Method of use of polyphenylene ether, rubber composition for outsoles, outsoles and shoes

Abstract

This invention provides a rubber composition for outsoles that can achieve a high level of flexibility, tensile strength, wet grip, and ice grip, as well as a novel method for using polyphenylene ether as a raw material for the outsole rubber composition. [Solution] In order to solve the above problems, the present invention is characterized by using a polyphenylene ether (A) having a glass transition temperature of less than 150°C as measured by differential scanning calorimetry (DSC) as a raw material for an outsole rubber composition.

Description

Technical Field

[0001] The present invention relates to a method of using polyphenylene ether, a rubber composition for an outsole, an outsole, and a shoe.

Background Art

[0002] Conventionally, rubber compositions have been widely used in the field of industrial parts such as automobile members, tire members, packings, gaskets, sealing materials, vibration-proof rubber, vibration-isolation rubber, vibration-damping materials, shoe outsoles, shoe midsoles, and the like. And, for a rubber composition (hereinafter sometimes simply referred to as "outsole rubber composition") used as a shoe outsole (hereinafter sometimes simply referred to as "outsole"), as a performance, grip property against the ground for enhancing safety is required. In particular, since the ground wet with water or the ground in a cold environment is slippery, it is required to improve the grip property against the ground wet with water or the ground in a cold environment (hereinafter, in this specification, "grip property against the ground wet with water" may be referred to as "wet grip property". Also, "grip property against the ground in a cold environment" may be referred to as "ice grip property").

[0003] Here, generally, inorganic fillers such as carbon black, calcium carbonate, and silica are blended in the outsole composition. However, since inorganic fillers such as silica are inferior in affinity with rubber compared with carbon black, the dispersibility of silica in rubber is not always good, and problems such as a decrease in flexibility and tensile strength occur due to this poor dispersibility.

[0004] In response to such problems, in Patent Document 1, a rubber composition for a shoe sole mainly composed of a conjugated diene rubber having a structure in which a specific functional group is bonded to a conjugated diene polymer chain has been proposed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, according to Patent Document 1, although the processability is improved, the effect of improving the grip property as an outsole is not yet sufficient, and further improvement has been desired.

[0007] Therefore, in the technical field of rubber compositions used for outsoles and the like, it is technically difficult to achieve both flexibility and various grip properties and tensile strength, and it is required to achieve these properties at a high level.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the problems of the above-described conventional technologies, the present inventors have found that by using a polyphenylene ether having a specific glass transition temperature, it is possible to provide a rubber composition for an outsole that is excellent in flexibility, wet grip property and ice grip property, and also excellent in tensile strength, and have completed the present invention.

[0009] That is, the present invention is as follows. 〔1〕A method for using a polyphenylene ether, characterized in that a polyphenylene ether (A) having a glass transition temperature measured by differential scanning calorimetry (DSC) of less than 150°C is used as a raw material for a rubber composition for an outsole. 〔2〕The polyphenylene ether (A) includes a repeating unit derived from a phenol of the following formula (1) and a repeating unit derived from a phenol of the following formula (2), The method for using the polyphenylene ether according to [1], wherein the content ratio of the repeating unit derived from phenol of the following formula (1) is 6 mol% or more and 100 mol% with respect to a total of 100 mol% of the repeating units of the following formula (1) and the following formula (2), and the content ratio of the repeating unit derived from phenol of the following formula (2) is more than 0 mol% and 94 mol% or less.

Chemical formula

Chemical formula

Chemical formula

[0010] According to the present invention, a rubber composition for outsoles can be obtained that achieves a high level of balance between flexibility, tensile strength, wet grip, and ice grip. Furthermore, according to the present invention, a new method of using polyphenylene ether is provided, in which polyphenylene ether is used as a raw material for a rubber composition for outsoles. [Modes for carrying out the invention]

[0011] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. The following embodiments are illustrative examples for explaining the present invention, and the present invention is not limited to these embodiments. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0012] <How to use polyphenylene ether> In this embodiment, the polyphenylene ether is used as a raw material for the outsole composition, and its glass transition temperature, as measured by differential scanning calorimetry (DSC), is less than 150°C. By using polyphenylene ethers with a glass transition temperature of less than 150°C, as measured by differential scanning calorimetry (DSC), in a rubber composition, the composition can be made less viscous and more flexible. Furthermore, polyphenylene ethers with a glass transition temperature of less than 150°C have good dispersibility in the composition and have ample opportunities for crosslinking with other components, thus easily forming a large molecular network. This allows for improved tensile strength and control of molecular mobility, thereby reducing hysteresis loss in specific temperature ranges and providing wet grip and ice grip. As a result, a rubber composition for outsoles that achieves a high level of balance between flexibility, tensile strength, wet grip, and ice grip can be realized.

[0013] (Polyphenylene ether (A)) In the method of using polyphenylene ether according to this embodiment, the outsole rubber composition contains the polyphenylene ether (A), and the polyphenylene ether has a glass transition temperature of less than 150°C determined by DSC.

[0014] The glass transition temperature of the polyphenylene ether by DSC must be less than 150°C, preferably less than 50°C, and more preferably less than 0°C. If the glass transition temperature of the polyphenylene ether is less than 150°C, the resulting outsole rubber composition exhibits excellent flexibility, tensile strength, wet grip, and ice grip.

[0015] Furthermore, the glass transition temperature of the polyphenylene ether by DSC must be -100°C or higher, preferably -80°C or higher, and more preferably -50°C or higher. If the glass transition temperature of the polyphenylene ether by DSC is -100°C or higher, the balance of each of the properties of the resulting outsole rubber composition will be at a highly favorable level.

[0016] The polyphenylene ether (A) contained in the outsole rubber composition of this embodiment may be used alone or in combination of two or more types.

[0017] Furthermore, as a method for adjusting the glass transition temperature by DSC, for example, it is possible to lower the glass transition temperature by designing molecules that weaken the interactions between polymer chains and allow the polymer chains to move more easily. Although not particularly limited, for example, it is possible to lower the glass transition temperature by introducing repeating units having long-chain alkyl groups into polyphenylene ether. In addition, the glass transition temperature by DSC can be adjusted by appropriately adjusting the introduction ratio of repeating units having long-chain alkyl groups and the chain length of the long-chain alkyl groups. Furthermore, there are no particular limitations on the measuring device used to measure differential scanning calorimetry, and commercially available devices can be used. For example, the "DSC250" manufactured by T.A. Instruments Corporation can be used as the differential scanning calorimetry device.

[0018] Furthermore, the polyphenylene ether (A) preferably contains repeating units derived from phenol of the following formula (1) from the viewpoint of improving vulcanization reactivity with the outsole rubber composition. Polyphenylene ethers containing repeating units derived from phenol of formula (1) below exhibit high reactivity because multiple reaction sites are located on side chains that protrude from the molecular main chain, resulting in less steric hindrance and a higher frequency of intermolecular collisions. This improved vulcanization reactivity allows for a higher vulcanization rate, and the resulting outsole rubber composition tends to have superior tensile strength, wet grip, and ice grip. [ka]

[0019] In equation (1) above, R 13 R is a saturated or unsaturated hydrocarbon group having 15 carbon atoms, which may be substituted. 11 and R 12 Each of these is independently selected from the group consisting of a hydrogen atom, a linear saturated hydrocarbon group having 1 to 12 carbon atoms, and a substituent represented by formula (3).

[0020] Preferred R 11 and R 12 Each of these is independently selected from a hydrogen atom, a methyl group, an ethyl group, and a substituent represented by formula (3). More preferably, R 11 This is the substituent represented by formula (3). Particularly preferred, R 11 is a substituent represented by formula (3), and R 12 That is a hydrogen atom. [ka] (In formula (3), R 31 Each of these is independently a linear alkyl group having 1 to 8 carbon atoms, which may be substituted, or two R 31 However, the atoms contained in them are bonded to each other to form a cyclic alkyl group having 1 to 8 carbon atoms, R 32 Each of these is independently an alkylene group having 1 to 8 carbon atoms, which may be substituted, and each of these is independently 0 or 1, R 33(This is a hydrogen atom, an optionally substituted C1-C8 alkyl group, or an optionally substituted phenyl group.)

