JP2023094283A - Member for sole, shoe, and method for manufacturing member for sole - Google Patents

Abstract

To provide a member for a shoe which has improved adhesive strength between a first sole member and a second sole member through an adhesive layer containing a polyurethane resin.SOLUTION: A member for a shoe includes a first shoe member arranged at the bottom of the shoe and a second shoe member arranged on a side closer to the sole side of a wearer than the first shoe member, wherein the first shoe member and the second shoe member are bonded to each other through an adhesive layer containing a polyurethane resin, and the first shoe member is a crosslinked body of a rubber composition containing at least styrene-butadiene rubber and dry silica.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a shoe sole member that is used, for example, placed on the sole of a shoe. The present invention also relates to a shoe provided with the above-described shoe-sole member and a method for manufacturing the above-described shoe-sole member.

2. Description of the Related Art Conventionally, shoes having sole members are known. This type of shoe is for soles having, for example, a first sole member arranged on the sole of the shoe and a second sole member arranged on the sole of the wearer's foot rather than the first sole member. Equipped with members. The first sole member and the second sole member are formed of rubber compositions containing different types of rubber, and are adhered to each other. In other words, this type of shoe includes, as a sole member, a rubber laminate in which a first sole member and a second sole member are laminated, for example.

As a rubber laminate, although it is not a member for a shoe sole, for example, one in which at least two unvulcanized rubber layers made of an unvulcanized rubber composition are vulcanized and adhered is known (see, for example, Patent Document 1).
In the rubber laminate described in Patent Document 1, at least one unvulcanized rubber layer is an unvulcanized rubber containing 50 parts by weight or more of a non-diene rubber when the total amount of rubber components is 100 parts by weight. composition. Further, the rubber laminate described in Patent Document 1 includes a coating step of applying fatty acid zinc or fatty acid copper to the bonding surface of at least one of the unvulcanized rubber layers, and a bonding step in which fatty acid zinc or fatty acid copper is applied. After laminating the two unvulcanized rubber layers so that the surface faces the interface side, it is manufactured through a vulcanization adhesion step of vulcanization adhesion.
In the rubber laminate described in Patent Document 1, interfacial adhesion between two layers is improved.

JP 2012-121302 A

By the way, similar to the rubber laminated body described above, a general sole member provided in a shoe also has a laminated structure, for example, a first sole member and a second sole member are laminated. In this type of sole member, either the first sole member or the second sole member is a crosslinked rubber composition containing, for example, styrene-butadiene rubber. This type of shoe sole member is relatively often manufactured by bonding a first shoe sole member and a second shoe sole member with a general urethane resin-based adhesive containing polyurethane resin.

However, the sole member, in which the first sole member and the second sole member are simply adhered via the adhesive layer containing the polyurethane resin, does not adhere to the first sole member and the second sole member. Strength may not always be good. In other words, if the sole member is manufactured by simply adhering the first sole member and the second sole member with a commonly used urethane resin adhesive, the adhesion strength between the two members is not always improved. I have a problem that I can't

Therefore, there is a need for a shoe sole member in which the adhesive strength between the first sole member and the second sole member is improved through an adhesive layer containing a polyurethane resin, and a shoe equipped with the sole member. ing. Further, there is a demand for a method of manufacturing a shoe sole member that improves the adhesive strength between the first shoe sole member and the second shoe sole member via an adhesive layer containing a polyurethane resin.

In view of the above problems and demands, the present invention provides a shoe sole member in which the adhesive strength between a first shoe sole member and a second shoe sole member is improved via an adhesive layer containing a polyurethane resin. The task is to provide
Another object of the present invention is to provide a shoe including the sole member.
Further, the present invention provides a method for manufacturing a shoe sole member, which can manufacture a shoe sole member having improved adhesive strength between a first shoe sole member and a second shoe sole member via an adhesive layer containing a polyurethane resin. The task is to provide

In order to solve the above problems, a shoe sole member according to the present invention includes:
A first sole member arranged on the sole of the shoe, and a second sole member arranged on the sole of the wearer's foot rather than the first sole member,
The first sole member and the second sole member are adhered via an adhesive layer containing a polyurethane resin,
The first sole member is a crosslinked rubber composition containing at least styrene-butadiene rubber and dry silica.

A shoe according to the present invention includes the sole member described above.

A method for manufacturing a shoe sole member according to the present invention comprises a first shoe sole member to be placed on the bottom of a shoe, and a second shoe sole member to be placed on the sole of the wearer's foot rather than the first shoe sole member. A method for manufacturing a shoe sole member comprising
producing the first sole member by subjecting a rubber composition containing at least styrene-butadiene rubber and dry silica to a cross-linking treatment;
bonding the first sole member and the second sole member with an adhesive containing polyurethane resin.

