydrocarbon resin or an alkylphenol.

[13]

[0041] The rubber composition for outsole according to any one of [1] to

[12] above, wherein the mixture of the rubber and the tackifier has a Tg of one in differential scanning calorimetry (DSC).

[14]

[0043] The rubber composition for outsole according to any one of [2] to

[13] above, wherein the tackifier is a terpene compound, the content of aromatic vinyl monomer units of the conjugated diene polymer is 10% by mass or more and 50% by mass or less, and the vinyl bonding amount is 24% by more and 60% or less.

[15]

[0045] The rubber composition for outsole according to any one of [2] to

[14] above, wherein the tackifier is a petroleum hydrocarbon compound, the content of aromatic vinyl monomer units of the conjugated diene polymer is 20% or more by mass and 60% or less by mass, and the vinyl bonding amount is 20% or more and 55% or less.

[16]

[0047] The rubber composition for outsole according to any one of [1] to

[15] above, wherein the difference between the glass transition temperature of the rubber and the tackifier is 10°C or more and 180°C or less.

[17]

[0049] According to any one of the above-mentioned rubber compositions for outsoles [1] to

[16] , the content of the tackifier in the rubber composition for outsoles is 1 part by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the rubber.

[18]

[0051] The outsole rubber composition according to any one of [1] to

[17] above, wherein the haze is 50% or less.

[19]

[0053] The outsole rubber composition according to any one of [1] to

[18] above, wherein the rubber contains 10% by mass or more and less than 60% by mass of nitrile rubber as the rubber.

[20]

[0055] The outsole rubber composition according to any one of [1] to

[19] above, wherein the rubber contains 10% by mass and 90% by mass of epichlorohydrin rubber as the rubber. [twenty one]

[0057] The outsole rubber composition according to any one of [1] to

[20] above, wherein the rubber contains 10% by mass and 90% by mass of urethane rubber as the rubber. [twenty two]

[0059] The outsole rubber composition according to any one of [1] to

[21] above, wherein the rubber contains 10% by mass and 90% by mass of chlorosulfonated vinyl rubber as the rubber. [twenty three]

[0061] The outsole rubber composition according to any one of [1] to

[22] above, wherein the rubber contains 10% by mass and 90% by mass of acrylic rubber as the rubber. [twenty four]

[0063] The outsole rubber composition according to any one of [1] to

[23] above, wherein the rubber contains 10% by mass and 90% by mass of silicone rubber as the rubber.

[25]

[0065] The outsole rubber composition according to any one of [1] to

[24] above, wherein the rubber contains 10% by mass and 90% by mass of fluororubber as the rubber.

[26]

[0067] The rubber composition for outsole according to any one of [2] to

[25] above, wherein the conjugated diene polymer comprises polybutadiene and styrene-butadiene copolymer.

[27]

[0069] An outsole, which is a molded body of the rubber composition for outsole described in any one of [1] to

[26] above.

[0070] The effects of the invention

[0071] According to the present invention, it is possible to provide a rubber composition for outsoles and an outsole that has good practical strength, abrasion resistance, and excellent grip. Detailed Implementation

[0072] The specific embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail below.

[0073] It should be noted that the following embodiments are illustrative of the present invention, and the present invention is not limited to the following embodiments. The present invention can be suitably modified within the scope of its essential points.

[0074] [Rubber composition for outsole]

[0075] The rubber composition for the outsole in this embodiment contains rubber, filler, and tackifier.

[0076] In this manual, the outsole refers to the part of the shoe that comes into contact with the ground.

[0077] By designing the outsole to exert adhesion when in contact with the ground, that is, the outsole is attracted to the floor surface and does not leave the floor surface, the outsole is not easy to slip and can achieve excellent grip.

[0078] By using the rubber composition for outsoles of this embodiment, adhesion when used as an outsole can be improved without adding plasticizers, and it has practically good strength, abrasion resistance, and excellent grip.

[0079] Even when methods for improving tire grip are applied to the outsole to achieve excellent grip, sufficient grip is sometimes not obtained. This is believed to be because the mechanisms of grip performance differ between the tire and the outsole. Regarding the tire, energy loss due to tire deformation has a significant impact on grip performance, making it important to improve tanδ (0℃, 106Hz) in viscoelasticity measurements. Conversely, for the outsole, improving adhesion is crucial.

[0080] (rubber)

[0081] From the perspective of balancing abrasion resistance and grip performance, the outsole rubber composition of this embodiment contains rubber.

[0082] The aforementioned rubber may be either natural rubber or synthetic rubber.

[0083] Synthetic rubbers include, but are not limited to, polybutadiene rubber (BR), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (HSBR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), chloroprene rubber, butyl rubber (IIR), its bromides or chlorides, ethylene-propylene-diene rubber (EPDM), epichlorohydrin rubber (ECO), urethane rubber (U), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM), silicone rubber (Q), fluororubber (FKM), etc., as well as thermoplastic elastomers and thermosetting elastomers.

[0084] The rubber composition for the outsole in this embodiment may contain one type of rubber alone, or two or more types of rubber may be used together.

[0085] Furthermore, regarding the rubber content in the rubber composition for the outsole of this embodiment, from the perspective of elasticity and softness, it is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. On the other hand, from the perspective of cost and processability, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0086] From the perspectives of balancing abrasion resistance and grip, cost, and supply stability, the rubber composition for the outsole of this embodiment preferably contains at least one selected from the group consisting of polybutadiene rubber (BR), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), chloroprene rubber, butyl rubber (IIR), its bromide (BIIR) or chloride (CIIR), and ethylene-propylene-diene rubber (EPDM). In particular, from the perspective of ease of crosslinking, it is preferable to contain conjugated diene polymers comprising conjugated diene monomer units, as described later.

[0087] (Conjugated diene polymers)

[0088] The rubber composition for the outsole in this embodiment preferably contains a conjugated diene polymer as the rubber.

[0089] From the perspective of abrasion resistance of the outsole, the content of the conjugated diene polymer relative to the total rubber content is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. On the other hand, from the perspective of oil resistance of the outsole of this embodiment, it is preferably 100% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0090] Conjugated diene polymers contain at least structural units derived from conjugated diene compounds (hereinafter also referred to as "conjugated diene monomer units").

[0091] Examples of conjugated diene compounds include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene.

[0092] Among these, 1,3-butadiene and isoprene are preferred from the perspective of ease of industrial acquisition, with 1,3-butadiene being more preferred.

[0093] Furthermore, from the perspective of good winding properties for rollers used in the mixing of crosslinking agents and outsole compositions, conjugated diene polymers are preferably copolymers of aromatic vinyl compounds and conjugated diene compounds.

[0094] That is, the conjugated diene polymer preferably contains structural units derived from aromatic vinyl compounds (hereinafter also referred to as "aromatic vinyl monomer units").

[0095] Examples of aromatic vinyl compounds include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinyl ethylbenzene, vinyl xylene, vinyl naphthalene, and diphenylethylene.

[0096] Of these, styrene is preferred from the perspective of ease of industrial acquisition.

[0097] Conjugated diene polymers can be polymers containing only conjugated diene monomer units, or copolymers containing both conjugated diene monomer units and aromatic vinyl monomer units. To improve processability and the reproducibility of the physical properties of the rubber composition, it is preferable to have fewer other constituent components besides the conjugated diene monomer units and aromatic vinyl monomer units.

[0098] From the perspective of the elasticity of the rubber composition for the outsole in this embodiment, the total content of conjugated diene monomer units and aromatic vinyl monomer units in the conjugated diene polymer is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and even more preferably 100% by mass.

[0099] When the conjugated diene polymer is a copolymer of a conjugated diene compound and an aromatic vinyl compound, it is preferable to control the microstructure, such as the content of aromatic vinyl monomer units and the amount of 1,2-vinyl bonds.

[0100] Regarding the content of aromatic vinyl monomer units in the conjugated diene polymer, from the perspective of the strength and hardness of the rubber composition for outsoles in this embodiment, it is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Furthermore, in the case of outsoles with high transparency, it is preferably 40% by mass or more, more preferably 41% by mass or more, and even more preferably 42% by mass or more. Furthermore, from the perspective of the moldability and pulverability of the conjugated diene polymer block, it is preferably 63% by mass or less, more preferably 60% by mass or less, more preferably 58% by mass or less, even more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0101] The content of aromatic vinyl monomer units can be controlled within the above-mentioned range by adjusting the amount of aromatic vinyl compounds added during polymerization.

[0102] The 1,2-vinyl bond amount is the molar ratio of the 1,2-vinyl bond amount based on the content of conjugated diene monomer units. From the perspective of the processability, crosslinking and softness of the rubber composition for the outsole of this embodiment, it is preferably 18% or more, more preferably 20% or more, further preferably 22% or more, and even more preferably 24% or more.

[0103] On the other hand, from the perspective of ease of polymerization and difficulty of gelation of conjugated diene polymers, it is preferable to have 70% or less, more preferably 65% ​​or less, further preferably 63% or less, and even more preferably 60% or less.

[0104] The amount of 1,2-vinyl bonds can be controlled within the above-mentioned range by adjusting the reaction initiation temperature, reaction termination temperature, type and amount of polar substances added during the polymerization of conjugated diene polymers.

[0105] The content of aromatic vinyl monomer units and the amount of 1,2-vinyl bonds in conjugated diene polymers can be determined by the methods described in the examples below.

[0106] Furthermore, the conjugated diene polymer may contain aromatic vinyl monomer blocks. When the conjugated diene polymer contains aromatic vinyl monomer blocks, from the perspective of the abrasion resistance of the outsole rubber composition of this embodiment, the content of aromatic vinyl monomer blocks relative to the conjugated diene polymer is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. On the other hand, from the perspective of the polymerization stability of the conjugated diene polymer, it is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1.15% by mass or more.

[0107] The content of aromatic vinyl monomer blocks in conjugated diene polymers can be determined by a known method, which involves decomposing the copolymer using the osmium tetroxide decomposition method described in IM Kolthoff, et al., J. Polym. Sci. 1, 429 (1946) and analyzing the amount of styrene blocks that are insoluble in methanol.

[0108] The content of aromatic vinyl monomer blocks can be controlled within the above-mentioned range by adjusting the amount and timing of addition of aromatic vinyl compounds during polymerization.

[0109] Furthermore, the conjugated diene polymer contained in the rubber composition for the outsole of this embodiment can be hydrogenated. The method for hydrogenating the conjugated diene polymer is not particularly limited; for example, the method described in International Publication No. 2021 / 206068 can be used.

[0110] <Content of copolymers of conjugated diene compounds and aromatic vinyl compounds>

[0111] As the rubber constituting the outsole rubber composition of this embodiment, the conjugated diene polymer can be used alone or in combination with two or more.

[0112] When at least one of the conjugated diene polymers is a copolymer of a conjugated diene compound and an aromatic vinyl compound, from the perspective of the grip of the outsole rubber composition of this embodiment, the content of the copolymer of the conjugated diene compound and the aromatic vinyl compound is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more relative to the total rubber. Furthermore, from the perspective of the transparency of the outsole rubber composition of this embodiment, it is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more relative to the total rubber. Moreover, from the perspective of transparency, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less relative to the total rubber.

[0113] <Molecular weight of conjugated diene polymers>

[0114] From the perspectives of shape stability, tensile strength, and abrasion resistance of the outsole rubber composition of this embodiment, the weight-average molecular weight of the conjugated diene polymer is preferably 150,000 or more, more preferably 200,000 or more. On the other hand, from the perspective of processability of the outsole rubber composition of this embodiment, it is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 400,000 or less.

[0115] Regarding the molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the conjugated diene polymer, from the perspective of the tensile strength of the rubber composition for outsoles in this embodiment, it is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.6 or less. On the other hand, from the perspective of the processability of the rubber composition for outsoles in this embodiment, the molecular weight distribution of the conjugated diene polymer is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.20 or more.

[0116] The weight-average molecular weight and molecular weight distribution can be calculated from the molecular weight of polystyrene determined by GPC (gel permeation chromatography).