[0021] Furthermore, the substituent represented by formula (3) above is preferably a group containing secondary and / or tertiary carbons, such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2,2-dimethylpropyl group, cyclohexyl group, and groups in which the hydrogen of the terminal hydrocarbon group in these groups is substituted with a phenyl group. More preferably, the substituent represented by formula (3) above is a tert-butyl group or a cyclohexyl group, and even more preferably a tert-butyl group. In addition, the atoms contained therein may be bonded to each other to form a cyclic structure.

[0022] Furthermore, in the method of using polyphenylene ether according to this embodiment, in formula (1) above, R 11 is a t-butyl group, and R 12 A configuration in which is a hydrogen atom is preferred.

[0023] Note that in equation (1) above, R 13 is a saturated or unsaturated hydrocarbon group having 15 carbon atoms, which may be substituted, preferably R 13 C 15 H 31-2n (where n is an independent integer between 0 and 3)

[0024] Furthermore, in the method of using polyphenylene ether according to this embodiment, from the viewpoint of the heat resistance of the resulting outsole rubber composition, the polyphenylene ether may contain not only repeating units derived from phenol of formula (1) but also repeating units derived from phenol of formula (2). [ka] (In formula (2), R 21 Each of these is independently a saturated hydrocarbon group having 1 to 6 carbon atoms, which may be substituted, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and R22 Each of these is independently a hydrogen atom, an optionally substituted C1-C6 hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0025] Furthermore, in equation (2) above, R 21 Each of these is preferably an independently saturated hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group, and even more preferably a methyl group. In addition, in formula (2) above, the two R 21 It is preferable that both have the same structure.

[0026] Furthermore, in equation (2) above, R 22 Each of these is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. In the above formula (2), the two R 22 They may be the same or different.

[0027] In a preferred embodiment, two R 22 Examples include embodiments in which both are hydrogen atoms, or embodiments in which one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (more preferably a methyl group).

[0028] In this embodiment, the structure of the polyphenylene ether can be identified by analyzing it using techniques such as NMR and mass spectrometry.

[0029] Specific methods for identifying the structure of the aforementioned polyphenylene ether include performing field desorption mass spectrometry (FD-MS), which is known to be less prone to fragmentation, and estimating the repeating units based on the spacing of the detected ions. Furthermore, methods for estimating the structure of the polyphenylene ether include combining electron ionization (EI) peak analysis of fragment ions with NMR structural analysis. Also, for example, 1 This can be determined using analytical methods such as 1H NMR.

[0030] Furthermore, it is preferable that the polyphenylene ether (A) has a content ratio of repeating units derived from phenol of formula (1) of formula (1) to 6 mol% or more and 100 mol% or less, with a content ratio of repeating units derived from phenol of formula (2) of formula (2) of more than 0 mol% and 94 mol% or less, based on a total of 100 mol% of repeating units derived from phenol of formula (1) and repeating units derived from phenol of formula (2).

[0031] Furthermore, from the viewpoint of achieving a high level of flexibility, tensile strength, wet grip, and ice grip in the resulting outsole rubber composition, the content ratio of the repeating units derived from phenol of formula (1) to the total of 100 mol% of the repeating units derived from phenol of formula (2) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more. On the other hand, there is no upper limit on the content ratio of formula (1).

[0032] Furthermore, the content of the repeating units derived from phenol in formula (2) can be appropriately selected depending on the application. For example, if you want to improve heat resistance, it is preferable to have a larger amount of the repeating units derived from phenol in formula (2).

[0033] In this embodiment, the total molar ratio of the repeating units derived from the phenol of formula (1) and the repeating units derived from the phenol of formula (2) to 100 mol% of the polyphenylene ether is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and may also be 100 mol%.

[0034] The molar ratio of the repeating units derived from phenol in formula (1) and the molar ratio of the repeating units derived from phenol in formula (2) to the total of 100 mol% of the repeating units derived from phenol in formula (1) and the repeating units derived from phenol in formula (2) is, for example, 1 H-NMR, 13 It can be determined using analytical techniques such as 13C-NMR, and more specifically, it can be measured by the method described in the examples below.

[0035] Furthermore, the polyphenylene ether (A) may contain repeating units derived from phenol of the following formula (4). In this case, the Tg of the outsole rubber composition can be lowered, thereby improving wet grip. [ka] In the above equation (4), R 41 , R 42 , R 43 Each is independently a C7-C25 organic group having one or more atoms selected from the group consisting of a linear saturated hydrocarbon group having 1 to 12 carbon atoms and optionally substituted nitrogen, oxygen, and sulfur atoms, and R 41 , R 42 , R 43 One or more of these are organic groups having 7 to 25 carbon atoms, each containing one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms.

[0036] Also, in equation (4) above, R 41 , R 42 , R 43 Preferably, one or more of these are organic groups having 8 to 20 carbon atoms and containing a sulfur atom, and more preferably, organic groups having 9 to 15 carbon atoms and containing a sulfur atom.

[0037] Furthermore, the phenol in formula (4) above is preferably 4,6-bis(octylthiomethyl)-o-cresol or 4,6-bis(dodecylthiomethyl)-o-cresol.

[0038] Furthermore, the polyphenylene ether may contain, in addition to the repeating units derived from the phenol of formula (4), the repeating units derived from the phenol of formula (2).

[0039] The polyphenylene ether preferably contains 7 to 50 mol% of the repeating units derived from formula (4) and 50 to 93 mol% of the repeating units derived from formula (2), with a total of 100 mol% of the repeating units derived from formula (4) and the repeating units derived from formula (2).

[0040] From the viewpoint of the flexibility of the resulting outsole rubber composition, the content ratio of the repeating units derived from phenol of formula (4) to the total of 100 mol% of the repeating units derived from phenol of formula (2) is preferably 7 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more.

[0041] Furthermore, from the viewpoint of the wet grip and ice grip properties of the resulting outsole rubber composition, the content ratio of the repeating units derived from the phenol of formula (4) to the total of 100 mol% of the repeating units derived from the phenol of formula (2) in the polyphenylene ether is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0042] Furthermore, the total molar ratio of the repeating units derived from the phenol of formula (4) and the repeating units derived from the phenol of formula (2) to 100 mol% of the total polyphenylene ether is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and may be 100 mol%.

[0043] The polyphenylene ether may have at least one substructure selected from the group consisting of the substructure of formula (10), the substructure of formula (11), the substructure of formula (12), and the substructure of formula (13). [ka] [ka] [ka] (In formula (12), R 4 R is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the above saturated or unsaturated hydrocarbon is R 4 The substituents may be present within the range of 1 to 10 total carbon atoms. [ka] (In formula (13), R 5 R is a saturated or unsaturated divalent hydrocarbon group having 1 to 10 carbon atoms, and the above saturated or unsaturated divalent hydrocarbon is R 5 The substituents may be within the range of 1 to 10 carbon atoms, R 6 R is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the saturated or unsaturated hydrocarbon is R 6 The substituents may be within the range of 1 to 10 total carbon atoms.

[0044] Furthermore, at least one substructure selected from the group consisting of the substructure of formula (10), the substructure of formula (11), the substructure of formula (12), and the substructure of formula (13) may be introduced by a modification process described later, and may directly bond with the oxygen atom of the hydroxyl group contained in the polyphenylene ether.

[0045] (Method for producing polyphenylene ether) Furthermore, the polyphenylene ether (A) can be obtained by a method that includes, for example, at least a step of oxidative polymerization of a monovalent raw material phenol containing the phenol of formula (1) above. Preferably, the step of oxidative polymerization is a step of oxidative polymerization of a raw material phenol containing the phenol of formula (1) above and the phenol of formula (2) above.

[0046] Examples of the phenol of formula (1) above include 3-pentadecylphenol, commercially available cardanol, modified 3-pentadecylphenol obtained by introducing a linear saturated hydrocarbon group having 1 to 12 carbon atoms or a substituent represented by formula (3) above into 3-pentadecylphenol, and modified cardanol obtained by introducing a linear saturated hydrocarbon group having 1 to 12 carbon atoms or a substituent represented by formula (3) above into commercially available cardanol. From the viewpoint of suppressing multi-branching and gelation, R 11 By introducing bulky substituents such as tert-butyl groups and cyclohexyl groups, or R 11 and R 12 It is preferable to introduce methyl groups to both R 11 and R 12 Methods for introducing substituents to the compound include A) reacting an alkyl halide in the presence of a Lewis acid, and B) reacting isobutene or the like in the presence of a Brønsted acid. The phenol in formula (1) above may be used individually or in combination of multiple types.