In the shoe sole member and the shoe according to the present invention, the adhesion strength between the first sole member and the second sole member is improved through the adhesive layer containing the polyurethane resin. The method for manufacturing a shoe sole member according to the present invention can manufacture a shoe sole member with improved adhesive strength between the first shoe sole member and the second shoe sole member via the adhesive layer containing the polyurethane resin.

FIG. 1 is a schematic diagram showing the outer appearance of a shoe sole member and a shoe according to the present embodiment. FIG. 2 is a schematic cross-sectional view showing an example of the shoe sole member according to the present embodiment cut in the vertical direction when the shoe is worn. FIG. 3 is a schematic cross-sectional view showing a vertical cross-section of another example of the shoe sole member according to the present embodiment when the shoe is worn. FIG. 4 is a schematic diagram schematically showing an example of the method for manufacturing a shoe sole member according to the present embodiment. FIG. 5 is a schematic diagram schematically showing another example of the method for manufacturing a shoe sole member according to the present embodiment.

An embodiment of a shoe sole member and a shoe according to the present invention will be described below with reference to the drawings. A shoe 100 of the present embodiment includes a sole member 10 of the present embodiment, as shown in FIG.

A shoe 100 of this embodiment includes an upper member 50 and a sole member 10, as shown in FIG. The sole member 10 has a first sole member 11 arranged on the sole of the shoe and a second sole member 12 arranged on the sole of the wearer's foot rather than the first sole member 11 . As shown in FIG. 2 or 3, the first sole member 11 and the second sole member 12 are adhered via an adhesive layer 13 containing polyurethane resin. In addition, each figure in drawing is a schematic diagram, and is not necessarily the same as the length-to-width ratio in the real thing.

In this embodiment, the first sole member 11 is, for example, an outer sole, and the second sole member 12 is, for example, a midsole or upper material.
The first sole member 11 in this embodiment may constitute the entire outer sole, or may constitute a part of the outer sole. The shoe 100 may include a first sole member 11 whose surface is exposed at the side surface or the sole of the shoe 100, as shown in FIG. 1, for example. The surface of the first sole member 11 may not be exposed on the side surface of the shoe 100 or on the sole.

The first sole member 11 and the second sole member 12 in one example of this embodiment are each formed in a plate shape. The shape of the first sole member 11 and the second sole member 12 when viewed from one side in the thickness direction is, for example, similar to the shape of the sole of the wearer's foot. The first sole member 11 and the second sole member 12 are arranged on the bottom of the shoe 100, laminated in the thickness direction, and adhered to each other via an adhesive layer 13 containing polyurethane resin.
The shape of the first sole member 11 may be a sheet shape that covers the entire sole. On the other hand, the first sole member 11 may have, for example, a plurality of parts (member pieces) that are discontinuous in the plane direction (front, back, left, and right directions when worn) (see FIG. 3). For example, when the first sole member 11 having a plurality of sheet members is viewed from one side in the thickness direction, one or more holes may be formed in the central portion or the like. Similarly, when viewed from one side in the thickness direction, the first sole member 11 may be composed of a plurality of parts separated from each other in the plane direction.

The thickness of the first sole member 11 is not particularly limited, and may be, for example, 1 mm or more and 20 mm or less, preferably 2 mm or more and 10 mm or less. The thickness of the first sole member 11 may be thicker than the thickness of the second sole member 12 .

The first sole member 11 is a crosslinked rubber composition containing at least styrene-butadiene rubber and dry silica. In this embodiment, the above rubber composition may further include butadiene rubber, isoprene rubber, ethylene propylene diene rubber (EPDM), etc. as rubber components. In addition, the above rubber composition may further contain wet silica as silica. In this embodiment, the rubber composition described above may further include a coupling agent, a cross-linking agent, and the like.

Styrene-butadiene rubber is not particularly limited as long as it is a rubber obtained from a copolymer of styrene and butadiene. Styrene-butadiene rubber is, for example, a rubber obtained from a copolymer of styrene and 1,3-butadiene.
Since the rubber composition contains styrene-butadiene rubber and dry silica, the adhesion strength between the first sole member 11 and the second sole member 12 via the adhesive layer 13 containing the polyurethane resin is improved. there is

The styrene content in the styrene-butadiene rubber is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. By including such a styrene-butadiene rubber in the rubber composition, the first sole member 11, which is a cured product of such a rubber composition, can have better strength. Also, the first sole member 11 and the second sole member 12 can be more strongly bonded via the adhesive layer 13 containing polyurethane resin. The styrene content may be 60% by mass or less, or may be 50% by mass or less. In addition, styrene content is calculated|required by JISK6239.