[0117] Mooney viscosity of conjugated diene polymers

[0118] Regarding the Mooney viscosity of the aforementioned conjugated diene polymer, from the perspective of processability of the outsole rubber composition of this embodiment, it is preferably 120 or less, more preferably 90 or less, and even more preferably 60 or less. On the other hand, from the perspective of abrasion resistance of the outsole rubber composition of this embodiment, it is preferably 30 or more, more preferably 40 or more, and even more preferably 45 or more.

[0119] <Coupling-type conjugated diene polymers>

[0120] Regarding the conjugated diene polymer used as the rubber in the outsole rubber composition of this embodiment, it can be a coupling type conjugated diene polymer, which is obtained by coupling the active ends of the conjugated diene polymer obtained through a polymerization process with a reactive compound with two or more functions (hereinafter also referred to as a "coupling agent").

[0121] Examples of coupling agents include, but are not limited to, coupling agents having one or more functional groups selected from epoxy, carbonyl, carboxylic ester, carboxylic amide, acid anhydride, phosphate ester, phosphite, cyclosulfide, thiocarbonyl, thiocarboxylic ester, dithiocarboxylic ester, thiocarboxylic amide, imino, ethyleneimino, halogen, alkoxysilyl, isocyanate, thioisocyanate, conjugated diene, aryl vinyl, etc.

[0122] Examples of coupling agents include, but are not limited to, halosilane compounds such as silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, monomethyl silicon trichloride, monoethyl silicon trichloride, monobutyl silicon trichloride, monohexyl silicon trichloride, monomethyl silicon tribromide, bis(trichlorosilyl)ethane, monochlorotrimethoxysilane, monobromotrimethoxysilane, dichlorodimethoxysilane, dibromodimethoxysilane, trichloromethoxysilane, and tribromomethoxysilane.

[0123] In addition, examples of coupling agents include, but are not limited to, alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and alkyltriphenoxysilane.

[0124] In addition, the coupling agent can be a nitrogen-containing compound, including but not limited to isocyanate compounds, isothiocyanate compounds, isocyanuric acid derivatives, carbonyl compounds containing nitrogen groups, vinyl compounds containing nitrogen groups, epoxy compounds containing nitrogen groups, etc. (Hereinafter, such nitrogen-containing compounds used as coupling agents are sometimes referred to as coupling nitrogen-containing compounds).

[0125] The aforementioned coupling nitrogen-containing compounds are preferably compounds having nitrogen-containing functional groups. Among these compounds, amine compounds without active hydrogen are preferred. Examples include tertiary amine compounds, protected amine compounds in which the active hydrogen has been substituted with a protecting group, imine compounds represented by the general formula -N=C, and alkoxysilane compounds that have been bonded to the aforementioned nitrogen-containing functional groups.

[0126] Examples of the aforementioned coupling nitrogen-containing compounds include, but are not limited to, compounds containing imino and alkoxysilyl groups, such as tritrimethoxysilylpropylamine, triethoxysilylpropylamine, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine, N-(1,3-dimethylbutylidene)-3-(tributoxysilyl)-1-propaneamine, N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propaneamine, N-ethidene-3-(triethoxysilyl)-1-propaneamine, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, tetraglycidyl-m-phenylenediamine, tetraglycidyl-aminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidyl-aminomethylcyclohexane, and tetraglycidyl-1,3-diaminomethylcyclohexane.

[0127] In addition, examples of the aforementioned coupling nitrogen-containing compounds include, but are not limited to, isocyanate compounds such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, diphenylethane diisocyanate, and 1,3,5-benzene triisocyanate.

[0128] Furthermore, examples of the aforementioned coupling nitrogen-containing compounds include, but are not limited to, 3-(4-methylpiperazin-1-yl)propyltriethoxysilane, 1-[3-(diethoxyethylsilyl)propyl]-4-methylpiperazine, 1-[3-(trimethoxysilyl)propyl]-3-methylimidazolidine, 1-[3-(diethoxysilyl)propyl]-3-ethylimidazolidine, and 1-[3-(triethoxysilyl)propyl]-3-methylhexahydropyrimidine. 1-[3-(dimethoxymethylsilyl)propyl]-3-methylhexahydropyrimidine, 3-[3-(tributoxysilyl)propyl]-1-methyl-1,2,3,4-tetrahydropyrimidine, 3-[3-(dimethoxymethylsilyl)propyl]-1-ethyl-1,2,3,4-tetrahydropyrimidine, 1-(2-ethoxyethyl)-3-[3-(trimethoxysilyl)propyl]imidazolidine, (2-{3-[3-(trimethylsilyl)propyl] [Propyl]tetrahydropyrimidinyl)ethyl)dimethylamine, 1-[3-(triethoxysilyl)propyl]-4-(trimethylsilyl)piperazine, 1-[3-(dimethoxymethylsilyl)propyl]-4-(trimethylsilyl)piperazine, 1-[3-(tributoxysilyl)propyl]-4-(trimethylsilyl)piperazine, 1-[3-(diethoxyethylsilyl)propyl]-3-(triethylsilyl)imidazolidine, 2-(trimethyl) Examples of imidazolium compounds include 1-[3-(triethoxysilyl)propyl]-3-(trimethylsilyl)imidazolium, 1-[3-(dimethoxymethylsilyl)propyl]-3-(trimethylsilyl)hexahydropyrimidine, 1-[3-(triethoxysilyl)propyl]-3-(trimethylsilyl)hexahydropyrimidine, and 1-[4-(triethoxysilyl)propyl]-4-(trimethylsilyl)piperazine.

[0129] Furthermore, examples of the aforementioned coupling nitrogen-containing compounds include, but are not limited to, 2-[3-(trimethoxysilyl)propyl]-1,3-dimethylimidazolidine, 2-[3-(trimethoxysilyl)propyl]-1,3-(bistrimethylsilyl)imidazolidine, 2-(diethoxydiethylsilyl)-1,3-diethylimidazolidine, 2-(triethoxysilyl)-1,4-diethylpiperazine, 2-(dimethoxymethylsilyl)-1,4-dimethylpiperazine, 5-(triethoxysilyl)-1,3-dipropylhexahydropyrimidine, 5-(diethoxysilyl)-1,3-dipropylhexahydropyrimidine, etc. {2-[3-(2-dimethylaminoethyl)-2-(ethyldimethoxysilyl)-imidazolium-1-yl]-ethyl}-dimethylamine, 5-(trimethoxysilyl)-1,3-bis-(2-methoxyethyl)-hexahydropyrimidine, 5-(ethyldimethoxysilyl)-1,3-bis-(2-trimethylsilylethyl)-hexahydropyrimidinyl-1,3-dimethylimidazolium, 2-(3-diethoxyethylsilylpropyl)-1,3-diethylimidazolium, 2-(3-triethoxysilylpropyl) 1,4-Diethylpiperazine, 2-(3-Dimethoxymethylsilylpropyl)-1,4-dimethylpiperazine, 5-(3-triethoxysilylpropyl)-1,3-dipropylhexahydropyrimidine, 5-(3-diethoxyethylsilylpropyl)-1,3-diethylhexahydropyrimidine, {2-[3-(2-dimethylaminoethyl)-2-(3-ethyldimethoxysilylpropyl)-imidazolidine-1-yl]-ethyl}-dimethylamine, 5-(3-trimethoxysilylpropyl)-1,3-bis-(2-methoxyethyl)-hexahydropyrimidine, 5-(3-ethyldimethyl)-1,3-bis-(2-methoxyethyl)-hexahydropyrimidine, 5-(3-ethyldimethyl)-1,3-diethylhexahydropyrimidine, Examples of compounds include (2-(trimethylsilyl)propyl)-1,3-bis-(2-trimethylsilylethyl)-hexahydropyrimidine, 2-[3-(trimethoxysilyl)propyl]-1,3-bis(trimethylsilyl)imidazolidine, 2-(diethoxyethylsilyl)-1,3-bis(triethylsilyl)imidazolidine, 2-(triethoxysilyl)-1,4-bis(trimethylsilyl)piperazine, 2-(diethoxymethylsilyl)-1,4-bis(trimethylsilyl)piperazine, and 5-(triethoxysilyl)-1,3-bis(tripropylsilyl)hexahydropyrimidine.

[0130] Furthermore, examples of the aforementioned coupling nitrogen-containing compounds include, but are not limited to, [3-(1-hexamethyleneimino)propyl]triethoxysilane, [3-(1-hexamethyleneimino)propyl]trimethoxysilane, [2-(1-hexamethyleneimino)ethyl]triethoxysilane, [2-(1-hexamethyleneimino)ethyl]trimethoxysilane, [3-(1-pyrrolidinyl)propyl]triethoxysilane, [3-(1-pyrrolidinyl)propyl]trimethoxysilane, [3-( [1-Dodecylimino)propyl]triethoxysilane, [3-(1-hexamethyleneimino)propyl]diethoxymethylsilane, [3-(1-hexamethyleneimino)propyl]diethoxyethylsilane, N-[3-(triethoxysilyl)propyl]-N,N'-diethyl-N'-trimethylsilyl-ethane-1,2-diamine, N-[2-(trimethoxysilyl)ethyl]-N,N',N'-trimethylethane-1,2-diamine, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, etc.

[0131] Furthermore, examples of the aforementioned coupling nitrogen-containing compounds include, but are not limited to, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silazane, 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silazane, 2,2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silazane, 2,2-dimethoxy-1-(5-trimethoxysilylpentyl)-1-aza-2-silazane, and 2,2-dimethoxy-1-(3-dimethoxymethylsilylpropyl)-1-aza-2- Silzacyclopentane, 2,2-diethoxy-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silzacyclopentane, 2-methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silzacyclopentane, 2-ethoxy-2-ethyl-1-(3-triethoxysilylpropyl)-1-aza-2-silzacyclopentane, 2-methoxy-2-methyl-1-(3-diethoxymethylsilylpropyl)-1-aza-2-silzacyclopentane, 2-ethoxy-2-ethyl-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silzacyclopentane, etc.

[0132] From the perspective of the reactivity and interaction between the functional groups of the aforementioned coupling nitrogen-containing compounds and inorganic fillers such as silicon dioxide (described later), and from the perspective of the processability of the rubber composition for outsoles in this embodiment, the aforementioned coupling nitrogen-containing compounds are preferably 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silazopentanane or 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silazopentanane.

[0133] <Modified Conjugated Diene Polymers>

[0134] Regarding the conjugated diene polymer of the rubber used as the outsole rubber composition in this embodiment, it can be modified.

[0135] Modification refers to the modification of conjugated diene polymers using nitrogen-containing compounds.

[0136] Examples of modification methods include, but are not limited to, using polymerization initiators containing nitrogen-containing compounds; using nitrogen-containing compounds as polymerization monomers; reacting the aforementioned coupled or uncoupled nitrogen-containing compounds with the reaction termination terminator; modifying the double bonds of the polymerized conjugated diene polymer by reacting them with nitrogen-containing compounds; and so on.

[0137] Examples of polymerization initiators containing nitrogen-containing compounds include, but are not limited to, reactants with organolithium compounds such as dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, methylphenethylamine, piperidine, hexamethyleneimine, aziridine, 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, 1,2,3,6-tetrahydropyridine, and 3,5-dimethylpiperidine.

[0138] In addition, examples of non-coupled nitrogen-containing compounds include, but are not limited to, 1,3-diethyl-2-imidazolinone, 1,3-dimethyl-2-imidazolinone, 1,3-dipropyl-2-imidazolinone, 1-methyl-3-ethyl-2-imidazolinone, 1-methyl-3-propyl-2-imidazolinone, 1-methyl-3-butyl-2-imidazolinone, and 1,3-dihydro-1,3-dimethyl-2H-imidazolinone.

[0139] <Modification Rate>

[0140] In this specification, unless otherwise stated, "modification rate" refers to the mass ratio of polymers with nitrogen-containing functional groups to the total amount of polymers.

[0141] For example, when a modifier that is a nitrogen-containing compound reacts with the terminal end of a polymer, the mass ratio of the polymer having nitrogen-containing functional groups based on the modifier to the total amount of polymer is expressed as the modification rate.

[0142] In addition, when a branching agent containing nitrogen atoms is used to branch the polymer, the resulting branched polymer also has nitrogen-containing functional groups, so the branched polymer is also counted when calculating the modification rate.