[0047] Examples of phenols in formula (2) above include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, and 2,6-dimethyl-3-t-butylphenol. In particular, 2,6-dimethylphenol, 2,3,6-trimethylphenol, and 2,6-diphenylphenol are preferred because they are inexpensive and readily available. The phenol in formula (2) above may be used individually or in combination of multiple types.

[0048] Furthermore, the polyphenylene ether (A) can be obtained by a method that includes, for example, at least a step of oxidative polymerization of a monovalent raw material phenol containing the phenol of formula (4) above. Preferably, the step of oxidative polymerization is a step of oxidative polymerization of a raw material phenol containing the phenol of formula (4) above and the phenol of formula (2) above.

[0049] As for the phenol in formula (4) above, commercially available products that are preferred are 4,6-bis(octylthiomethyl)-o-cresol and 4,6-bis(dodecylthiomethyl)-o-cresol. In the method for producing polyphenylene ether (A), an aromatic solvent, which is a good solvent for polyphenylene ether, can be used as the polymerization solvent in the oxidative polymerization step. Here, a good solvent for polyphenylene ether is a solvent that can dissolve polyphenylene ether. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including o-, m-, and p- isomers), and ethylbenzene, as well as halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; and nitro compounds such as nitrobenzene.

[0050] As the polymerization catalyst used in this embodiment, any known catalyst system that can be used in the production of polyphenylene ethers can be used. Commonly known catalyst systems consist of a transition metal ion having redox activity and an amine compound that can form a complex with the transition metal ion. Examples include catalyst systems consisting of a copper compound and an amine compound, a catalyst system consisting of a manganese compound and an amine compound, a catalyst system consisting of a cobalt compound and an amine compound, and so on. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a small amount of alkali or further amine compounds may be added.

[0051] The polymerization catalyst preferred in this embodiment is a catalyst comprising a copper compound, a halogen compound, and an amine compound as catalyst components, and more preferably a catalyst containing a diamine compound represented by the following formula (14) as the amine compound. [ka] (In formula (14), R 14 , R 15 , R 16 , R 17 Each of these is independently a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and not all of them are hydrogen atoms at the same time. 18 (This refers to an alkylene group having 2 to 5 carbon atoms, either linear or methyl-branched.)

[0052] Examples of copper compounds used as catalyst components are listed below. Suitable copper compounds include cuprous compounds, cupric compounds, or mixtures thereof. Examples of cupric compounds include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, and cuprous sulfate. Among these, particularly preferred metallic compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may also be synthesized at the time of use from oxides (e.g., cuprous oxide), carbonates, hydroxides, and corresponding halogens or acids. A frequently used method is to prepare them by mixing the previously exemplified cuprous oxide with hydrogen halides (or solutions of hydrogen halides).

[0053] Examples of the halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. These can also be used as aqueous solutions or solutions with a suitable solvent. These halogen compounds can be used individually or in combination of two or more. Preferred halogen compounds are aqueous solutions of hydrogen chloride and aqueous solutions of hydrogen bromide.

[0054] The amount of these compounds used is not particularly limited, but it is preferable that the amount of halogen atoms be between 2 and 20 times the number of moles of copper atoms, and the preferred amount of copper atoms to be used per 100 moles of phenol compound added to the polymerization reaction is in the range of 0.02 moles to 0.6 moles. Next, we will list examples of diamine compounds that are catalyst components. For example, N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diethylethylenediamine, N-ethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N,N'-n-propylethylenediamine, Ni-propylethylenediamine, N,N'-i-propylethylenediamine, Nn-butylethylenediamine Examples include methyl ethylenediamine, N,N'-n-butylethylenediamine, Ni-butylethylenediamine, N,N'-i-butylethylenediamine, Nt-butylethylenediamine, N,N'-t-butylethylenediamine, N,N,N'-tetramethyl-1,3-diaminopropane, N,N,N'-trimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N-methyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,3-diamino-1-methylpropane, N,N,N',N'-tetramethyl-1,3-diamino-2-methylpropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, and N,N,N',N'-tetramethyl-1,5-diaminopentane. For this embodiment, preferred diamine compounds are those in which the alkylene group connecting two nitrogen atoms has two or three carbon atoms. The amount of these diamine compounds used is not particularly limited, but it is preferably in the range of 0.01 moles to 10 moles per 100 moles of the phenol compound added to the polymerization reaction.

[0055] In this embodiment, the polymerization catalyst may include primary amines and secondary monoamines as constituent components. Examples of secondary monoamines, but not limited to the following, include dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2',6'-dimethylphenyl)ethanolamine, N-(p-chlorophenyl)ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, and diphenylamine.

[0056] Furthermore, the polymerization catalyst may also contain a tertiary monoamine compound. A tertiary monoamine compound is an aliphatic tertiary amine, including alicyclic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, and N-methylcyclohexylamine. These tertiary monoamines may be used individually or in combination of two or more types. The amount used is not particularly limited, but it is preferably in the range of 15 moles or less per 100 moles of the phenol compound added to the polymerization reaction.

[0057] In this embodiment, there are no restrictions on adding surfactants that are conventionally known to have an effect of improving polymerization activity. Examples of such surfactants include trioctylmethylammonium chloride, known by the trade names Aliquat 336 and Capriquat. The amount used is preferably not more than 0.1% by mass relative to 100% by mass of the total amount of the polymerization reaction mixture.

[0058] In this embodiment, the oxygen-containing gas used in polymerization can be pure oxygen, a mixture of oxygen and an inert gas such as nitrogen in any proportion, air, or a mixture of air and an inert gas such as nitrogen in any proportion. While atmospheric pressure is sufficient for the system pressure during the polymerization reaction, it can be reduced or increased as needed. The polymerization temperature is not particularly limited, but if it is too low, the reaction will not proceed easily, and if it is too high, the reaction selectivity may decrease or a gel may form. Therefore, it is in the range of 0 to 60°C, preferably 10 to 40°C.

[0059] Furthermore, in the method for producing the polyphenylene ether (A), polymerization can also be carried out in a poor solvent such as an alcohol.

[0060] In this embodiment, there are no particular restrictions on the post-treatment method after the polymerization reaction is completed. Typically, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc., are added to the reaction solution to deactivate the catalyst. In addition, the removal of divalent phenol by-products generated by the polymerization of polyphenylene ether can be carried out using conventionally known methods. If the metal ions that act as catalysts are substantially deactivated as described above, the mixture can be decolorized simply by heating it. Alternatively, it is also possible to add the required amount of a known reducing agent. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0061] In the method for producing the polyphenylene ether (A) described above, water may be added to extract the compound from which the copper catalyst has been deactivated, and after liquid-liquid separation into an organic phase and an aqueous phase, the copper catalyst may be removed from the organic phase by removing the aqueous phase. This liquid-liquid separation step is not particularly limited, but examples include static separation and separation by centrifugation. To promote the above liquid-liquid separation, known surfactants and the like may be used.

[0062] Next, in the method for producing the polyphenylene ether (A), the organic phase containing the polyphenylene ether after liquid-liquid separation may be concentrated and dried by volatilizing the solvent. The method for volatilizing the solvent contained in the organic phase is not particularly limited, but examples include transferring the organic phase to a high-temperature concentration tank and distilling off the solvent to concentrate it, or using equipment such as a rotary evaporator to distill off toluene and concentrate it. From the viewpoint of suppressing thermal degradation due to heating, low-temperature concentration under reduced pressure is more preferable.

[0063] The drying temperature in the drying process is preferably at least 60°C, more preferably 80°C, and even more preferably 110°C. Drying polyphenylene ether at a temperature of 60°C or higher efficiently reduces the content of high-boiling point volatile components in the polyphenylene ether powder.

[0064] To obtain the aforementioned polyphenylene ether with high efficiency, methods such as increasing the drying temperature, increasing the vacuum level in the drying atmosphere, and stirring during drying are effective, but increasing the drying temperature is particularly preferred from the viewpoint of manufacturing efficiency. In the drying process, it is preferable to use a dryer equipped with a mixing function. Examples of mixing functions include agitation type and tumbling type dryers. This allows for a larger processing volume and maintains high productivity.