As the styrene-butadiene rubber, those obtained by emulsion polymerization, those obtained by solution polymerization, and the like can be used. As the styrene-butadiene rubber, those obtained by solution polymerization are preferable in that the block arrangement or random arrangement in the molecule is appropriately adjusted by living polymerization using an organic lithium catalyst or the like.
The number average molecular weight of the styrene-butadiene rubber may be, for example, about 10,000 to 500,000.

The rubber composition may contain one type of styrene-butadiene rubber, or may contain multiple types of styrene-butadiene rubbers.

Preferably, the above rubber composition further contains butadiene rubber. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.

The butadiene rubber is not particularly limited as long as it is a rubber obtained from a butadiene polymer. Butadiene rubber may be, for example, so-called low-cis type or high-cis type. In the lo-cis type butadiene rubber, the main unit constituting the molecular chain is the trans-1,4 unit, and the other units are the 1,2 unit (vinyl unit) or the cis-1,4 unit. In the high-cis type butadiene rubber, 80% or more of the units constituting the molecular chain are cis-1,4 units. A high-cis type is preferable as the butadiene rubber.

Also, the butadiene rubber may be a butadiene rubber other than the general butadiene rubber as described above. Examples of butadiene rubbers include functional group-containing butadiene rubbers in which functional groups such as hydroxyl groups, carboxyl groups, acryl groups, and isocyanate groups are introduced at the ends of molecules.
In addition, said rubber composition may contain one type of butadiene rubber, and may contain multiple types of butadiene rubbers.

The isoprene rubber is not particularly limited as long as it is a rubber obtained from an isoprene polymer. Isoprene rubber usually has a cis-1,4 polyisoprene structure in its molecule. The isoprene rubber may have a 1,2-polyisoprene structure, a 3,4-polyisoprene structure, a 1,2-polyisoprene structure, or a trans-1,4-polyisoprene structure in the molecule.

Ethylene propylene diene rubber (EPDM) is not particularly limited as long as it is a rubber obtained from a copolymer of ethylene, propylene and diene. Ethylene propylene diene rubber (EPDM) usually employs 5-ethylidene-2-norbornene (ENB) as the diene. Dicyclopentadiene (DCP) or 1,4-hexadiene (HD) may be employed as part of the diene. The copolymerization ratio of ethylene and propylene may be, for example, ethylene:propylene=0.1 to 9:1 in mass ratio. In other words, the copolymerization ratio may be 10 parts by mass or more and 900 parts by mass or less of ethylene with respect to 100 parts by mass of propylene. Further, the copolymerization ratio of the total amount of ethylene and propylene to the diene may be, for example, (ethylene and propylene):diene=4 to 99:1 in mass ratio. In other words, the copolymerization ratio may be such that the total amount of ethylene and propylene is 4 parts by mass or more and 99 parts by mass or less with respect to 1 part by mass of diene.

The content of the rubber component (including styrene-butadiene rubber, butadiene rubber, isoprene rubber, ethylene propylene diene rubber, etc.) in the rubber composition is preferably at least 60% by mass, and at least 65% by mass. is more preferred. As a result, the first sole member 11, which is the crosslinked rubber composition, can have appropriate softness. Therefore, the shoe 100 including the sole member 10 having the first sole member 11 has a good fit to the sole of the wearer's foot, and can have good flexibility during walking. .
In addition, the content of the rubber component in the rubber composition may be 90% by mass or less, or may be 85% by mass or less.

The mass ratio of the styrene-butadiene rubber to the rubber component in the rubber composition is preferably at least half. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin. More preferably, the styrene-butadiene rubber accounts for 60 parts by mass or more in 100 parts by mass of the rubber component. The amount of styrene-butadiene rubber may be 80 parts by mass or less in 100 parts by mass of the rubber component.

It is preferable that the butadiene rubber accounts for 20 parts by mass or more of 100 parts by mass of the rubber component in the rubber composition (when the amount of the rubber component is 100 parts by mass). Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin. The amount of butadiene rubber may be 70 parts by mass or less in 100 parts by mass of the rubber component.

It is preferable that the amount of isoprene rubber is less than 20 parts by mass out of 100 parts by mass of the rubber component in the rubber composition. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.

It is preferable that ethylene propylene diene rubber (EPDM) accounts for 10 parts by mass or more of 100 parts by mass of the rubber component in the rubber composition. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin. The amount of ethylene propylene diene rubber (EPDM) may be 30 parts by mass or less in 100 parts by mass of the rubber component.