[0143] Furthermore, when using the aforementioned coupling nitrogen-containing compounds to form polymers with nitrogen-containing functional groups, the modification rate is also taken into account when calculating the modification rate.

[0144] That is, in this specification, a polymer having nitrogen-containing functional groups refers to a polymer having nitrogen-containing functional groups based on a nitrogen-containing modifier, a branched polymer based on a branching agent having nitrogen-containing functional groups, and a polymer having nitrogen-containing functional groups based on a coupling nitrogen compound, the total mass ratio of which is the "modification rate".

[0145] Regarding the conjugated diene polymer used as the rubber in the outsole rubber composition of this embodiment, from the perspective of improved processability, improved filler dispersibility, and improved quality stability, the modification rate (hereinafter also referred to as "modification rate") measured by column adsorption GPC method relative to the total amount of conjugated diene polymer is preferably 30% or more, more preferably 40% or more, and even more preferably 60% or more.

[0146] On the other hand, from the perspective of processability and polymerization stability, it is preferable to have 90% or less, more preferably 80% or less, and it can also be unmodified.

[0147] The modification rate can be determined, for example, by a chromatographic method that can separate the modified and unmodified components containing functional groups.

[0148] As an example of using this chromatographic method, a method for quantification can be described using a gel permeation chromatography column that uses polar substances such as silica that adsorb specific functional groups as the packing material, and comparing it with an internal standard of the non-adsorbed component (column adsorption GPC method).

[0149] More specifically, the modification rate can be determined as follows: the amount of adsorption on the silica column is measured by measuring the difference between the chromatogram obtained by measuring the sample solution containing the sample and the low molecular weight internal standard polystyrene using a polystyrene-based gel column and the chromatogram obtained by measuring the sample solution using a silica-based column, and the modification rate is thus determined.

[0150] More specifically, the modification rate can be determined using the methods described in the examples.

[0151] In the conjugated diene polymer used in the outsole rubber composition of this embodiment, the modification rate can be controlled, for example, by adjusting the amount of the modifier added and the reaction method.

[0152] <Nitrogen content>

[0153] From the perspective of tear resistance, the nitrogen content contained in the conjugated diene polymer of the rubber used in the outsole rubber composition of this embodiment is preferably 0 ppm or more and 5000 ppm or less, more preferably 0 ppm or more and 2000 ppm or less, further preferably 0 ppm or more and 1500 ppm or less, and even more preferably 0 ppm or more and 1000 ppm or less.

[0154] The nitrogen content can be controlled within the above-mentioned range by adjusting the type of monomer used in polymer polymerization and the amount of the aforementioned modifier.

[0155] In this embodiment, when the outsole rubber composition contains nitrile rubber as the rubber, from the perspective of grip, the content of nitrile rubber relative to the total rubber is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. On the other hand, from the perspective of abrasion resistance, the content of the outsole rubber composition of this embodiment is preferably less than 60% by mass, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0156] Furthermore, regarding the proportion of acrylonitrile in the overall nitrile rubber, from the perspective of oil resistance, it is preferably 17% by mass or more, more preferably 23% by mass or more, and even more preferably 28% by mass or more. On the other hand, from the perspective of cold resistance, it is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0157] In the outsole rubber composition of this embodiment, from the perspective of processability, the Mooney viscosity is preferably 120 or less, more preferably 90 or less, and even more preferably 60 or less.

[0158] On the other hand, from the perspective of the tensile strength of the rubber composition for the outsole in this embodiment, it is preferably 25 or more, more preferably 35 or more, and even more preferably 45 or more.

[0159] In this embodiment, when the rubber composition for the outsole contains butyl rubber, its bromide, or its chloride as the aforementioned rubber, from the perspective of weather resistance, the content of these components relative to the total rubber is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. On the other hand, from the perspective of oil resistance, it is preferably 85% by mass or less, more preferably 75% by mass or less, and even more preferably 65% ​​by mass or less.

[0160] The butyl rubber is preferably a copolymer of isobutylene and isoprene. From the perspective of vulcanizability, the isoprene content in the copolymer is preferably 1 mol% or more, more preferably 1.5 mol% or more, and even more preferably 2 mol% or more.

[0161] In this embodiment, when the outsole rubber composition contains epichlorohydrin rubber (ECO) as the rubber, from the perspective of oil resistance, the content relative to the total rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of processability, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0162] In this embodiment, when the outsole rubber composition contains urethane rubber (U) as the rubber, from the perspective of tear strength, the content relative to the total rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of heat resistance, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0163] In this embodiment, when the outsole rubber composition contains chlorosulfonated polyethylene (CSM) as the rubber, from the perspective of abrasion resistance, the content relative to the total rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of cold resistance, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0164] In this embodiment, when the outsole rubber composition contains acrylic rubber (ACM) as the rubber, from the perspective of heat resistance, the content relative to the total rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of tensile strength, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0165] In this embodiment, when the outsole rubber composition contains silicone rubber (Q) as the rubber, from the perspective of weather resistance, the content relative to the total rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of tear strength, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0166] In this embodiment, when the outsole rubber composition contains fluororubber (FKM) as the rubber, from the perspective of weather resistance, the content relative to the total rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of cold resistance, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0167] (Liquid rubber)

[0168] In this embodiment, the rubber composition for the outsole may contain liquid rubber to improve processability and softness.

[0169] Liquid rubber is a low molecular weight rubber-like polymer, such as liquid styrene-butadiene rubber (liquid SBR), liquid butadiene rubber (liquid BR), and liquid isoprene rubber (liquid IR).

[0170] It should be noted that "liquid rubber" is any component that can be distinguished from the rubber that is a component of the outsole rubber composition of this embodiment by difference in form (solid or liquid).

[0171] That is, the liquid rubber described above is liquid at 23°C and 1 atmosphere, while the rubber that is a component of the rubber composition for the outsole in this embodiment is solid under the above conditions.

[0172] There is no particular limitation on the cis content of liquid BR; it can include any of the high cis, medium cis, and low cis liquid BR.

[0173] There are no particular limitations on the liquid rubber as long as it is in a liquid state, but the peak molecular weight determined by GPC is preferably in the range of 1000 to 50000. The peak molecular weight of the liquid rubber determined by GPC is preferably 4000 to 35000, more preferably 7000 to 30000. By keeping the peak molecular weight of the liquid rubber within the above range, the processability and flexibility of the rubber composition for the outsole are further improved. It should be noted that when using liquid rubber with a low molecular weight, processability is improved, but strength tends to decrease.

[0174] The amount of liquid rubber mixed is not particularly limited. Relative to 100 parts by weight of the total rubber used in the rubber composition for the outsole in this embodiment, the amount of liquid rubber mixed can be, for example, 0 to 15 parts by weight. The amount of liquid rubber mixed is preferably 0.10 to 10.0 parts by weight, more preferably 0.20 to 7.0 parts by weight, and even more preferably 0.30 to 4.0 parts by weight.

[0175] By keeping the amount of liquid rubber mixed within the above-mentioned range, the processability and softness of the outsole rubber composition of this embodiment tend to be further improved.

[0176] (filler)

[0177] The rubber composition for the outsole in this embodiment contains a filler.

[0178] From the perspective of the hardness and strength of the rubber composition for the outsole in this embodiment, the content of filler is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and even more preferably 18 parts by mass or more, relative to 100 parts by mass of the rubber.

[0179] On the other hand, from the perspective of processability, it is preferred to have 80 parts by weight or less, more preferably 60 parts by weight or less, further preferably 55 parts by weight or less, and even more preferably 50 parts by weight or less.

[0180] There are no particular limitations on the type of filler used as a material in rubber compositions for outsoles, as long as it is commonly used. Examples include silica (dry silica, wet silica, colloidal silica), synthetic silicate silica, calcium carbonate, titanium dioxide, talc, and carbon black. One of these fillers can be used alone, or two or more can be used in combination.

[0181] Silica is particularly preferred as a filler.

[0182] When using silica as a filler, to improve the dispersibility, performance stability, and reproducibility of silica, it is preferable to add substances such as silane coupling agents to enhance the affinity between the inorganic filler and the rubber component. Details regarding silane coupling agents are described below.

[0183] Fillers can be obtained by purchasing commercially available products or by manufacturing them using existing known methods.

[0184] Furthermore, from the perspective of the rigidity of the rubber composition for the outsole in this embodiment, the content of silica relative to the total mass of the filler is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0185] Furthermore, when obtaining a highly transparent outsole or when coloring the outsole, it is preferable not to include carbon black as a filler.

[0186] (Adhesive)

[0187] The rubber composition for the outsole in this embodiment contains an adhesive.

[0188] Tackifiers are typically amorphous oligomers with molecular weights ranging from hundreds to thousands. They are added to elastomers to exhibit flowability and adhesion, thereby improving adhesive properties.

[0189] The outsole rubber composition of this embodiment, by containing an tackifier, gives the outsole a flexibility that allows it to deform in response to the unevenness of the floor surface. This increases the actual contact area with the floor surface, generating friction and thus tending to increase grip. Furthermore, the presence of the tackifier enhances the stickiness, thereby further increasing grip.

[0190] The content of the tackifier in the rubber composition for the outsole of this embodiment, from the perspective of improving grip, is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 4 parts by mass or more, further preferably 5 parts by mass or more, further more preferably 7 parts by mass or more, even more preferably 8 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the rubber.

[0191] On the other hand, from the perspective of suppressing excessive stickiness and dust adhesion, the content of the tackifier is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, even more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less, relative to 100 parts by weight of the rubber.

[0192] In addition, from the perspective of suppressing dust adhesion of the rubber composition for outsole in this embodiment, the softening point of the tackifier is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 55°C or higher.

[0193] On the other hand, from the perspective of processability, the softening point of the tackifier is preferably below 180°C, more preferably below 170°C, further preferably below 160°C, and even more preferably below 150°C.

[0194] The softening point of the tackifier can be determined by the ring and ball method according to JIS K 5601-2-2, and can be controlled within the above temperature range by selecting the material.

[0195] From the perspective of the softness of the rubber composition for the outsole in this embodiment, the glass transition temperature of the tackifier is preferably -20°C or higher, more preferably 0°C or higher, and even more preferably 10°C or higher. On the other hand, since it needs to be melted and incorporated into the rubber during mixing, it is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 100°C or lower. The glass transition temperature of the tackifier can be determined by differential scanning calorimetry (DSC), and can be controlled within the above temperature range by selecting the materials.

[0196] Tackifiers can be selected in a wide variety of ways depending on the intended use, required performance, and rubber composition of the outsole rubber composition.

[0197] For example, the terpene compounds described below have good compatibility with natural rubber. Therefore, by using terpene compounds as tackifiers and natural rubber as rubber, the exudation of terpene compounds can be suppressed.

[0198] Examples of tackifiers include, but are not limited to, rosin-based compounds such as natural rosin, modified rosin, glycerol esters of natural rosin, glycerol esters of modified rosin, pentaerythritol esters of natural rosin, pentaerythritol esters of modified rosin, hydrogenated rosin, and pentaerythritol esters of hydrogenated rosin; copolymers of natural terpenes, three-dimensional polymers of natural terpenes, aromatic modified terpene resins, hydrogenated derivatives of aromatic modified terpene resins, terpene phenol resins, hydrogenated derivatives of terpene phenol resins, terpene resins (monoterpenes, diterpenes, triterpenes, polyterpenes, etc.), hydrogenated terpene resins, and hydrogenated terpene resins. Terpenoid compounds such as hydrogenated derivatives; aliphatic petroleum hydrocarbon resins (C5 series resins), aliphatic tackifiers such as hydrogenated derivatives of aliphatic petroleum hydrocarbon resins; aromatic petroleum hydrocarbon resins (C9 series resins), aromatic tackifiers such as hydrogenated derivatives of aromatic petroleum hydrocarbon resins; dicyclopentadiene resins, hydrogenated derivatives of dicyclopentadiene resins; C5 / C9 copolymer resins, hydrogenated derivatives of C5 / C9 copolymer resins; cyclic aliphatic petroleum hydrocarbon resins, hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins, and other petroleum hydrocarbon compounds; and resins containing aromatic groups.

[0199] These adhesives can be used alone or in combination of two or more.

[0200] It should be noted that the C5 / C9 copolymer system refers to a copolymer petroleum resin produced by polymerizing a mixture of C5 and C9 fractions as raw materials.