[0065] The polyphenylene ether (A) can also be produced by a redistribution reaction in which a polyphenylene ether derived from the phenol of formula (2) is equilibrated with the phenol compound of formula (1) in the presence of an oxidizing agent. The redistribution reaction is known in the art and is described, for example, in U.S. Patent No. 3,496,236 by Cooper et al. and U.S. Patent No. 5,880,221 by Liska et al. Furthermore, there are no limitations on the method for introducing functional groups to the hydroxyl groups of unmodified polyphenylene ether. For example, it can be obtained by the formation reaction of an ester bond between the hydroxyl groups of unmodified polyphenylene ether and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid).

[0066] Furthermore, various known methods can be used to form ester bonds. For example, a. reaction between a carboxylic acid halide and a hydroxyl group at the polymer terminal, b. formation of ester bonds by reaction with a carboxylic acid anhydride, c. direct reaction with a carboxylic acid, and d. transesterification.

[0067] The reaction with the carboxylic acid halide described in (a) above is one of the most common methods. While chlorides and bromides are commonly used as carboxylic acid halides, other halogens may also be used. The reaction can be either a direct reaction with the hydroxyl group or a reaction with an alkali metal salt of the hydroxyl group. Since the direct reaction between the carboxylic acid halide and the hydroxyl group generates acids such as hydrogen halides, a weak base such as an amine may be present to trap the acid.

[0068] In the reaction with the carboxylic acid anhydride described in (b) above, and in the direct reaction with the carboxylic acid described in (c) above, compounds such as carbodiimides or dimethylaminopyridine may be present to activate the reaction site and promote the reaction.

[0069] In the case of the transesterification reaction described in d above, it is desirable to remove the alcohols produced as needed. Known metal catalysts may also be present to accelerate the reaction. After the reaction, the polymer solution may be washed with water, an acidic, or alkaline aqueous solution to remove by-products such as amine salts, or the polymer solution may be dropped into a poor solvent such as an alcohol and the target product recovered by reprecipitation. Alternatively, after washing the polymer solution, the solvent may be removed under reduced pressure to recover the polymer.

[0070] The method for producing the modified polyphenylene ether described above is not limited to the method for producing the polyfunctional modified polyphenylene ether of this embodiment, and the order and number of times of the above-described oxidative polymerization step, copper extraction and by-product removal step, liquid-liquid separation step, and concentration and drying step may be adjusted as appropriate.

[0071] Furthermore, the polyphenylene ether may be obtained by oxidative polymerization of 3-pentadecylphenol, commercially available cardanol, and optionally 2,6-dimethylphenol as the phenol of formula (2) above, and then introducing at least one substructure selected from the group consisting of formulas (10), (11), (12), and (13) above into the resulting polyphenylene ether. Also, the polyphenylene ether of this embodiment may be obtained by modifying 3-pentadecylphenol or modified cardanol as the phenol of formula (1) above, and optionally 2,6-dimethylphenol as the phenol of formula (2) above. It may also be obtained by oxidative polymerization of ,6-dimethylphenol, and more specifically, the polyphenylene ether of this embodiment may be obtained by oxidative polymerization of modified 3-pentadecylphenol or modified cardanol as the phenol of formula (1) and optionally 2,6-dimethylphenol as the phenol of formula (2), and then introducing at least one substructure selected from the group consisting of formulas (10), (11), (12), and (13) into the resulting polyphenylene ether.

[0072] Also, to give an example, the polyphenylene ether of this embodiment is 4,6-bis(octylthiomethyl)-o-cresol as the phenol of formula (4) above, 4,6-bis( The polyphenylene ether may be obtained by oxidative polymerization of dodecylthiomethyl)-o-cresol and optionally 2,6-dimethylphenol as the phenol of formula (2) above, and then introducing at least one substructure selected from the group consisting of formulas (10), (11), (12), and (13) above into the resulting polyphenylene ether.

[0073] (Diene-based elastomer (B)) In the method of using polyphenylene ether according to this embodiment, the rubber composition for the outsole further comprises the diene-based elastomer (B). The aforementioned (B) diene elastomer is selected from at least one of synthetic rubber and natural rubber. Note that one type of synthetic rubber or natural rubber may be used alone, or two or more types may be used in combination.

[0074] Examples of the aforementioned synthetic rubbers include styrene-butadiene rubber, butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, butadiene acrylonitrile polymer rubber, and chloroprene rubber. Among these, styrene-butadiene rubber, butadiene rubber, and isoprene rubber are preferred.

[0075] • Styrene-butadiene rubber (SBR) As the SBR, a general type used in rubber compositions for outsoles can be used, but specifically, one with a styrene content of 0.1 to 70% by mass is preferred, one with a styrene content of 5 to 60% by mass is more preferred, and one with a styrene content of 5 to 50% by mass is even more preferred. Furthermore, one with a vinyl content of 0.1 to 80% by mass is preferred, and one with a vinyl content of 5 to 70% by mass is even more preferred. The weight-average molecular weight (Mw) of the SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and even more preferably 150,000 to 1,500,000.

[0076] The glass transition temperature (Tg) of the SBR determined by differential thermal analysis is preferably -95 to 0°C, more preferably -95 to -5°C, even more preferably -95 to -10°C, even more preferably -95 to -15°C, and even more preferably -95 to -20°C. There are no particular restrictions on the method for producing the SBR; emulsion polymerization, solution polymerization, gas-phase polymerization, and bulk polymerization can all be used, with emulsion polymerization and solution polymerization being particularly preferred.

[0077] (i) Emulsified polymerized styrene-butadiene rubber (E-SBR) E-SBR can be produced by a conventional emulsion polymerization method, for example, by emulsifying and dispersing a predetermined amount of styrene and butadiene monomers in the presence of an emulsifier, and then emulsion polymerization is carried out with a radical polymerization initiator. As emulsifiers, for example, long-chain fatty acid salts or rosinates having 10 or more carbon atoms are used. Specific examples include potassium or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid. Water is usually used as the dispersion medium, and may also contain water-soluble organic solvents such as methanol and ethanol, as long as the stability during polymerization is not inhibited. Examples of radical polymerization initiators include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide. A chain transfer agent may also be used to adjust the molecular weight of the resulting E-SBR. Examples of chain transfer agents include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, terpinolene, γ-terpinene, and α-methylstyrene dimer. The emulsion polymerization temperature can be appropriately selected depending on the type of radical polymerization initiator used, but is generally preferably 0 to 100°C, and more preferably 0 to 60°C. The polymerization mode may be either continuous polymerization or batch polymerization. The polymerization reaction can be stopped by adding a polymerization stopper. Examples of polymerization stoppers include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine; quinone compounds such as hydroquinone and benzoquinone; and sodium nitrite. After stopping the polymerization reaction, an antioxidant may be added as needed. After the polymerization reaction is stopped, unreacted monomers are removed from the obtained latex as needed. Then, using salts such as sodium chloride, calcium chloride, and potassium chloride as coagulants, and adding acids such as nitric acid and sulfuric acid as needed to adjust the pH of the coagulation system to a predetermined value, the polymer is coagulated. After that, the polymer can be recovered as crumb by separating the dispersed solvent. The crumb is washed with water, then dehydrated, and dried with a band dryer or the like to obtain E-SBR. Alternatively, during coagulation, the latex may be mixed with an emulsified dispersion of spreading oil beforehand and recovered as oil-expanded rubber.

[0078] (ii) Solution-polymerized styrene-butadiene rubber (S-SBR) S-SBR can be produced by conventional solution polymerization methods, for example, by polymerizing styrene and butadiene using an anionically polymerizable active metal in a solvent, optionally in the presence of a polar compound. Examples of anionically polymerizable active metals include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide rare earth metals such as lanthanum and neodymium. Among these, alkali metals and alkaline earth metals are preferred, with alkali metals being more preferred. Furthermore, among alkali metals, organoalkali metal compounds are more preferably used. Examples of solvents include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents are preferably used in a range where the monomer concentration is 1 to 50% by mass.

[0079] Examples of organoalkali metal compounds include organomonolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenithium; polyfunctional organolithium compounds such as dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Among these, organolithium compounds are preferred, and organomonolithium compounds are more preferred. The amount of organoalkali metal compound used is appropriately determined according to the required molecular weight of S-SBR. Organoalkali metal compounds can also be reacted with secondary amines such as dibutylamine, dihexylamine, and dibenzylamine to be used as organoalkali metal amides. As for polar compounds, there are no particular restrictions as long as they are commonly used in anionic polymerization to adjust the microstructure of the butadiene moiety and the distribution of styrene in the polymer chain without deactivating the reaction. Examples include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides, phosphine compounds, etc.