In this embodiment, the rubber composition contains at least dry silica as silica. The rubber composition described above may contain wet silica as silica. The silica contained in the rubber composition is particulate.

Since the above rubber composition contains dry silica, the first sole member 11, which is a crosslinked product of the above rubber composition, can have good strength. Further, the adhesive strength between the first sole member 11 and the second sole member 12 is improved through the adhesive layer 13 containing polyurethane resin.

Dry silica is obtained in a form close to primary particles by a dry method such as a combustion method or an arc method. Fumed silica is preferred as fumed silica. The dry silica preferably has an average particle size of 5 nm or more and 50 nm or less. The specific surface area of the dry silica measured by the BET method is preferably 50 m ² /g or more and 500 m ² /g or less.

Wet silica is obtained as aggregated particles by a wet method such as a sedimentation method or a gel method.

The rubber composition preferably contains 20 parts by mass or more and 60 parts by mass or less dry silica with respect to 100 parts by mass of the total amount of rubber components (styrene-butadiene rubber, butadiene rubber, isoprene rubber, EPDM, etc.), It is more preferable to contain 35 parts by mass or more and 45 parts by mass or less of dry silica.
The total content of silica (the total content of dry silica and wet silica) in the rubber composition is preferably 20% by mass or more and 60% by mass or less.

In the present embodiment, the rubber composition preferably contains at least one of a coupling agent and a cross-linking agent, and more preferably contains both a coupling agent and a cross-linking agent. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.

In this embodiment, the rubber composition may include at least a coupling agent for chemically bonding the styrene-butadiene rubber and dry silica.
A coupling agent (silane coupling agent) is a compound having at least an alkoxysilane structure in its molecule.

The above rubber composition preferably contains 5 parts by mass or more and 10 parts by mass or less of a coupling agent with respect to 100 parts by mass of silica (total amount of dry silica and wet silica).

A silane coupling agent (alkoxysilane compound) or the like can be used as the coupling agent. Examples of coupling agents include mercapto-based silane coupling agents, monosulfide-based silane coupling agents, epoxy-based silane coupling agents, and tetrasulfide-based silane coupling agents. As the silane coupling agent, one or more selected from the group consisting of mercapto-based silane coupling agents and monosulfide-based silane coupling agents is used in that the first sole member 11 can have greater strength. preferable.

The mercapto-based silane coupling agent can more fully disperse dry silica in the rubber composition. Therefore, the first sole member 11 can have greater strength.
Mercapto-based silane coupling agents include, for example, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, and 3-mercaptopropyltrimethoxysilane. silane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane and the like. Mercapto-based silane coupling agents include silane coupling agents obtained by substituting and condensing the methoxy group or ethoxy group of the alkoxysilane compound with a diol.
As the mercapto-based silane coupling agent, a silane coupling agent having an ethoxy group or a silane coupling agent obtained by substituting/condensing an ethoxy group with a diol is preferable.

ただし、一般式（１）において、「Ｒ^１」は、炭素数１以上２０以下の、アルキル基、アルケニル基、又は、アシル基のいずれかであり、前記アルキル基、前記アルケニル基、又は、前記アシル基は、１以上の置換基を有してもよい。「Ｒ^２」は、炭素数１以上２０以下の、アルカンジイル基、アルケンジイル基、カルボニル基のいずれかであり、前記のアルカンジイル基、アルケンジイル基、又は、カルボニル基は、１以上の置換基を有してもよい。「Ｘ」は、下記一般式（２）で表されるアルコキシシリル基である。

（ただし、式中の「Ｒ^３」、「Ｒ^４」、及び、「Ｒ^５」は、それぞれ独立して、水素原子、炭素数１以上４以下のアルキル基、又は、アルコキシ基のいずれかであり、「Ｒ^３」、「Ｒ^４」、及び「Ｒ^５」のうちの少なくとも１つがアルコキシ基である。） A monosulfide-based silane coupling agent is represented, for example, by the following general formula (1).

However, in the general formula (1), "R ¹ " is either an alkyl group, an alkenyl group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group, the alkenyl group, or the Acyl groups may have one or more substituents. "R ² " is an alkanediyl group, an alkenediyl group, or a carbonyl group having 1 to 20 carbon atoms, and the alkanediyl group, alkenediyl group, or carbonyl group has one or more substituents. may have. "X" is an alkoxysilyl group represented by the following general formula (2).

(However, "R ³ ", "R ⁴ ", and "R ⁵ " in the formula are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. and at least one of “R ³ ”, “R ⁴ ”, and “R ⁵ ” is an alkoxy group.)