[0201] Tackifiers can also be liquid tackifiers that are colorless to pale yellow, practically odorless, and have good thermal stability.

[0202] The following describes in more detail the preferred tackifiers corresponding to the application and performance.

[0203] <Hydrogenated Derivatives as Thickeners>

[0204] From the perspectives of low odor and quality stability, hydrogenated derivatives are preferred as adhesives.

[0205] Examples of hydrogenated derivatives include, but are not limited to, hydrogenated derivatives of aromatic modified terpene resins, hydrogenated derivatives of terpene phenol resins, hydrogenated derivatives of hydrogenated terpene resins, hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 series resins), hydrogenated derivatives of aromatic petroleum hydrocarbon resins (C9 series resins), hydrogenated derivatives of dicyclopentadiene resins, hydrogenated derivatives of C5 / C9 copolymer resins, and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins.

[0206] Among them, hydrogenated derivatives of aromatic petroleum hydrocarbon resins (C9 series resins), hydrogenated derivatives of dicyclopentadiene resins, and hydrogenated derivatives of hydrogenated terpene resins are particularly preferred.

[0207] Commercially available products that are such hydrogenated derivatives include, but are not limited to, Arkon P and M series (trade names) manufactured by Arakawa Chemical Co., Ltd., I-Marv S and P series manufactured by Idemitsu Kosan Co., Ltd., ESCOREZ5000 series (trade names) manufactured by ExxonMobil Co., Ltd., and Cleanon P series manufactured by Yasuhara Chemical Co., Ltd.

[0208] In addition, examples of the ESCOREZ 5000 series include ESCOREZ 5600, which is a hydrogenated derivative of a copolymer of dicyclopentadiene and an aromatic compound, and ESCOREZ 5300 and ESCOREZ 5400, which are hydrogenated derivatives of dicyclopentadiene.

[0209] <Adhesives other than hydrogenated derivatives>

[0210] Examples of tackifiers other than hydrogenated derivatives include, but are not limited to: natural rosin, modified rosin, glycerol esters of natural rosin, glycerol esters of modified rosin, pentaerythritol esters of natural rosin, pentaerythritol esters of modified rosin, hydrogenated rosin, pentaerythritol esters of hydrogenated rosin; copolymers of natural terpenes, three-dimensional polymers of natural terpenes, aromatic modified terpene resins, terpene phenol resins, terpene resins, hydrogenated terpene resins; aliphatic petroleum hydrocarbon resins (C5 series resins), aromatic petroleum hydrocarbon resins (C9 series resins), dicyclopentadiene resins, C5 / C9 copolymer resins, cyclic aliphatic petroleum hydrocarbon resins, and alkylphenols.

[0211] Among these, aliphatic petroleum hydrocarbon resins (C5 series resins), aromatic petroleum hydrocarbon resins (C9 series resins), C5 / C9 copolymer resins, cyclic aliphatic petroleum hydrocarbon resins, terpene resins, natural and modified rosin esters, and mixtures thereof are preferred.

[0212] Commercially available products are not limited to the following substances, but examples include, for example, aliphatic petroleum hydrocarbon resins (C5 series resins), such as the QUINTON 100 series (trade name) manufactured by Zeon Corporation of Japan, the ESCOREZ1000 series manufactured by ExxonMobil Corporation, and the WINGTACK series (trade name) manufactured by Cray Valley; aromatic petroleum hydrocarbon resins (C9 series resins) and C5 / C9 copolymer resins, such as the PICCOTAC series (trade name) manufactured by Eastman Chemical Company, the Escorez 2000 series (trade name) manufactured by ExxonMobil Chemical Company, and the FTR series (trade name) manufactured by Mitsui Chemicals Corporation; and terpene resins, natural and modified rosin esters, such as the SYLVALITE series and SYLVARES series (trade name) manufactured by Arizona Chemical Company, and the PICCOLYTE series (trade name) manufactured by PINOVA Company.

[0213] <Aliphatic adhesives>

[0214] From the perspectives of obtaining a rubber composition for outsoles with high grip and economic efficiency, it is preferable to use an aliphatic tackifier as the tackifier.

[0215] Examples of aliphatic adhesives include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 series resins), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 series resins), C5 / C9 copolymer resins, and hydrogenated derivatives of C5 / C9 copolymer resins.

[0216] It should be noted that aliphatic tackifiers refer to tackifiers in which the content of aliphatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further more preferably 88% by mass or more, and even more preferably 95% by mass or more. By setting the content of aliphatic hydrocarbon groups within the above range, there is a tendency to further improve adhesion, holding power, and economy.

[0217] Aliphatic tackifiers can be manufactured by homopolymerizing or copolymerizing monomers having aliphatic groups and polymerizable unsaturated groups.

[0218] Monomers having aliphatic groups and polymerizable unsaturated groups include, but are not limited to, natural and synthetic terpenes containing C5 or C6 cyclopentyl or cyclohexyl groups. Other monomers that can be used in copolymerization include, but are not limited to, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpenes, terpene-phenol resins, etc.

[0219] <Aromatic Adhesives>

[0220] From the perspective of processability and obtaining an outsole rubber composition that suppresses leakage through high compatibility with the aforementioned rubber, aromatic tackifiers are preferred as tackifiers.

[0221] Examples of aromatic adhesives include, but are not limited to, aromatic petroleum hydrocarbon resins (C9 resins) and C5 / C9 copolymer resins.

[0222] It should be noted that aromatic tackifiers refer to tackifiers in which the content of aromatic hydrocarbon groups is preferably 50% or more by mass, more preferably 70% or more by mass, further preferably 80% or more by mass, further preferably 88% or more by mass, and even more preferably 95% or more by mass.

[0223] By keeping the content of aromatic hydrocarbon groups within the above range, there is a tendency to further improve adhesion and coatability.

[0224] Aromatic adhesives can be manufactured by homopolymerizing or copolymerizing monomers having aromatic groups and polymerizable unsaturated groups, respectively.

[0225] Monomers having both an aromatic group and a polymerizable unsaturated group can be, but are not limited to, styrene, α-methylstyrene, vinyltoluene, methoxystyrene, tert-butylstyrene, chlorostyrene, and indene monomers (including methylindene). Other monomers that can be used in copolymerization are not particularly limited, and examples include 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpenes, and terpene-phenol resins.

[0226] As the tackifier used in the rubber composition for the outsole in this embodiment, it is preferable to use a tackifier with high affinity for the rubber described above.

[0227] As the tackifier used in the rubber composition for the outsole of this embodiment, it is preferable to select a tackifier that, when measured by differential scanning calorimetry (DSC) for the mixture with the above-mentioned conjugated diene polymer, has one inflection point originating from the glass transition observed when the temperature is increased from -120°C to 0°C at a rate of 10°C / min.

[0228] The rubber composition for the outsole in this embodiment preferably uses a conjugated diene polymer as the rubber, and polybutadiene or styrene-butadiene copolymer is preferably used as the conjugated diene polymer. When this polybutadiene or styrene-butadiene copolymer and a tackifier are included, the inflection point originating from the glass transition temperature occurs between -120°C and 0°C. To ensure that there is only one inflection point originating from the glass transition, a tackifier with good compatibility with the conjugated diene polymer is preferably used, and a small difference in the SP values ​​between the rubber and the tackifier is an indicator of good compatibility.

[0229] Meeting the above conditions means that the conjugated diene polymer and the tackifier have relatively high compatibility. As a result, there is less exudation to the surface, and it can stably exhibit a high level of balance between grip and abrasion resistance.

[0230] On the other hand, when the compatibility between the conjugated diene polymer and the tackifier is poor, there is a tendency for a slight increase in the exudation of the tackifier, which may result in a sticky residue. In this case, the amount of tackifier added is preferably 10 parts by weight or less relative to 100 parts by weight of the conjugated diene polymer.

[0231] From the perspective of transparency, the difference in SP value between the tackifier used in the rubber composition for the outsole of this embodiment and the aforementioned rubber is preferably 0.8 (cal / cm). 3 ) 2 The following, and more preferably, is 0.55 (cal / cm). 3 ) 2 The following, and more preferably, is 0.3 (cal / cm³). 3 ) 2 the following.

[0232] Furthermore, when the tackifier used in the rubber composition for the outsole in this embodiment is the aforementioned terpene resin, from the perspective of the compatibility between the rubber and the tackifier, the content of the aromatic vinyl monomer unit of the conjugated diene polymer of the rubber is preferably 10% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less. In addition, the vinyl bonding amount is preferably 24% by more and 60% or less, more preferably 28% by more and 58% or less, and even more preferably 29% by more and 57% or less.

[0233] When the tackifier used in the rubber composition for the outsole in this embodiment is the aforementioned petroleum hydrocarbon compound, from the perspective of the compatibility between the rubber and the tackifier, the content of aromatic vinyl monomer units in the conjugated diene polymer of the rubber is preferably 20% by mass or more and 60% by mass or less, more preferably 24% by mass or more and 60% by mass or less, and even more preferably 30% by mass or more and 58% by mass or less, and the vinyl bonding amount is preferably 20% by mass or more and 55% by mole or less, more preferably 22% by mass or more and 55% by mole or less, and even more preferably 23% by mass or more and 54% by mole or less.

[0234] From the perspective of suppressing hardening of the outsole at low temperatures, the difference between the tackifier used in the rubber composition for the outsole of this embodiment and the glass transition temperature of the rubber is preferably 10°C or more, more preferably 20°C or more, and even more preferably 30°C or more.

[0235] On the other hand, from the perspective of suppressing dust adhesion, the difference in glass transition temperature is preferably 180°C or less, more preferably 170°C or less, and even more preferably 160°C or less.

[0236] From an aesthetic point of view, the tackifier b used in the outsole rubber composition of this embodiment The value is preferably 50 or less, more preferably 35 or less, and even more preferably 20 or less.

[0237] From a processability perspective, the mixture of the rubber and the tackifier constituting the outsole rubber composition of this embodiment preferably has a Tg of one in differential scanning calorimetry (DSC).

[0238] (Cross-linking agent)

[0239] The rubber composition for the outsole in this embodiment is preferably a crosslinked composition containing a specified crosslinking agent in addition to rubber, filler, and tackifier.

[0240] There are no particular limitations on crosslinking agents; any existing and known crosslinking agents used in the crosslinking of rubber compositions may be used.

[0241] Suitable crosslinking agents include, for example, sulfur, sulfur-containing compounds, organic peroxides, and free radical crosslinking agents.

[0242] Examples of organic peroxides include, but are not limited to, dicumyl peroxide, benzoyl peroxide, di-tert-hexyl peroxide, tert-butylcumyl peroxide, diisobutyryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, di(2-tert-butylperoxyisopropyl)benzene, cumyl peroxyneodecanate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanate, and di(4-tert-butylcyclohexyl)peroxydicarbonate. Carbonates, di(2-ethylhexyl) peroxydicarbonate, tert-hexyl peroxynedecanoate, tert-butyl peroxynedecanoate, tert-butyl peroxyneheptanoate, tert-hexyl peroxynepentanoate, tert-butyl peroxynepentanoate, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, succinyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxide)hexane, tert-hexyl peroxide-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, tert-butyl peroxide (2-ethylhexanoate), di(3-methyl Benzoyl peroxide, benzoyl(3-methylbenzoyl) peroxide, dibenzoyl peroxide, 1,1-di(tert-butylperoxy)-2-methylcyclohexane, 1,1-di(tert-hexylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 2,2-di(4,4-di-(tert-butylperoxy)cyclohexyl)propane, tert-hexyl isopropyl monocarbonate peroxide, tert-butyl maleate peroxide, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl laurate peroxide, tert-butyl isopropyl monocarbonate peroxide Ester, tert-butyl percarbonate 2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, tert-butyl peroxyacetate, 2,2-di(tert-butyl peroxide)butane, tert-butyl peroxybenzoate, n-butyl 4,4-di(tert-butyl peroxide)valerate, di(2-tert-butyl peroxyisopropyl)benzene, di-tert-butyl peroxide, p-menthane hydrogen peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexyn-3, diisopropylbenzene hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydrogen peroxide, isopropylbenzene hydrogen peroxide, and tert-butyl hydrogen peroxide.