[0080] The polymerization reaction temperature in solution polymerization is typically in the range of -80 to 150°C, preferably 0 to 100°C, and more preferably 30 to 90°C. The polymerization method may be batch polymerization or continuous polymerization. Furthermore, in order to improve the random copolymerizability of styrene and butadiene, it is preferable to continuously or intermittently supply styrene and butadiene to the reaction solution so that the composition ratio of styrene and butadiene in the polymerization system is within a specific range. The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization stopper. Before adding the polymerization stopper, coupling agents such as tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolidyleneisocyanate, or polymerization end modifiers such as 4,4'-bis(diethylamino)benzophenone or N-vinylpyrrolidone, which can react with the polymerization active ends, may be added. After the polymerization reaction has stopped, the polymerization solution can be recovered as S-SBR by separating the solvent through methods such as direct drying or steam stripping. Alternatively, the polymerization solution and the spreading oil may be mixed beforehand and recovered as oil-spread rubber.

[0081] (iii) Modified styrene-butadiene rubber (modified SBR) Furthermore, in this embodiment, modified SBRs in which functional groups have been introduced into SBRs may be used. Examples of functional groups include amino groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, carboxyl groups, and the like. As a method for producing modified SBRs, for example, one may add a coupling agent that can react with the polymerization active ends, such as tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolidylenediisocyanate, or a polymerization end modifier such as 4,4'-bis(diethylamino)benzophenone, N-vinylpyrrolidone, or other modifiers described in Japanese Patent Application Publication No. 2011-132298, before adding a polymerization inhibitor. In this modified SBR, the position of the polymer into which the functional group is introduced may be at the polymerization end or on a side chain of the polymer chain.

[0082] Butadiene rubber (BR) As the butadiene rubber, for example, Ziegler-type catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel can be used; lanthanide-type rare earth metal catalysts such as triethylaluminum-organic acid neodymium-Lewis acid; or commercially available butadiene rubber polymerized using an organic alkali metal compound similar to S-SBR can be used. Butadiene rubber polymerized with a Ziegler-type catalyst is preferred because it has a high cis isomer content. Alternatively, butadiene rubber with an ultra-high cis isomer content (e.g., cis isomer content of 95% or more) obtained using a lanthanide-type rare earth metal catalyst may be used. The weight-average molecular weight (Mw) of the butadiene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. Butadiene rubber may have a branched structure or polar functional groups formed by using a polyfunctional modifier, such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in its molecule, or an amino group-containing alkoxysilane.

[0083] • Isoprene rubber (IR) As the isoprene rubber, for example, Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; lanthanide-based rare earth metal catalysts such as triethylaluminum-organic acid neodymium-Lewis acid; or commercially available isoprene rubber polymerized using an organoalkali metal compound similar to S-SBR can be used. Isoprene rubber polymerized with a Ziegler catalyst is preferred because it has a high cis isomer content. Alternatively, isoprene rubber with an ultra-high cis isomer content obtained using a lanthanide-based rare earth metal catalyst may be used.

[0084] The glass transition temperature is preferably -20°C or lower, and more preferably -30°C or lower. The weight-average molecular weight (Mw) of the isoprene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. The isoprene rubber may have a branched structure or polar functional groups formed by using a polyfunctional modifier, such as tin tetrachloride, silicon tetrachloride, alkoxysilane having an epoxy group in its molecule, or amino group-containing alkoxysilane.

[0085] • Natural rubber Examples of natural rubber used in the diene-based elastomer (B) include commonly used natural rubber, high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, grafted natural rubber, and other modified natural rubbers. These may be used individually or in combination of two or more types.

[0086] Furthermore, from the viewpoint of achieving a high level of balance between flexibility, tensile strength, wet grip, and ice grip in the resulting outsole rubber composition, it is preferable to contain 0.01 to 65 parts by mass of the polyphenylene ether (A) per 100 parts by mass of the diene elastomer (B), more preferably 0.01 to 55 parts by mass, and even more preferably 0.01 to 45 parts by mass.

[0087] (Other ingredients) In the method of using polyphenylene ether according to this embodiment, the outsole rubber composition may contain other components in addition to the polyphenylene ether (A) and diene elastomer (B) described above, such as fillers, silane coupling agents, vulcanizing agents, vulcanization accelerators, and vulcanization aids, as long as they do not hinder the effects of the present invention.

[0088] Furthermore, there are no particular restrictions on the filler, as long as it is one that is commonly used in rubber compositions for outsoles. Examples include silica, carbon black, and other fillers, as shown below. ·silica Examples of the silica mentioned above include wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, and aluminum silicate. These may be used individually or in combination of two or more types.

[0089] The average particle size of the silica is preferably 0.5 nm or larger, more preferably 2 nm or larger, even more preferably 5 nm or larger, even more preferably 8 nm or larger, even more preferably 10 nm or larger, and preferably 200 nm or smaller, more preferably 150 nm or smaller, even more preferably 100 nm or smaller, even more preferably 50 nm or smaller, even more preferably 30 nm or smaller, and even more preferably 20 nm or smaller. The average particle size of the silica can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating the average value.

[0090] • Carbon Black As the carbon black, for example, furnace black, channel black, thermal black, acetylene black, and Ketjen black can be used.

[0091] The average particle size of the carbon black is preferably 5 nm or larger, more preferably 10 nm or larger, even more preferably 15 nm or larger, and preferably 100 nm or smaller, more preferably 80 nm or smaller, even more preferably 70 nm or smaller, and even more preferably 60 nm or smaller, from the viewpoint of achieving a high level of balance between flexibility, tensile strength, wet grip, and ice grip of the outsole rubber composition. The average particle size of the carbon black can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating the average value. The particle size of the carbon black can be adjusted by grinding or other means.

[0092] Other fillers The rubber composition for outsoles may contain fillers other than silica and carbon black (other fillers) for the purpose of improving the mechanical strength of the rubber composition and improving manufacturing costs by incorporating fillers as bulking agents. Examples of fillers other than silica and carbon black include organic fillers, and inorganic fillers such as clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium dioxide, glass fibers, fibrous fillers, and glass balloons. These fillers may be used individually or in combination of two or more.

[0093] Furthermore, when the filler is incorporated into the outsole rubber composition of this embodiment, the content of the filler is preferably 10 to 150 parts by mass per 100 parts by mass of the diene-based elastomer (B). When the amount of the filler is within this range, the tensile strength, wet grip, and ice grip of the outsole rubber composition can be further improved. From a similar viewpoint, the content of the filler is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and preferably 120 parts by mass or less, more preferably 100 parts by mass or less, per 100 parts by mass of the diene-based elastomer (B).

[0094] • Silane coupling agent Examples of the silane coupling agent include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, and chloro compounds.

[0095] Examples of the aforementioned sulfide compounds include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, and 3-trimethoxy Examples include silylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, and 3-trimethoxysilylpropyl methacrylate monosulfide.

[0096] Examples of the mercapto compounds include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.

[0097] Examples of the aforementioned vinyl compounds include vinyltriethoxysilane and vinyltrimethoxysilane.

[0098] Examples of the amino compounds mentioned above include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0099] Examples of the glycidoxy compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane.

[0100] Examples of the nitro compounds mentioned above include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.

[0101] Examples of the chloro-based compounds include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.

[0102] These silane coupling agents may be used individually or in combination of two or more. Among them, silane coupling agents containing sulfur, such as sulfide compounds and mercapto compounds, are preferred from the viewpoint of providing a greater reinforcing effect.

[0103] Furthermore, in the method of using polyphenylene ether in this embodiment, if the outsole rubber composition contains a silane coupling agent, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, per 100 parts by mass of the diene-based elastomer (B). When the amount of silane coupling agent is within the above range, the tensile strength of the outsole rubber composition is improved.

[0104] vulcanizing agent Examples of the vulcanizing agent include sulfur and sulfur compounds. These may be used individually or in combination of two or more.

[0105] In the method of using polyphenylene ether of this embodiment, if the outsole rubber composition contains a vulcanizing agent, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.8 to 5 parts by mass, per 100 parts by mass of the diene-based elastomer (B).

[0106] • Vulcanization accelerator Examples of the aforementioned vulcanization accelerators include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamate compounds, aldehyde-amine compounds, aldehyde-ammonia compounds, imidazoline compounds, and xanthate compounds. These may be used individually or in combination of two or more.