[0243] Examples of free radical crosslinking agents include, but are not limited to, ethylene glycol methacrylate (EGDMA), trimethylolpropane trimethacrylate, triallyl isocyanurate, triallyl cyanurate, diethylene glycol diacrylate, and neobenzene glycol diacrylate.

[0244] When minimal pollution to the product is desired, or when transparency, colorability, and heat resistance are important considerations, peroxides are preferred as crosslinking agents. Further preferred crosslinking agents, considering odor and minimal residue, include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(2-tert-butylperoxyisopropyl)benzene, and 1,1-di(tert-butylperoxy)cyclohexane.

[0245] In addition, when using rubbers with fewer double bonds, such as butyl rubber, silicone rubber, and fluororubber, organic peroxides are preferred as crosslinking agents.

[0246] On the other hand, when cost, tensile properties, and ease of processing are important considerations, sulfur or sulfur-containing compounds and sulfurization accelerators are preferred for crosslinking. Sulfur-containing compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, and high-molecular-weight polysulfide compounds.

[0247] The above-mentioned crosslinking agents can be used alone or in combination of two or more.

[0248] In the outsole manufacturing process, the content of crosslinking agent in the rubber composition for the outsole before molding is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the aforementioned rubber. As a vulcanization method, existing known methods can be used, and the vulcanization temperature is preferably 120°C or more and 200°C or less, more preferably 140°C or more and 180°C or less.

[0249] When using sulfur or sulfur-containing compounds for sulfidation, sulfidation accelerators can be used as needed.

[0250] As a vulcanization accelerator, existing known materials can be used, including, but not limited to, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-amine-based, thiazole-based, thiourea-based, and dithiocarbamate-based vulcanization accelerators. Additionally, as a vulcanization aid, examples include, but are not limited to, zinc oxide, stearic acid, and triallyl isocyanurate. The content of the vulcanization accelerator relative to 100 parts by weight of the rubber component is preferably 0.01 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight or more and 15 parts by weight or less.

[0251] (Other ingredients)

[0252] In this embodiment, when silica is used as a filler, the rubber composition for the outsole preferably contains a silane coupling agent. This approach tends to improve the dispersibility of the inorganic filler, enhance its adhesion to the rubber, and further increase transparency and strength.

[0253] Examples of silane coupling agents include, but are not limited to, tetraethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, 3-aminopropyltriethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, bis-[3-(triethoxysilyl)-propyl]tetrasulfide, bis-[3-(triethoxysilyl)-propyl]disulfide, and triethoxysilylpropyl-methacrylate-monosulfide, etc., alkoxysilane compounds.

[0254] The silane coupling agent is preferably a polysiloxane containing vinyl and alkoxy groups, more preferably a polysiloxane containing vinyl and ethoxy or methoxy groups, and even more preferably vinyltrimethoxysilane or vinyltri(2-methoxyethoxy)silane.

[0255] The above-mentioned silane coupling agents can be used alone or in combination of two or more.

[0256] The content of the silane coupling agent is not particularly limited, and may be, for example, 0 to 20 parts by weight relative to 100 parts by weight of the rubber. More preferably, the content of the silane coupling agent is 0.50 to 10 parts by weight.

[0257] The rubber composition for the outsole of this embodiment may further include other components. Examples of other components include antioxidants, colorants, modifiers, processing agents (fatty acids, etc.), reducing agents, deoxidizers, light stabilizers, pH stabilizers, surface treatment agents, heat stabilizers, colorants, fillers (talc and calcium carbonate, etc.), surfactants, gelling agents, UV absorbers (salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and hindered amines, etc.), separating powders (polyolefins such as polyethylene, talc and calcium carbonate powder, etc.), and polyphosphoric acid.

[0258] These ingredients can be used alone or in combination of two or more.

[0259] As antioxidants, examples include, but are not limited to, monophenolic, bisphenolic, polyphenolic, sulfur-based, and phosphorus-based compounds. Specifically, examples include NOCRAC SP (manufactured by Ouchi Shinshin Chemical Industry), IRGANOX 1076 (manufactured by BASF), Irgafos 168 (manufactured by BASF), and IRGANOX 1520 (manufactured by BASF).

[0260] Colorants can be used when it is desired to color the outsole.

[0261] As such a colorant, any known colorant can be used, such as coloring pigments, extender pigments, anti-rust pigments, and functional pigments (e.g., phthalocyanine green, titanium, ultramarine, iron oxide, lead monoxide, and zinc sulfide).

[0262] In the rubber composition for the outsole of this embodiment, relative to 100 parts by weight of the rubber component, it may contain one or more of the following components in a total amount ranging from, for example, 0.1 to 15 parts by weight: antioxidant, colorant, modifier, processing agent, reducing agent, deoxidizer, light stabilizer, pH stabilizer, surface treatment agent, heat stabilizer, colorant, filler, surfactant, gelling agent, UV absorber, blocking powder, and polyphosphoric acid. When these components are included, the total content of these components is preferably 0.2 to 10 parts by weight, more preferably 0.20 to 5.0 parts by weight, and even more preferably 0.25 to 2.0 parts by weight.

[0263] (Transparency)

[0264] The rubber composition for the outsole in this embodiment can be used for highly transparent outsoles.

[0265] The transparency of the outsole was evaluated using HAZE.

[0266] A lower HAZE indicates higher transparency. Generally, outsoles with a HAZE greater than 50% are considered "opaque" or "semi-transparent," while outsoles with a HAZE of 50% or less are considered "transparent." From the perspective of achieving excellent transparency, the HAZE of the rubber composition used for the outsole in this embodiment is preferably 50% or less.

[0267] "Haze" refers to the degree of obscurity of a transparent material as measured according to Japanese Industrial Standard JIS K7136 (or ISO 14782). In this specification, haze can be measured using a 3.00 mm thick sheet as the test sample, using a testing apparatus according to the aforementioned standard. Specifically, it can be measured using the method described in the examples below.

[0268] The HAZE of the rubber composition for the outsole in this embodiment can be controlled within the aforementioned range by selecting the constituent materials. For example, silica is preferably used as a filler.

[0269] [Outsole]

[0270] The outsole of this embodiment is a molded body of the rubber composition used for the outsole of this embodiment.

[0271] The outsole of this embodiment can be manufactured by crosslinking the rubber composition for the outsole of this embodiment containing the above-mentioned rubber, filler, and tackifier using a crosslinking agent, and optionally adding other components in an appropriate mixing ratio and then mixing.

[0272] More specifically, for example, the following methods can be used.

[0273] As an example, the outsole manufacturing method of this embodiment includes the following steps: a step of mixing a conjugated diene polymer and other diene rubbers as rubber, silica as a filler, optional tackifier, and silane coupling agent, crosslinking agent, crosslinking aid, and antioxidant; and a step of molding the resulting mixture.

[0274] The above-mentioned mixing process can be performed using, for example, an open mill, a Banbury mixer, a kneader, a twin-screw extruder, and / or a torque rheometer (LABO PLASTOMILL). In the mixing process, the above components can be mixed in one step, or other additives can be mixed after the rubber is mixed with fillers and silane coupling agents.

[0275] From the perspective of ensuring uniform mixing of the components, the compounding with rubber can be carried out at a temperature of 120–160°C, for example.

[0276] From the perspective of suppressing side reactions, the mixing after adding the crosslinking agent can be carried out at a temperature of, for example, below 120°C. The temperature during the mixing after adding the crosslinking agent is preferably below 100°C, more preferably below 80°C, and even more preferably 0 to 50°C.

[0277] In the above-mentioned mixing process, other components may be appropriately added.

[0278] A molding process, which involves shaping the compound, can yield a cross-linked rubber composition of a desired shape. The molding process can be, for example, a process of loading the compound obtained from the mixing process into a compression mold of a suitable shape and then heating it.

[0279] The molding temperature in the molding process is not particularly limited, but it is preferably 140-180°C, and more preferably 150-170°C.

[0280] The outsole in this embodiment is used as the outsole for shoes.

[0281] [Purpose of the outsole]

[0282] The rubber composition for the outsole of this embodiment can be used regardless of the purpose of the shoe, but the required performance and the physical properties that are considered practically acceptable will vary depending on the application. For example, sports shoes need to have the strength, abrasion resistance, and grip to withstand intense exercise. Therefore, compared with common shoes, a higher level of balance between strength, abrasion resistance, and grip is required, especially in sports such as basketball where repeated rapid acceleration and stopping are common, grip becomes very important.

[0283] Additionally, when using the product on wet outdoor surfaces during exercise or on floors that are damp with sweat, wet grip is also important to prevent slipping.

[0284] In addition, hiking boots are used when walking on slippery wooden paths or rocks wet by streams in the mountains. Since slipping would be more dangerous than usual, they need to have high grip. In addition, they also need to be wear-resistant and strong enough to withstand wear even when climbing rocks.

[0285] These uses are examples of the uses of the outsole in this embodiment. Depending on the use, the physical property values ​​that are considered to be practically harmless can be appropriately adjusted.

[0286] Example

[0287] The following specific manufacturing examples, embodiments, and comparative examples further illustrate this embodiment in detail, but the present invention is not limited to the following manufacturing examples, embodiments, and comparative examples.

[0288] It should be noted that the various physical properties in the manufacturing examples, embodiments, and comparative examples were measured using the methods shown below.

[0289] [Methods for determining physical properties]

[0290] [Peak molecular weight, weight-average molecular weight]

[0291] Chromatograms were determined using a GPC assay apparatus with three columns packed with polystyrene-based gels. The weight-average molecular weight and peak molecular weight were calculated based on a calibration curve using standard polystyrene.

[0292] It should be noted that Table 1 shows the peak molecular weight of the uncoupled and coupled molecules.

[0293] The specific measurement conditions are as follows.

[0294] Inject 20 μL of the following assay solution into the GPC assay apparatus for measurement.

[0295] (Measurement conditions)

[0296] Device: Trademark name "HLC-8320GPC" manufactured by Tosoh Corporation

[0297] Eluent: Tetrahydrofuran (THF) containing 5 mmol / L triethylamine.

[0298] Guard column: Manufactured by Tosoh Corporation under the trade name "TSKguardcolumn SuperH-H" Separation column: A column made by sequentially connecting the products manufactured by Tosoh Corporation under the trade names "TSKgel SuperH5000", "TSKgel SuperH6000" and "TSKgel SuperH7000".

[0299] Oven temperature: 40℃

[0300] Flow rate: 0.6 mL / min

[0301] Detector: RI detector (manufactured by Tosoh Corporation, trade name "HLC8020")

[0302] Assay solution: The assay solution is prepared by dissolving 10 mg of the sample in 20 mL of THF.

[0303] [Modification Rate]

[0304] Regarding the modification rate, the column adsorption GPC method was used to determine the modification rate by utilizing the characteristic that the modified polymer is adsorbed by the column.

[0305] The modification rate is determined by measuring the amount of adsorption on the silica column based on the difference between the chromatogram obtained by measuring the sample solution containing the sample and the low molecular weight internal standard polystyrene using a column filled with polystyrene gel and the chromatogram obtained by measuring the sample solution using a column filled with silica gel.

[0306] (GPC determination conditions using polystyrene-based columns)

[0307] The GPC measurement conditions using a polystyrene column are as follows. Inject 20 μL of the following assay solution into the GPC measurement apparatus and perform the measurement.

[0308] Device: Trademark name "HLC-8320GPC" manufactured by Tosoh Corporation

[0309] Eluent: THF containing 5 mmol / L triethylamine

[0310] Protective column: Manufactured by Tosoh Corporation under the trade name "TSKguardcolumn SuperH-H"

[0311] Pillar: A pillar formed by sequentially linking the product names "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" manufactured by Tosoh Corporation.

[0312] Oven temperature: 40℃

[0313] Flow rate: 0.6 mL / min

[0314] Detector: RI detector (HLC8020 manufactured by Tosoh Corporation)

[0315] Test solution: Dissolve 10 mg of the sample and 5 mg of standard polystyrene in 20 mL of THF to prepare the sample solution.

[0316] (GPC determination conditions using silica-based columns)

[0317] The GPC measurement conditions using a silica-based column are shown below. Inject 50 μL of the following assay solution into the GPC measurement apparatus and perform the measurement.