[0107] In the method of using polyphenylene ether according to this embodiment, if the outsole rubber composition contains a vulcanization accelerator, the amount is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the diene-based elastomer (B).

[0108] • vulcanization aid Examples of the aforementioned vulcanization aids include fatty acids such as stearic acid, metal oxides such as zinc oxide, and fatty acid metal salts such as zinc stearate. These may be used individually or in combination of two or more.

[0109] In the method of using polyphenylene ether of this embodiment, if the outsole rubber composition contains a vulcanization aid, the amount thereof is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the diene-based elastomer (B).

[0110] ·others In the method of using polyphenylene ether according to this embodiment, the rubber composition for the outsole may contain, as necessary, process oils such as silicone oil, aroma oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (Residual Aromatic Extracts), paraffin oil, naphthenic oil, resin components such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 resins, rosin resins, coumarone-indene resins, and phenolic resins, as well as liquid polymers such as low molecular weight polybutadiene, low molecular weight polyisoprene, low molecular weight styrene-butadiene polymer, and low molecular weight styrene-isoprene polymer as softeners for the purpose of improving flexibility, fluidity, etc.

[0111] Furthermore, in the method of using polyphenylene ether according to this embodiment, the rubber composition for the outsole may contain one or more additives such as anti-aging agents, antioxidants, waxes, lubricants, light stabilizers, anti-scorch agents, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, anti-blocking agents, ultraviolet absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, and fragrances, for the purpose of improving weather resistance, heat resistance, and oxidation resistance.

[0112] Examples of the aforementioned antioxidants include hindered phenol compounds, phosphorus compounds, lactone compounds, and hydroxyl compounds.

[0113] Examples of the aforementioned anti-aging agents include amine-ketone compounds, imidazole compounds, amine compounds, phenolic compounds, sulfur compounds, and phosphorus compounds.

[0114] In the polyphenylene ether usage method of this embodiment, the outsole rubber composition may contain a crosslinking agent in addition to the vulcanizing agent. Examples of crosslinking agents include oxygen, organic peroxides, phenolic resins, amino resins, quinones and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides, organometallic halides, and silane compounds. These may be used individually or in combination of two or more. The amount of crosslinking agent is preferably 0.1 to 10 parts by mass per 100 parts by mass of diene elastomer (B).

[0115] <Method for manufacturing rubber composition for outsoles> The method for manufacturing the rubber composition for outsoles in this embodiment is not limited as long as the above components can be mixed uniformly. Examples of methods for uniform mixing include tangential or interlocking closed-type kneaders such as kneader-ruders, brabenders, Banbury mixers, and internal mixers, as well as single-screw extruders, twin-screw extruders, mixing rolls, and rollers, and can usually be carried out in a temperature range of 30 to 270°C.

[0116] The rubber composition for the outsole is preferably used as vulcanized rubber. There are no particular restrictions on the vulcanization conditions and methods, but it is preferable to use a vulcanization mold and perform the vulcanization at a vulcanization temperature of 120 to 200°C and a vulcanization pressure of 0.5 to 20 MPa.

[0117] <Rubber composition for outsoles> The rubber composition for the outsole of this embodiment comprises a polyphenylene ether (A) having a glass transition temperature of less than 150°C as measured by differential scanning calorimetry (DSC) as described above, and a diene elastomer (B). The rubber composition for outsoles of this embodiment, by containing the above-described components (A) and (B), can achieve a high level of balance between flexibility, tensile strength, wet grip, and ice grip. Therefore, it can be used as a sole material for all kinds of footwear, including, but is not limited to, trekking shoes, walking shoes, golf shoes, fishing boots, diving shoes, deck shoes, motorcycle shoes, bath shoes, rain shoes, and beach sandals.

[0118] The composition of the polyphenylene ether (A) and diene elastomer (B) contained in the outsole rubber composition of this embodiment, as well as the other components, is the same as that described in the section above on the method of using the polyphenylene ether of this embodiment.

[0119] <Outsole> The outsole of this embodiment can be obtained from the outsole rubber composition of this embodiment. There are no particular restrictions on the method of manufacturing the outsole, but the outsole rubber composition of this embodiment can be manufactured by known methods using a mold having a cavity of the same shape as the outsole. By using the outsole rubber composition of this embodiment, an outsole with excellent flexibility, wet grip and ice grip, and tensile strength can be provided.

[0120] <Shoes> The shoe of this embodiment can be obtained from the outsole of this embodiment. There are no particular restrictions on the method of manufacturing the shoe, but the shoe is manufactured by joining the outsole of this embodiment with the upper, insole, and midsole by known means. By using the outsole of this embodiment, the outsole has excellent flexibility, wet grip and ice grip, and excellent tensile strength, so it is possible to provide a shoe that puts less load on the foot and ankle, a shoe that can be used on wet ground, a shoe that can be used in low temperature environments, and a strong shoe that maintains these properties over a long period of time. [Examples]

[0121] The embodiment will be described in more detail below based on the following examples, but this embodiment is not limited to the following examples.

[0122] The following describes the methods for measuring the various physical properties of polyphenylene ethers, which will be discussed later. (1) Number average molecular weight and weight average molecular weight of polyphenylene ether As the measuring instrument, a gel permeation chromatography system (Shimadzu Corporation, LC-2030C Plus) was used to create a calibration curve using standard polystyrene and ethylbenzene. Using this calibration curve, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the obtained modified polyphenylene ethers were measured. The standard polystyrenes used had molecular weights of 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, and 550. The column used consisted of two Showa Denko K.K. K-805L columns connected in series. Chloroform was used as the solvent, with a solvent flow rate of 1.0 mL / min and a column temperature of 40°C. A 1 g / L chloroform solution of polyphenylene ether was prepared and used as the sample for measurement. The UV wavelength of the detection unit was set to 254 nm for standard polystyrene and 283 nm for polyphenylene ether. Based on the above measurement data, the number-average molecular weight and weight-average molecular weight were calculated from the percentage of peak areas on the molecular weight distribution curve obtained by GPC.

[0123] (2) Measurement of glass transition temperature The glass transition temperature of polyphenylene ether was measured using a differential scanning calorimetry system (DSC250) (TA Instruments). The sample was heated from -120°C to 250°C in a nitrogen atmosphere at a heating rate of 10°C / min, then cooled to -120°C at a rate of 20°C / min, and finally the glass transition temperature was measured at a heating rate of 10°C / min.

[0124] <Synthesis of polyphenylene ethers (PPE-1 to PPE9)> In the examples and comparative examples described later, the polyphenylene ethers (PPE-1 to PPE9) obtained as described below were used.

[0125] (Synthesis of denatured cardanol) Modified cardanol, used in the synthesis of polyphenylene ethers (PPE-1 to PPE5), was synthesized as follows. Cardanol (product name NX-2026, manufactured by Cardolite, 345g) and p-toluenesulfonic acid monohydrate (5.9g) were sequentially added to a 1L flask connected to a -10°C Dewar condenser, and the mixture was stirred with a stirring blade. Then, the mixture was heated in an aluminum block heating device with the ambient temperature set to 80°C. Isobutene (100g) was gradually introduced over 10 hours. The supply of isobutene was stopped, and stirring was continued at 80°C for 15 hours. The temperature of the reaction solution was lowered to 40°C, and toluene (300g) was added to the reaction solution. A 5% sodium hydroxide aqueous solution (27g) was then added dropwise. Deionized water (320g) was added, the temperature of the reaction solution was raised to 70°C, and after stirring for 30 minutes, the organic layer was collected using a separatory funnel. 760g of deionized water was added to the recovered organic layer, the reaction solution was heated to 70°C, stirred for 30 minutes, and then allowed to stand. The organic layer was collected using a separatory funnel. The washed organic layer was concentrated using a rotary evaporator to obtain 370g of pale yellow, oily modified cardanol. The structural identification of the obtained compound is as follows: 1 The analysis was performed using 1H-NMR. The results showed that the main component was cardanol in which a tert-butyl group was introduced at the 2-position of the cardanol starting material before the reaction. Cardanol raw materials: 11H-NMR (CDCl3) δ 7.15 - 7.10 (m, 1H), 6.78 - 6.73 (m, 1H), 6.68 - 6.62 (m, 2H), 5.88 - 5.77 (m, 0.37H), 5.50 - 5.29 (m, 3.44H), 5.10 - 4.95 (m, 0.80H), 4.81 - 4.64 (m, 1H), 2.88 - 2.75 (m, 2.14H), 2.55 (t, 2.13H), 2.08 - 1.98 (m, 3.31H), 1.69 - 1.53 (m, 3.15H), 1.51 - 1.12 (m, 14.10H), 0.94 - 0.85 (m, 1.95H) Modified cardanol (product): 1 1H-NMR (CDCl3) δ 7.16 (d, 1H), 6.69 (dd, 1H), 6.49 (d, 1H), 5.88 - 5.77 (m, 0.39H), 5.50 - 5.29 (m, 3.56H), 5.10 - 4.95 (m, 0.80H), 4.64 (s, 1H), 2.87 - 2.75 (m, 2.12H), 2.56 - 2.46 (m, 2.22H), 2.12 - 1.95 (m, 3.60), 1.65 - 1.53 (m, 2.62H), 1.43 - 1.24 (m, 23.42H), 0.96 - 0.80 (m, 2.20H)