[0318] Device: Trademark name "HLC-8320GPC" manufactured by Tosoh Corporation

[0319] Elution buffer: THF

[0320] Protective pillar: Manufactured by GL Sciences under the trade name "DIOL 4.6×12.5mm 5micron"

[0321] Separation column: A column made by sequentially connecting the trade names "Zorbax PSM-1000S", "PSM-300S", and "PSM-60S" manufactured by Agilent Technologies.

[0322] Oven temperature: 40℃ Flow rate: 0.5 mL / min Detector: RI detector (HLC8020 manufactured by Tosoh Corporation) (Method for calculating modification rate): Set the peak area of ​​the chromatogram obtained using a polystyrene column to 100, the peak area of ​​the sample to P1, and the peak area of ​​the standard polystyrene to P2. Set the peak area of ​​the chromatogram obtained using a silica column to 100, the peak area of ​​the sample to P3, and the peak area of ​​the standard polystyrene to P4. Calculate the modification rate (%) using the following formula.

[0323] Modification rate (%) = [1 - (P2 × P3) / (P1 × P4)] × 100

[0324] (Where, P1 + P2 = P3 + P4 = 100)

[0325] [Couple Rate]

[0326] The chromatogram is measured using the same methods as described above for determining weight-average molecular weight and peak molecular weight. When there are two or more peaks, the coupling rate is calculated based on the ratio of the peak area of ​​the uncoupled peak (the peak on the low molecular weight side) to the peak area of ​​the coupled peak (the peak on the high molecular weight side). If there is only one peak, the coupling rate is considered to be 0%. If there are three or more peaks, the peak with the lowest molecular weight is considered the peak of the uncoupled component, and the peak of the component located closer to the high molecular weight side than this peak is considered the coupled peak.

[0327] In this embodiment, a peak refers to the portion that has a maximum value, is sandwiched between a baseline or a minimum value when measuring GPC. It refers to the portion at the maximum value where the molecular weight is above 10,000 and the peak area is above 5%.

[0328] Mooney viscosity

[0329] The Mooney viscosity of each polymer was measured using a Mooney viscometer (trade name "VR1132" manufactured by Uejima Seisakusho Co., Ltd.) according to JIS K6300 (ISO289-1) and ISO289-4. The measurement temperature was set to 100°C.

[0330] Here, after preheating the sample for 1 minute, the rotor is rotated at 2 rpm, and the torque is measured after 4 minutes, which is taken as the Mooney viscosity (ML). (1+4) ).

[0331] [Content of bonded styrene, amount of 1,2-vinyl bonds in the butadiene moiety]

[0332] Using conjugated diene polymers as samples, through 1 The content of aromatic vinyl monomer units (bonded styrene content) and the amount of 1,2-vinyl bonds were determined by H-NMR.

[0333] <Measurement Conditions>

[0334] Measurement equipment: JNM-LA400 (manufactured by JEOL)

[0335] Solvent: Deuterated chloroform

[0336] Sample tested: Conjugated diene polymers

[0337] Sample concentration: 50 mg / mL

[0338] Observation frequency: 400MHz

[0339] Chemical shift benchmark: relative to the addition of 5% by weight of TMS (tetramethylsilane) in deuterated chloroform.

[0340] Pulse delay: 2.904 seconds

[0341] Number of scans: 64

[0342] Pulse width: 45°

[0343] Measurement temperature: 26℃

[0344] [Content of styrene blocks]

[0345] The content of aromatic vinyl monomer blocks (styrene blocks) was determined according to the osmium tetroxide decomposition method described in IM Kolthoff, et al., J. Polym. Sci. 1, 429 (1946).

[0346] More specifically, 0.050 g of styrene-butadiene copolymer rubber was dissolved in 10 ml of chloroform, and 16 mL of a 69% (w / w) aqueous solution of tert-butyl hydroperoxide and 4.0 mL of a 0.050% (w / w) chloroform solution of osmium tetroxide were added. The mixture was refluxed in a 90°C bath for 12 minutes to carry out an oxidative decomposition reaction. After the reaction was completed, the reaction solution was cooled, and 200 mL of methanol was added to the reaction solution with stirring to precipitate the styrene block components. The precipitate was then filtered out through a 5 μm glass filter. The styrene block content was determined by dividing the mass of the obtained substance by the total mass of the styrene-butadiene copolymer rubber.

[0347] [Preparation of conjugated diene polymers]

[0348] ((Manufacturing Example 1) Conjugated diene polymer 1)

[0349] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 648g of 1,3-butadiene, 552g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 0.772mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances), and 0.458mmol of potassium tert-amyloxide were added to the reactor, and the reactor temperature was maintained at 51°C.

[0350] 5.72 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0351] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction, with a peak temperature of 81°C. 5.72 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0352] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 1.

[0353] The obtained conjugated diene polymer 1 was analyzed using the above method, and the analytical results are shown in Table 1.

[0354] ((Manufacturing Example 2) Conjugated diene polymer 2)

[0355] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 454g of 1,3-butadiene, 468g of styrene, 5,600g of cyclohexane, 7.81mmol of tetrahydrofuran (THF) and 0.858mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances) were added to the reactor, and the reactor temperature was maintained at 52°C.

[0356] 6.20 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0357] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction, and a reaction peak was confirmed at 76 °C. Subsequently, 194 g of 1,3-butadiene was added to the reactor, and a reaction peak was confirmed at 79 °C. Furthermore, 80 g of styrene was added to the reactor, and a reaction peak was confirmed at 81 °C. 6.20 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0358] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as an antioxidant and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 2.

[0359] The obtained conjugated diene polymer 2 was analyzed using the above method, and the analytical results are shown in Table 1.

[0360] ((Manufacturing Example 3) Conjugated diene polymer 3)

[0361] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 454g of 1,3-butadiene, 552g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 0.824mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances) were added to the reactor, and the reactor temperature was maintained at 52°C.

[0362] 5.77 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0363] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction, and a reaction peak was confirmed at 76 °C. Subsequently, 194 g of 1,3-butadiene was added to the reactor, and a reaction peak was confirmed at 84 °C. 5.77 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0364] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 3.

[0365] The obtained conjugated diene polymer 3 was analyzed using the above method, and the analytical results are shown in Table 1.

[0366] ((Manufacturing Example 4) Conjugated diene polymer 4)

[0367] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 454g of 1,3-butadiene, 552g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 0.824mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances) were added to the reactor, and the reactor temperature was maintained at 48°C.

[0368] 5.77 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0369] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction, and a reaction peak was confirmed at 73°C. Subsequently, 194 g of 1,3-butadiene was added to the reactor, and a reaction peak was confirmed at 78°C. 5.77 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0370] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)-o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 4.

[0371] The obtained conjugated diene polymer 4 was analyzed using the above method, and the analytical results are shown in Table 1.

[0372] ((Manufacturing Example 5) Conjugated diene polymer 5)

[0373] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 444g of 1,3-butadiene, 756g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 5.17mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances), and 0.245mmol of potassium tert-amyloxide were added to the reactor, and the reactor temperature was maintained at 43°C.

[0374] 6.86 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0375] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction. After reaching the peak reaction temperature of 87°C, 1.37 mmol of 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane was added as a coupling agent, and the mixture was stirred for 5 minutes. The coupling rate was 79.6%. Then, 1.37 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0376] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 5.

[0377] The obtained conjugated diene polymer 5 was analyzed using the above method, and the analytical results are shown in Table 1.

[0378] ((Manufacturing Example 6) Conjugated diene polymer 6)

[0379] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 444g of 1,3-butadiene, 756g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 4.043mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances), and 0.656mmol of potassium tert-amyloxide were added to the reactor, and the reactor temperature was maintained at 44°C.

[0380] 8.20 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0381] After the polymerization reaction begins, the temperature inside the reactor rises due to the exothermic reaction, with a peak temperature of 85°C. 8.20 mmol of ethanol is added to the polymer solution as a reaction terminator.

[0382] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 6.

[0383] The obtained conjugated diene polymer 6 was analyzed using the above method, and the analytical results are shown in Table 1.

[0384] ((Manufacturing Example 7) Conjugated diene polymer 7)

[0385] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 690g of 1,3-butadiene, 510g of styrene, 5,600g of cyclohexane, 7.81mmol of tetrahydrofuran (THF) and 1.045mmol of potassium tert-amyl alcohol were added to the reactor after impurities were removed. The reactor temperature was maintained at 56°C.

[0386] 5.23 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0387] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction, with a peak temperature of 77°C. 5.23 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0388] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 7.

[0389] The obtained conjugated diene polymer 7 was analyzed using the above method, and the analytical results are shown in Table 1.

[0390] ((Manufacturing Example 8) Conjugated diene polymer 8)

[0391] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 1140g of 1,3-butadiene, 60g of styrene, 5,600g of cyclohexane, 7.81mmol of tetrahydrofuran (THF) and 5.465mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances) were added to the reactor, and the reactor temperature was maintained at 48°C.

[0392] 13.27 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0393] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction. After reaching the peak reaction temperature of 88°C, 2.99 mmol of 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane was added as a coupling agent, and the mixture was stirred for 5 minutes. The coupling rate was 87.2%. 13.27 mmol of ethanol was then added to the polymer solution as a reaction terminator.

[0394] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 8.

[0395] The obtained conjugated diene polymer 8 was analyzed using the above method, and the analytical results are shown in Table 1.

[0396] ((Manufacturing Example 9) Conjugated diene polymer 9)

[0397] A 10L autoclave equipped with a stirrer and jacket and capable of temperature control was used as the reactor. 1128g of 1,3-butadiene, 72g of styrene, 5,600g of cyclohexane, and 7.81mmol of tetrahydrofuran (THF) as a polar substance were added to the reactor beforehand, and the internal temperature of the reactor was maintained at 56°C.

[0398] 21.35 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0399] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction. After reaching the peak reaction temperature of 91°C, 4.80 mmol of 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane was added as a coupling agent, and the mixture was stirred for 5 minutes. The coupling efficiency was 89.6%. 21.35 mmol of ethanol was then added to the polymer solution as a reaction terminator.

[0400] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)-o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 9.

[0401] The obtained conjugated diene polymer 9 was analyzed using the above method, and the analytical results are shown in Table 1.

[0402] ((Manufacturing Example 10) Conjugated diene polymer 10)

[0403] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 732g of 1,3-butadiene, 468g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 0.742mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances), and 0.440mmol of potassium tert-amyloxide were added to the reactor, and the reactor temperature was maintained at 50°C.

[0404] 5.50 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0405] After the polymerization reaction begins, the temperature inside the reactor rises due to the exothermic reaction, with a peak temperature of 82°C. 5.50 mmol of ethanol is added to the polymer solution as a reaction terminator.

[0406] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid and 1.4 g of 4,6-bis(octylthiomethyl)-o-cresol as antioxidants to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 10.

[0407] The obtained conjugated diene polymer 10 was analyzed using the above method, and the analytical results are shown in Table 1.

[0408] ((Manufacturing Example 11) Conjugated diene polymer 11)

[0409] A 10L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 574g of 1,3-butadiene, 626g of styrene, 5,600g of cyclohexane (pre-removed impurities), 7.81mmol of tetrahydrofuran (THF) and 1.086mmol of 2,2-bis(2-tetrahydrofuranyl)propane (as polar substances), and 0.646mmol of potassium tert-amyloxide were added to the reactor, and the reactor temperature was maintained at 53°C.

[0410] 6.21 mmol of n-butyllithium, used as a polymerization initiator, was supplied to the reactor described above.

[0411] After the polymerization reaction began, the temperature inside the reactor rose due to the exothermic reaction, with a peak temperature of 84°C. 6.21 mmol of ethanol was added to the polymer solution as a reaction terminator.

[0412] Add 4.4 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid as antioxidants and 1.4 g of 4,6-bis(octylthiomethyl)o-cresol to the obtained polymer solution. Then, add the conjugated diene polymer solution dropwise to warm water to remove the solvent. Dry the solution using a dryer to obtain conjugated diene polymer 11.

[0413] The obtained conjugated diene polymer 11 was analyzed using the above method, and the analytical results are shown in Table 1.