[0126] (Synthesis of polyphenylene ether 1 (PPE-1)) In a 1.5-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.24 L / min. A pre-prepared mixture of 0.064 g of cuprous oxide and 0.482 g of 47% hydrogen bromide, along with 0.154 g of N,N'-di-t-butylethylenediamine, 2.28 g of dimethyl-n-butylamine, 0.748 g of di-n-butylamine, 80.0 g of modified cardanol, 0.05 g of methyltri-n-octylammonium chloride, and 716 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the sparger while vigorously stirring. The polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 35°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 0.689 g of ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 80.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase containing the catalyst metal by static separation. The solvent in the organic phase was removed using a rotary evaporator. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0127] (Synthesis of polyphenylene ether 2 (PPE-2)) In a 1.5-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.24 L / min. A pre-prepared mixture of 0.080 g of cuprous oxide and 0.601 g of 47% hydrogen bromide, along with 0.193 g of N,N'-di-t-butylethylenediamine, 2.84 g of dimethyl-n-butylamine, 0.932 g of di-n-butylamine, 10.2 g of 2,6-dimethylphenol, 69.8 g of modified cardanol, 0.05 g of methyltri-n-octylammonium chloride, and 715 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the sparger while vigorously stirring. The polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 35°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 0.859 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 80.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase containing the catalyst metal by static separation. The solvent in the organic phase was removed using a rotary evaporator. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0128] (Synthesis of polyphenylene ether 3 (PPE-3)) In a 1.5-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.24 L / min. A pre-prepared mixture of 0.106 g of cuprous oxide and 0.797 g of 47% hydrogen bromide, along with 0.255 g of N,N'-di-t-butylethylenediamine, 3.76 g of dimethyl-n-butylamine, 1.24 g of di-n-butylamine, 27.1 g of 2,6-dimethylphenol, 52.9 g of modified cardanol, 0.05 g of methyltri-n-octylammonium chloride, and 714 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the sparger while vigorously stirring. The polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 35°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 1.14 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 80.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase to which the catalyst metal had been transferred by static separation. The solvent in the organic phase was removed using a rotary evaporator. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0129] (Synthesis of polyphenylene ether 4 (PPE-4)) In a 1.5-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.24 L / min. A pre-prepared mixture of 0.119 g of cuprous oxide and 0.894 g of 47% hydrogen bromide, along with 0.286 g of N,N'-di-t-butylethylenediamine, 4.22 g of dimethyl-n-butylamine, 1.39 g of di-n-butylamine, 35.5 g of 2,6-dimethylphenol, 44.5 g of modified cardanol, 0.05 g of methyltri-n-octylammonium chloride, and 713 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the sparger while vigorously stirring. The polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 35°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 1.28 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 80.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase containing the catalyst metal by static separation. The solvent in the organic phase was removed using a rotary evaporator. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0130] (Synthesis of polyphenylene ether 5 (PPE-5)) In a 1.5-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.24 L / min. A pre-prepared mixture of 0.157 g of cuprous oxide and 1.18 g of 47% hydrogen bromide, along with 0.379 g of N,N'-di-t-butylethylenediamine, 5.58 g of dimethyl-n-butylamine, 1.83 g of di-n-butylamine, 60.4 g of 2,6-dimethylphenol, 19.6 g of modified cardanol, 0.05 g of methyltri-n-octylammonium chloride, and 711 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the sparger while vigorously stirring. The polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 35°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 1.69 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 80.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase containing the catalyst metal by static separation. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 25% by mass. The above solution was mixed with methanol in a ratio of 5 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. The wet polyphenylene ether was then washed with methanol in a ratio of 3 to the wet polyphenylene ether. The above washing operation was repeated three times. Next, the wet polyphenylene ether was held at 140°C and 1 mmHg for 240 minutes to obtain dry polyphenylene ether. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0131] (Synthesis of polyphenylene ether 6 (PPE-6)) In a 1.0-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.16 L / min while a pre-prepared mixture of 0.068 g of cuprous oxide and 0.511 g of 47% hydrogen bromide was added, along with 0.164 g of N,N'-di-t-butylethylenediamine, 2.41 g of dimethyl-n-butylamine, 0.793 g of di-n-butylamine, 43.8 g of 2,6-dimethylphenol, 31.2 g of 4,6-bis(octylthiomethyl)-o-cresol, 0.05 g of methyltri-n-octylammonium chloride, and 421 g of toluene. Then, air was introduced into the reactor at a rate of 0.79 L / min through the sparger while vigorously stirring. The polymerization temperature was maintained at 40°C by passing a heat transfer medium through the jacket. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 0.73 g of ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 50.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase containing the catalyst metal by static separation. The solvent in the organic phase was removed using a rotary evaporator. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0132] (Synthesis of polyphenylene ether 7 (PPE-7)) In a 1.5-liter jacketed reactor equipped with a line for introducing nitrogen gas at the top of the reactor, a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor, nitrogen gas was introduced at a rate of 1.24 L / min. A pre-prepared mixture of 0.084 g of cuprous oxide and 0.634 g of 47% hydrogen bromide, along with 0.203 g of N,N'-di-t-butylethylenediamine, 3.00 g of dimethyl-n-butylamine, 0.984 g of di-n-butylamine, 80.0 g of 2,6-dimethylphenol, 0.05 g of methyltri-n-octylammonium chloride, and 715 g of toluene were added. Then, air was introduced into the reactor at a rate of 0.84 L / min through the sparger while vigorously stirring. The polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 35°C. 150 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 0.906 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added as an aqueous solution in 80.0 g of water. The mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. Subsequently, the mixture was separated into a polyphenylene ether solution (organic phase) and an aqueous phase containing the catalyst metal by static separation. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 33% by mass. The above solution was mixed with methanol in a ratio of 4 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. The wet polyphenylene ether was then washed with methanol in a ratio of 3 to the wet polyphenylene ether. The above washing operation was repeated three times. Next, the wet polyphenylene ether was held at 140°C and 1 mmHg for 240 minutes to obtain dry polyphenylene ether. The obtained polyphenylene ether was subjected to the measurements described above. The results of each analysis are shown in Table 1.

[0133] (Polyphenylene ether 8 (PPE-8)) Poly(2,6-dimethyl-1,4-phenylene ether):Xyron TMS201A (manufactured by Asahi Kasei Corporation)

[0134] (Polyphenylene ether 9 (PPE-9)) Poly(2,6-dimethyl-1,4-phenylene ether):Noryl TM SA120 (manufactured by Sabic)

[0135] [Table 1]

[0136] [Examples 1-10, Comparative Examples 1-4] A sample of the material was prepared. The components, other than polyphenylene ether (A), were uniformly blended as shown below. For the mixing of each component constituting the rubber composition, a sealed kneader (capacity 0.5L) equipped with a temperature control device was used. In the first stage of mixing, materials other than sulfur and vulcanization accelerators were mixed under conditions of a filling rate of 65% and a rotor rotation speed of 50-90 rpm. At this time, the temperature of the sealed kneader was controlled, and the compound was obtained at a discharge temperature of 150-160°C. Next, in the second stage of mixing, the mixture obtained above was cooled to room temperature and then mixed again to improve the dispersion of the reinforcing filler. In this case as well, the discharge temperature of the mixture was adjusted to 150-160°C by controlling the temperature of the mixer. After cooling, in the third stage of kneading, the mixture was kneaded in an open roll oven set to 70°C with a vulcanization accelerator and sulfur to obtain an unvulcanized rubber composition. Subsequently, the mixture was molded and vulcanized using a vulcanization press at 160°C for a predetermined vulcanization time to obtain the vulcanized rubber composition. The vulcanization time was set to the 90% vulcanization time of the unvulcanized rubber composition plus 5 minutes.