[0414] [Table 1]

[0415] [Rubber composition for outsole and manufacture of outsole]

[0416] (Example 1)

[0417] The rubber composition for the outsole and the outsole are prepared according to the following proportions.

[0418] Composition of the rubber composition for outsoles

[0419] Rubber component 1 (ASAPRENE 303 [manufactured by Asahi Kasei Corporation]): 30.0 parts by weight

[0420] Rubber component 2 (BR1208 [manufactured by LG Chem]): 70.0 parts by weight

[0421] Filler (REOLOSIL QS20 [manufactured by Tokuyama Corporation]): 30.0 parts by weight

[0422] Silane coupling agent (Dynasylan 6498 [manufactured by Evonik]): 2.0 parts by weight

[0423] Tackifier (Arkon M-100 [manufactured by Arakawa Chemical Industry Co., Ltd.]): 2.0 parts by weight

[0424] Antioxidant (NOCRAC SP [manufactured by Ouchi Shinshin Chemical Co., Ltd.]): 0.5 parts by weight

[0425] Crosslinking agent (Percumyl D [manufactured by Nippon Oil Company])

[0426] Total: 134.5 parts by weight

[0427] The above materials are mixed by the following method to obtain a rubber composition for outsoles and an outsole.

[0428] Using a 0.6L Bamberley mixer (Toyo Seiki Manufacturing, LABO PLASTOMILL 10C100, B600 torque rheometer) as the first stage of mixing, under the conditions of 65% filler, rotor speed 35 rpm, and initial set temperature 95°C, rubber component 1 (ASAPRENE303), filler (REOLOSIL QS20), silane coupling agent (Dynasylan6498), tackifier (Arkon M-100), and antioxidant (NOCRAC SP) were mixed for 7 minutes to obtain the first stage compound (outsole rubber composition without crosslinking agent).

[0429] Next, after cooling, as the second stage of mixing, a crosslinking agent is added, and the mixture is mixed using an open mill set to 35°C to obtain a compound (a rubber composition for outsoles containing the crosslinking agent).

[0430] Finally, a hot press is used to crosslink the material for about 13 minutes at 160°C and a pressure of about 15 MPa to obtain the crosslinked outsole composition, which is equivalent to the molded body of the outsole.

[0431] After cross-linking, the physical properties of the molded body, which is equivalent to the outsole, are measured.

[0432] The results of the physical property tests are shown in Table 2 below.

[0433] It should be noted that the ML viscosity of the second-stage mixture and the physical properties of the molded body of the outsole after cross-linking as described above were measured using the following method.

[0434] (Examples 2-23, Examples 54-57, Comparative Examples 1-4)

[0435] By changing the compounding materials and composition of the rubber composition for the outsole as shown in Tables 2 to 4 below, Examples 2 to 23, Examples 54 to 57 and Comparative Examples 1 to 4 were obtained using the same method as Example 1.

[0436] The blended materials, composition ratios, and physical properties are shown in Tables 2 to 4.

[0437] The following shows the rubber, tackifier, thermoplastic resin, and liquid rubber used in Examples 2-23, Examples 54-57, and Comparative Examples 1-4.

[0438] Rubber ASAPRENE 303 [Manufactured by Asahi Kasei Corporation] Conjugated diene polymer 1 Conjugated diene polymer 2 Conjugated diene polymers 3 Conjugated diene polymers 4 Conjugated diene polymers 10 Conjugated diene polymers 11 BR1208 [Manufactured by LG Chem] <Adhesive> Arkon M-100 [Manufactured by Arakawa Chemical Industry Co., Ltd.] ESCORE Z5600 [Manufactured by ExxonMobil] YS resin TO115 [manufactured by Yasuhara Chemical Co., Ltd.] PINECRYSTAL KE100 [Manufactured by Arakawa Chemical Industry Co., Ltd.] <Thermoplastic Resins> NOVATEC LL [Manufactured by Japan Polyethylene Co., Ltd.] Liquid rubber LBR-302 [Manufactured by KURARAY] [Evaluation of the physical properties of the outsole] ((1) complexML) The outsole rubber composition (containing a crosslinking agent) after the second stage of mixing was used as the test sample, and the test was performed using the same method as the Mooney viscosity test method described above.

[0439] ((2) Type A Shore hardness (hardness))

[0440] Regarding Shore A hardness, according to Japanese Industrial Standard JIS K6253-3, a test specimen (6.00 mm thick) is made by overlapping two sheets of material with a bottom thickness of 3.00 mm. The test specimen is then used for measurement. After the punch is pressed against the sheet with a certain indentation, the penetration depth after 3 seconds is measured, which is taken as the Shore A hardness.

[0441] (3) HAZE value)

[0442] The HAZE value was measured according to Japanese Industrial Standard JIS K7136 (or ISO 14782).

[0443] The outsole was molded into a sheet with a thickness of 3.00 mm and measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

[0444] (4) Wear resistance (wear loss)

[0445] The wear was measured according to the DIN abrasion test in accordance with JIS K 6264, and evaluated using index values.

[0446] Specifically, the wear volume of the outsole of the examples and comparative examples was measured using the DIN abrasion test, and the abrasion resistance was determined based on the amount of abrasion.

[0447] (5) Tensile strength and elongation)

[0448] The tensile strength and elongation of the outsoles of the examples and comparative examples were measured according to Japanese Industrial Standard JIS K6251. Evaluation was performed using index values.

[0449] (6) Grip (coefficient of kinetic friction)

[0450] The coefficient of dynamic friction was determined using a friction and wear testing machine (HeidonTribo Gear Type 40) manufactured by Shin-Tung Science & Technology Co., Ltd., and the index value was used to evaluate grip performance.

[0451] The sliding surface is made of ceramic tile, which is lubricated by water. A sheet with a thickness of 3mm, a width of 30mm, and a depth of 30mm is brought into contact with the sliding surface. The sample is subjected to 10 cycles of sliding under the conditions of a load of 500gf, a sliding speed of 10mm / min, and a sliding distance of 80mm.

[0452] The dynamic friction coefficient of the 6th to 10th reciprocating strokes at this time is averaged to determine the grip.

[0453] Evaluation is conducted using index values.

[0454] [Table 2]

[0455] [Table 3]

[0456] [Table 4]

[0457] The evaluation of each embodiment in Tables 2 to 4 is based on the assumption of its intended use as an athletic shoe. In a practically sufficient benchmark evaluation, the grip (coefficient of kinetic friction) is 85 or higher, the abrasion resistance (abrasion loss) is 140 or lower, the tensile strength is 60 or higher, and the elongation is 70 or higher.

[0458] It can be seen that, compared with the outsoles of Comparative Examples 1 to 4, the outsoles of Examples 1 to 23 and Examples 54 to 57 have sufficient processability in practical use, and excellent strength, abrasion resistance and grip.

[0459] [Rubber composition for outsole and manufacture of outsole]

[0460] (Example 24)

[0461] The rubber composition for the outsole and the outsole are obtained according to the following proportions.

[0462] Composition of the rubber composition for outsoles

[0463] Rubber component 1 (conjugated diene polymer 5): 30.0 parts by weight

[0464] Rubber component 2 (UBEPOL BR150 [manufactured by UBE Elastomer]): 60.0 parts by weight

[0465] Rubber component 3 (Nipol IR2200 [manufactured by Zeon Corporation, Japan]): 10.0 parts by weight

[0466] Filler (Ultrasil VN3 [manufactured by Evonik]): 40.0 parts by weight

[0467] Silane coupling agent (Si69 [manufactured by Evonik]): 2.0 parts by weight

[0468] Tackifier (Arkon M-100 [manufactured by Arakawa Chemical Industry Co., Ltd.]): 2.0 parts by weight

[0469] Antioxidant (NOCRAC 6C [manufactured by Ouchi Shinshin Chemical Industry Co., Ltd.]): 1.0 part by weight

[0470] Vulcanizing aid (zinc white): 3.0 parts by weight

[0471] Vulcanizing aid (stearic acid): 2.0 parts by weight

[0472] Sulfur: 1.4 parts by weight

[0473] Vulcanization accelerator (MBT): 1.0 parts by weight

[0474] Vulcanization accelerator (TBBS): 1.0 parts by weight

[0475] Total: 153.0 parts by weight

[0476] The above materials are mixed by the following method to obtain a rubber composition for outsoles and an outsole.

[0477] Using a 0.6L Bamberley mixer (Toyo Seiki Manufacturing, LABO PLASTOMILL 10C100, B600 torque rheometer) as the first stage of mixing, under the conditions of 65% filler, rotor speed 35 rpm, and initial set temperature 75°C, rubber component 1 (conjugated diene polymer 5), rubber component 2 (UBEPOL BR150), rubber component 3 (NipolIR2200), filler (Ultrasil VN3), silane coupling agent (Si69), tackifier (Arkon M-100), and antioxidant (NOCRAC 6C) were mixed for 7 minutes to obtain the first stage compound (outsole rubber composition without crosslinking agent).

[0478] Next, after cooling, as the second stage of mixing, a crosslinking agent is added, and the mixture is mixed using a two-roll mill set to 80°C to obtain a compound (a rubber composition for outsoles containing the crosslinking agent).

[0479] Finally, the rubber composition for the outsole is cross-linked for about 13 minutes at 160°C and a pressure of about 15 MPa using a hot press to obtain the cross-linked rubber composition.

[0480] In addition, the ML viscosity of the second-stage compound and the physical properties of the outsole rubber composition after cross-linking and molding as described above were measured.

[0481] The results of the physical property measurements are shown in Table 5.

[0482] (Examples 25-45, Comparative Examples 5-6)

[0483] As shown in Tables 5 to 7 below, by changing the mixing materials and composition ratio of the rubber composition for the outsole, Examples 25 to 45 and Comparative Examples 5 to 6 were obtained using the same method as in Example 24.

[0484] The blended materials, composition ratios, and physical properties are shown in Tables 5 to 7.

[0485] The rubber, tackifier, and plasticizer used in Examples 25-45 and Comparative Examples 5-6 are shown below.

[0486] Rubber ASAPRENE Y031 [Manufactured by Asahi Kasei Corporation] Conjugated diene polymers 5 Conjugated diene polymers 6 Conjugated diene polymers 7 Conjugated diene polymers 8 Conjugated diene polymers 9 UBEPOL BR150 [Manufactured by UBE Elastomer] Nipol IR2200 [Manufactured by Zeon Corporation, Japan] <Adhesive> Arkon M-100 [Manufactured by Arakawa Chemical Industry Co., Ltd.] ESCORE Z5600 [Manufactured by ExxonMobil] YS resin TO115 [manufactured by Yasuhara Chemical Co., Ltd.] Tamanol 440 [Manufactured by Arakawa Chemical Industry Co., Ltd.] YS resin PX300N [manufactured by Yasuhara Chemical Co., Ltd.] Ardyme R-95 [Manufactured by Arakawa Chemical Industry Co., Ltd.] <Plasticizer> P-200 [Manufactured by ENEOS] The rubber compositions and outsoles used in Examples 24-45 and Comparative Examples 5-6 were evaluated for their physical properties in the same manner as in Example 1 above. The evaluation results are shown in Tables 5-7 below.

[0487] It should be noted that the Tg number of the mixture of conjugated diene polymer and tackifier was determined and evaluated as follows.

[0488] [Tg number of the mixture of conjugated diene polymers and tackifiers]

[0489] The Tg number of the mixture of conjugated diene polymer and tackifier can be determined by DSC measurement of the mixture according to Japanese Industrial Standard JIS K6240.

[0490] [Table 5]

[0491] [Table 6]

[0492] [Table 7]

[0493] The evaluation of each embodiment in Tables 5 to 7 is based on the assumption of walking applications. In a practically sufficient benchmark evaluation, the grip (coefficient of kinetic friction) is 80 or higher, the abrasion resistance (abrasion loss) is 135 or lower, the tensile strength is 63 or higher, and the elongation is 80 or higher.

[0494] It can be seen that, compared with the outsole rubber compositions of Comparative Examples 5-6, the outsole rubber compositions of Examples 24-45 have sufficient processability in practical use and excellent strength, abrasion resistance and grip.

[0495] [Rubber composition for outsole and manufacture of outsole]

[0496] (Example 46)

[0497] The rubber composition for the outsole and the outsole are obtained according to the following proportions.

[0498] Composition of the rubber composition for outsoles

[0499] Rubber component 1 (conjugated diene polymer 5): 100.0 parts by weight

[0500] Filler (Ultrasil VN3 [manufactured by Evonik]): 40.0 parts by weight

[0501] Silane coupling agent (Si69 [manufactured by Evonik]): 2.0 parts by weight

[0502] Tackifier (Arkon M-100 [manufactured by Arakawa Chemical Industry Co., Ltd.]): 2.0 parts by weight

[0503] Antioxidant (NOCRAC 6C [manufactured by Ouchi Shinshin Chemical Industry Co., Ltd.]): 1.0 part by weight

[0504] Vulcanizing aid (zinc white): 3.0 parts by weight

[0505] Vulcanizing aid (stearic acid): 2.0 parts by weight

[0506] Sulfur: 1.4 parts by weight

[0507] Vulcanization accelerator (MBT): 1.0 parts by weight

[0508] Vulcanization accelerator (TBBS): 1.0 parts by weight

[0509] Total: 153.0 parts by weight

[0510] The above materials are mixed by the following method to obtain a rubber composition for outsoles and an outsole.

[0511] Using a 0.6L Bamberley mixer (Toyo Seiki Manufacturing, LABO PLASTOMILL 10C100, B600 torque rheometer) as the first stage of mixing, under the conditions of 65% filler, rotor speed 35 rpm, and initial set temperature 75°C, rubber component 1 (conjugated diene polymer 5), filler (Ultrasil VN3), silane coupling agent (Si69), tackifier (Arkon M-100), and antioxidant (NOCRAC 6C) were mixed for 7 minutes to obtain the first stage compound (outsole rubber composition without crosslinking agent).

[0512] Next, after cooling, as the second stage of mixing, a crosslinking agent is added, and the mixture is mixed using a two-roll mill set to 80°C to obtain a compound (a rubber composition for outsoles containing the crosslinking agent).

[0513] Finally, the rubber composition for the outsole is obtained by cross-linking for about 13 minutes at 160°C and a pressure of about 15 MPa using a hot press.

[0514] In addition, the ML viscosity of the second-stage compound and the physical properties of the outsole rubber composition after cross-linking and molding as described above were measured.

[0515] The results of the physical property measurements are shown in Table 8.

[0516] (Examples 47-50, Comparative Examples 7-8)

[0517] As shown in Table 8 below, by changing the mixing materials and composition ratio of the rubber composition for the outsole, Examples 47-50 and Comparative Examples 7-8 were obtained using the same method as Example 46.

[0518] The blended materials, composition ratios, and physical properties are shown in Table 8.

[0519] The rubber, tackifier, and plasticizer used in Examples 47-50 and Comparative Examples 7-8 are shown below.

[0520] Rubber Conjugated diene polymers 5 ASAPRENE Y031 [Manufactured by Asahi Kasei Corporation] <Adhesive> Arkon M-100 [Manufactured by Arakawa Chemical Industry Co., Ltd.] <Plasticizer> P-200 [Manufactured by ENEOS] The rubber compositions and outsoles used in Examples 46-50 and Comparative Examples 7-8 were evaluated for their physical properties in the same manner as in Example 1 above. The results of the processing evaluation are shown in Table 8 below.

[0521] [Table 8]

[0522] The evaluation of each embodiment in Table 8 is based on the assumption of the intended use of hiking boots. In a practically sufficient benchmark evaluation, the grip (coefficient of kinetic friction) is 90 or higher, the abrasion resistance (abrasion loss) is 140 or lower, the tensile strength is 75 or higher, and the elongation is 80 or higher.

[0523] It can be seen that, compared with the outsole rubber compositions of Comparative Examples 7-8, the outsole rubber compositions obtained in Examples 46-50 have practically sufficient processability and excellent strength, abrasion resistance, and grip.

[0524] [Rubber composition for outsole and manufacture of outsole]

[0525] (Example 51)

[0526] The rubber composition for the outsole and the outsole are obtained according to the following proportions.

[0527] Composition of the rubber composition for outsoles

[0528] Rubber component 1 (UBEPOL BR150 [manufactured by UBE Elastomer]): 70.0 parts by weight

[0529] Rubber component 2 (Nipol DN4050 [manufactured by Zeon Corporation, Japan]): 30.0 parts by weight

[0530] Filler (Ultrasil VN3 [manufactured by Evonik]): 40.0 parts by weight

[0531] Silane coupling agent (Si69 [manufactured by Evonik]): 2.0 parts by weight

[0532] Tackifier (ESCOREZ 5600 [manufactured by ExxonMobil]): 10.0 parts by weight

[0533] Antioxidant (NOCRAC 6C [manufactured by Ouchi Shinshin Chemical Industry Co., Ltd.]): 1.0 part by weight

[0534] Vulcanizing aid (zinc white): 3.0 parts by weight

[0535] Vulcanizing aid (stearic acid): 2.0 parts by weight

[0536] Sulfur: 1.4 parts by weight

[0537] Vulcanization accelerator (MBT): 1.0 parts by weight

[0538] Vulcanization accelerator (TBBS): 1.0 parts by weight

[0539] Total: 153.0 parts by weight

[0540] The above materials are mixed by the following method to obtain a rubber composition for outsoles and an outsole.

[0541] Using a 0.6L Bamberley mixer (Toyo Seiki Manufacturing, LABO PLASTOMILL 10C100, B600 torque rheometer) as the first stage of mixing, under the conditions of 65% filler, rotor speed 35 rpm, and initial set temperature 75°C, rubber component 1 (UBEPOL BR150), rubber component 2 (Nipol DN4050), filler (Ultrasil VN3), silane coupling agent (Si69), tackifier (ESCOREZ5600), and antioxidant (NOCRAC 6C) were mixed for 7 minutes to obtain the first stage compound (outsole rubber composition without crosslinking agent).

[0542] Next, after cooling, as the second stage of mixing, a crosslinking agent is added, and the mixture is mixed using a two-roll mill set to 80°C to obtain a compound (a rubber composition for outsoles containing the crosslinking agent).

[0543] Finally, the rubber composition for the outsole is obtained by cross-linking for about 13 minutes at 160°C and a pressure of about 15 MPa using a hot press.

[0544] In addition, the ML viscosity of the second-stage compound and the physical properties of the outsole rubber composition after cross-linking and molding as described above were measured.

[0545] The results of the physical property measurements are shown in Table 9.

[0546] (Examples 52-53, Comparative Example 9)

[0547] As shown in Table 9 below, by changing the mixing materials and composition ratio of the rubber composition for the outsole, Examples 52-53 and Comparative Example 9 were obtained using the same method as Example 51.

[0548] The blended materials, composition ratios, and physical properties are shown in Table 9.

[0549] The rubber and tackifier used in Examples 52-53 and Comparative Example 9 are shown below.

[0550] Rubber UBEPOL BR150 [Manufactured by UBE Elastomer] ASAPRENE Y031 [Manufactured by Asahi Kasei Corporation] Nipol DN4050 [Manufactured by Zeon Corporation, Japan] Bromobutyl 2244 [Manufactured by ExxonMobil] <Adhesive> ESCORE Z5600 [Manufactured by ExxonMobil] The rubber compositions and outsoles used for the outsoles of Examples 51-53 and Comparative Example 9 were evaluated for their physical properties in the same manner as in Example 1 above. The evaluation results are shown in Table 9 below.

[0551] [Table 9]

[0552] The evaluation of each embodiment in Table 9 is based on the assumption of the intended use of the running shoe. In a practically sufficient benchmark evaluation, the grip (coefficient of kinetic friction) is 90 or higher, the abrasion resistance (abrasion loss) is 210 or lower, the tensile strength is 78 or higher, and the elongation is 76 or higher.

[0553] It can be seen that, compared with the outsole rubber composition of Comparative Example 9, the outsole rubber compositions obtained in Examples 51-53 have practically sufficient processability and excellent strength, abrasion resistance, and grip.

[0554] This application is based on Japanese Patent Application No. 2023-116818, filed with the Japan Patent Office on July 18, 2023, the contents of which are incorporated herein by reference.

[0555] Industrial applicability

[0556] The rubber composition for the outsole of this embodiment has industrial applicability as a material for sports shoes, walking shoes, and hiking shoes.

Claims

1. A rubber composition for outsoles, comprising rubber, filler, and tackifier.

2. The rubber composition for outsoles according to claim 1, wherein the rubber contains a conjugated diene polymer.

3. The rubber composition for outsoles according to claim 2, wherein, The conjugated diene polymer contains aromatic vinyl monomer units and conjugated diene monomer units.

4. The rubber composition for outsoles according to claim 3, wherein, In the conjugated diene polymer, the content of aromatic vinyl monomer units is more than 10% by mass and less than 60% by mass, and the vinyl bonding content is more than 20% and less than 70%.

5. The rubber composition for outsoles according to claim 3, wherein, In the conjugated diene polymer, the content of aromatic vinyl monomer blocks is less than 5% by mass.

6. The rubber composition for outsoles according to claim 1, wherein, The content of the filler is 15 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the rubber.

7. The rubber composition for outsoles according to claim 1, wherein, The filler contains more than 80% by mass of silicon dioxide relative to its total mass.

8. The rubber composition for outsoles according to claim 1, wherein, The softening point of the tackifier is 40℃~170℃.

9. The composition for outsoles according to claim 1, wherein, The glass transition temperature of the tackifier is above -20°C.

10. The rubber composition for outsoles according to claim 1, wherein, The adhesive is a terpene compound and / or a petroleum hydrocarbon compound.

11. The composition for outsoles according to claim 1, wherein, The tackifier b The value is below 50.

12. The rubber composition for outsoles according to claim 10, wherein, The petroleum hydrocarbon compounds are aromatic petroleum hydrocarbon resins or alkylphenols.

13. The rubber composition for outsoles according to claim 1, wherein, The mixture of the rubber and the tackifier has a Tg of one in differential scanning calorimetry (DSC).

14. The rubber composition for outsoles according to claim 2, wherein, The tackifier is a terpene compound, and the content of aromatic vinyl monomer units in the conjugated diene polymer is more than 10% by mass and less than 50% by mass, and the vinyl bonding content is more than 24% and less than 60%.

15. The rubber composition for outsoles according to claim 2, wherein, The tackifier is a petroleum hydrocarbon compound, and the content of aromatic vinyl monomer units in the conjugated diene polymer is more than 20% by mass and less than 60% by mass, and the vinyl bonding content is more than 20% and less than 55%.

16. The rubber composition for outsoles according to claim 1, wherein, The difference between the glass transition temperature of the rubber and the tackifier is greater than 10°C and less than 180°C.

17. The rubber composition for outsoles according to claim 1, wherein, The content of the tackifier in the rubber composition for the outsole is more than 1 part by weight and less than 30 parts by weight, relative to 100 parts by weight of the rubber.

18. The rubber composition for outsoles according to claim 1, wherein, The haze level is below 50%.

19. The rubber composition for outsoles according to claim 1, wherein, The rubber contains 10% by mass and less than 60% by mass of nitrile rubber.

20. The rubber composition for outsoles according to claim 1, wherein, The rubber contains more than 10% by mass and less than 90% by mass of epichlorohydrin rubber.

21. The rubber composition for outsoles according to claim 1, wherein, The rubber contains 10% or more but less than 90% by mass of urethane rubber.

22. The rubber composition for outsoles according to claim 1, wherein, The rubber contains 10% or more and 90% or less by mass of chlorosulfonated vinyl rubber.

23. The rubber composition for outsoles according to claim 1, wherein, The rubber contains 10% or more but less than 90% by mass of acrylic rubber.

24. The rubber composition for outsoles according to claim 1, wherein, The rubber contains 10% or more but less than 90% by mass of silicone rubber.

25. The rubber composition for outsoles according to claim 1, wherein, The rubber contains 10% or more and 90% or less of fluororubber.

26. The rubber composition for outsoles according to claim 2, wherein, The conjugated diene polymers include polybutadiene and styrene-butadiene copolymers.

27. An outsole, which is a molded body of the rubber composition for outsole according to any one of claims 1 to 26.

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