[0137] (Polyphenylene ether (A)) As shown in Table 1, PPE1 to PPE9 were used and mixed into rubber compositions with varying types and amounts.

[0138] (Diene-based elastomer (B)) • Styrene-butadiene rubber (SBR (Y031, manufactured by Asahi Kasei Corporation)): 30 parts by mass Butadiene rubber (BR (BR150, manufactured by UBE)): 60 parts by mass • Isoprene rubber (IR (IR2200, manufactured by ENEOS Material Co., Ltd.)): 60 parts by mass

[0139] (Other ingredients) Paraffin oil (JX Energy Corporation P-200): 5.0 parts by mass • Silica (Nipsil VN3, manufactured by Tosoh Silica Co., Ltd.): 40 parts by mass • Silane coupling agent (Evonik Japan, "Si69", bis(triethoxysilylpropyl)tetrasulfide): 2.0 parts by mass ·Zinc white: 3.0 parts by mass Stearic acid: 2.0 parts by mass • Anti-aging agent (Nocrac 6C, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.): 1.0 parts by mass ·Sulfur: 1.4 parts by mass • Vulcanization accelerator 1 (2-mercaptobenthiazole): 1.0 part by mass • Vulcanization accelerator 2 (Nt-butyl-2-benzothiazole sulfenamide): 1.0 part by mass

[0140] <Rating> The rubber composition and vulcanized rubber composition of each obtained sample were evaluated as follows. The evaluation results are shown in Table 2.

[0141] (1)Flexibility The durometer type A values ​​were measured for samples of the vulcanized rubber compositions obtained in the examples and comparative examples, in accordance with JIS K6253. The following indicators were used for evaluation. ○ (2 points): Durometer hardness less than 47 △ (1 point): Durometer hardness is 48 or higher but less than 49 × (0 points): Durometer hardness of 50 or higher

[0142] (2) Tensile strength The tensile strength of samples of the vulcanized rubber compositions obtained in the examples and comparative examples was measured in accordance with the tensile test method of JIS K6251. The following indicators were used for evaluation. ○ (2 points): Tensile strength of 14 MPa or higher △ (1 point): Tensile strength between 13 MPa and less than 14 MPa × (0 points): Tensile strength is less than 13 MPa

[0143] (3) Wet grip Samples of the vulcanized rubber compositions obtained in the examples and comparative examples were measured using a viscoelasticity tester "ARES" manufactured by Rheometrics Scientific, Inc., with torsional mode measurement of tanδ at 23°C, frequency of 10 Hz, and strain of 3%. The tanδ value was used as an indicator of wet grip performance. A higher tanδ value indicated better wet grip performance. The following indicators were used for evaluation. ○ (2 points): tanδ is 0.120 or higher △ (1 point): tanδ is 0.110 or greater and less than 0.120 × (0 points): tanδ is less than 0.110

[0144] (4) Ice grip performance Samples of the vulcanized rubber compositions obtained in the examples and comparative examples were measured using a viscoelasticity tester "ARES" manufactured by Rheometrics Scientific, Inc., with torsional mode measurement of tanδ at -20°C, frequency of 10 Hz, and strain of 3%. The tanδ value was used as an indicator of ice grip performance. A higher tanδ value indicated better ice grip performance. The following indicators were used for evaluation. ○ (2 points): tanδ is 0.20 or higher △ (1 point): tanδ is 0.17 or greater and less than 0.20 × (0 points): tanδ is less than 0.17

[0145] (5) Performance balance The performance balance was evaluated using the following indicators. ◎: Total score of (1) to (4) is 8 points 〇: Total score of (1) to (4) is 7 points △: The total score of (1) to (4) is 6 or 5 points. ×: The total score of (1) to (4) is 4 points or less.

[0146] [Table 2]

[0147] Table 2 shows that Examples 1-10 demonstrated well-balanced performance in all aspects, including flexibility, strength, wet grip performance, and ice grip performance. In Comparative Example 1 or 2, the rubber composition containing PPE-7 or 8 exhibited poor cohesion of the compound, making evaluation impossible. Therefore, it was considered to have poor performance in all aspects: flexibility, tensile strength, wet grip, and ice grip. In Comparative Examples 3 or 4, rubber compositions containing PPE-9, or those without PPE addition, were kneadable, but they exhibited poor performance in some or all aspects of flexibility, tensile strength, wet grip, and ice grip, and were found to be inferior to those in the Examples. [Industrial applicability]

[0148] The rubber composition of this embodiment is useful as a sole material for all types of footwear, particularly trekking shoes, walking shoes, golf shoes, fishing boots, diving shoes, deck shoes, motorcycle shoes, bath shoes, rain shoes, and flip-flops. Furthermore, it is also useful as a component material for tires such as truck tires, bus tires, automobile tires, motorcycle tires, off-road tires, and aircraft tires; as a component material for tire parts such as treads, sidewalls, chafer strips, tire rubber layers, reinforcing cord coating materials, and cushioning layers; and for industrial parts such as fibers, thin films, laminates, automobile parts, and medical parts. It has industrial potential as a material for molded parts such as container housings, consumer products, and packaging; belts such as tire curing bladders, inner tubes, air sleeves, hoses, conveyor belts or automotive belts; solid tires, retread tires; rollers for graphic art applications; vibration dampers; pharmaceutical equipment; adhesives; caulking materials; sealing materials; glazing compounds; protective coatings; air cushions; air springs; air bellows; accumulator bags; and various bladder materials for liquid storage and curing methods; as well as materials for molded rubber parts such as automotive suspension bumpers, automotive exhaust pipe hangers, and body mounts.

Claims

1. A method for using polyphenylene ether, characterized in that polyphenylene ether (A), having a glass transition temperature of less than 150°C as measured by differential scanning calorimetry (DSC), is used as a raw material for a rubber composition for outsoles.

2. The polyphenylene ether (A) comprises a repeating unit derived from the phenol of the following formula (1) and a repeating unit derived from the phenol of the following formula (2). A method for using polyphenylene ether according to claim 1, characterized in that, with respect to a total of 100 mol% of the repeating units of the following formulas (1) and (2), the content ratio of the repeating units derived from phenol of formula (1) is 6 mol% or more and 100 mol%, and the content ratio of the repeating units derived from phenol of formula (2) is greater than 0 mol% and 94 mol% or less. 【Chemistry 1】 (In formula (1), R １３ R is a saturated or unsaturated hydrocarbon group having 15 carbon atoms, which may be substituted. １１ and R １２ Each of these is independently a hydrogen atom, a linear saturated hydrocarbon group having 1 to 12 carbon atoms, and a substituent represented by the following formula (3). 【Chemistry 2】 (In formula (3), R ３１ Each independently forms a linear alkyl group having 1 to 8 carbon atoms, which may be substituted, or two R ３１ The atoms contained in are bonded to each other to form a cyclic alkyl group having 1 to 8 carbon atoms, R ３２ Each is independently an alkylene group having 1 to 8 carbon atoms, which may be substituted, and each is independently 0 or 1, R ３３ This is a hydrogen atom, an optionally substituted C1-C8 alkyl group, or an optionally substituted phenyl group. 【Transformation 3】 (In formula (2), R ２１ is each independently an optionally substituted saturated hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom, and R ２２ is each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom.)

3. The rubber composition for the outsole further comprises a diene elastomer (B), The method for using polyphenylene ether according to claim 1 or 2, characterized in that the content of the polyphenylene ether (A) in the outsole rubber composition is 0.01 to 65 parts by mass per 100 parts by mass of the diene elastomer (B).

4. The method for using polyphenylene ether according to claim 1 or 2, characterized in that the glass transition temperature of the polyphenylene ether (A), as measured by differential scanning calorimetry (DSC), is less than 0°C.

5. An outsole rubber composition characterized by comprising a polyphenylene ether (A) having a glass transition temperature of less than 150°C as measured by differential scanning calorimetry (DSC), and a diene-based elastomer (B).

6. An outsole characterized by comprising the rubber composition for outsoles described in claim 5.

7. A shoe characterized by including the outsole described in claim 6.

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