"R ¹ " is preferably an unsubstituted acyl group having 4 to 12 carbon atoms. “R ² ” is preferably an unsubstituted alkanediyl group having 2 to 5 carbon atoms. "X" is preferably a trimethoxysilyl group or a triethoxysilyl group.

The monosulfide-based silane coupling agent is 3-alkanoylthio-1-propyltrimethoxysilane or 3-alkanoylthio-1-propyltrimethoxysilane, represented by the following general formula (3) or general formula (4), respectively. Any ethoxysilane is preferred.

（ただし、「ｎ」は２以上１０以下の整数を表し「ｍ」は２以上５以下の整数を表している。）

(However, "n" represents an integer of 2 or more and 10 or less, and "m" represents an integer of 2 or more and 5 or less.)

（ただし、「ｎ」は２以上１０以下の整数を表し「ｍ」は２以上５以下の整数を表している。）

(However, "n" represents an integer of 2 or more and 10 or less, and "m" represents an integer of 2 or more and 5 or less.)

Among the monosulfide-based silane coupling agents represented by general formulas (3) and (4), those in which "n" is "6" and "m" is "3" are particularly preferred. Specifically, the monosulfide silane coupling agent is particularly preferably 3-octanoylthio-1-propyltrimethoxysilane or 3-octanoylthio-1-propyltriethoxysilane.
Such a preferred monosulfide-based silane coupling agent has an alkyl group with an appropriate length at the molecular terminal, so that the rubber composition can exhibit good plasticization. Also, the first sole member 11 obtained by cross-linking the rubber composition can have relatively low hardness.

Epoxy silane coupling agents include, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid xypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

Tetrasulfide-based silane coupling agents include, for example, bis(3-triethoxysilylpropyl) tetrasulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, 3- trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3- trimethoxysilylpropyl-benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide and the like.

The cross-linking agent that can be included in the rubber composition is a compound that accelerates the cross-linking reaction of the rubber component in the rubber composition. Examples of cross-linking agents include organic peroxides and sulfur.

In the present embodiment, the rubber composition preferably contains a cross-linking agent, and the cross-linking agent is an organic peroxide or sulfur. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.

Examples of organic peroxides include 1,1-bis(1,1-dimethylethylperoxy)cyclohexane, 1,1-bis(1,1-dimethylbutylperoxy)cyclohexane, 4,4-bis[( Butyl t-butyl)peroxy]pentanoate, dicumyl peroxide, t-butyl α-cumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-bis( t-butylperoxy)-2,5-dimethyl-3-hexyne, dibenzoyl peroxide, bis(4-methylbenzoyl) peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 1,1-bis(t-butyldioxy)-3,3,5-trimethylcyclohexane and the like.

The rubber composition may contain sulfur as a cross-linking agent and a cross-linking accelerator that accelerates the cross-linking reaction by sulfur. Examples of cross-linking accelerators include thiazole-based cross-linking accelerators and thiuram-based cross-linking accelerators.

Examples of thiazole cross-linking accelerators include 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazoline, dibenzothiazyl disulfide (di-2-benzothiazolyl disulfide), 2-(2, 4-dinitrophenylthio)benzothiazole, 2-(N,N-diethylthio carbamoylthio)benzothiazole, 2-(2,6-dimethyl-4-morpholinothio)benzothiazole, 2-(4'-morpholino dithio ) benzothiazole and the like.

Thiuram-based cross-linking accelerators include, for example, TMTD (tetramethylthiuram disulfide), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, and dipentamethylenethiuram disulfide.

The rubber composition described above may contain fatty acids. Fatty acids may be in the form of salts such as metal salts and ammonium salts.
Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
Salts of fatty acids include magnesium salts, calcium salts, zinc salts and the like.

The fatty acid content in the rubber composition is preferably less than 1% by mass, more preferably 0.5% by mass or less, and still more preferably free of fatty acids. Thereby, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.

In the present embodiment, the rubber composition contains 20 parts by mass or more and 40 parts by mass or less of styrene-butadiene rubber out of 100 parts by mass of the rubber component, and 40 parts by mass of dry silica with respect to 100 parts by mass of the rubber component. It is preferable to contain 80 parts by mass or less. At this time, the total amount of silica is preferably 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the rubber component. By using such a rubber composition, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.
In the present embodiment, the rubber composition contains 60 parts by mass or more and 80 parts by mass or less of styrene-butadiene rubber out of 100 parts by mass of the rubber component, and 20 parts by mass of dry silica per 100 parts by mass of the rubber component. It is preferable to include more than 60 parts by mass and less than 60 parts by mass. At this time, the total amount of silica is preferably 30 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the rubber component. By using such a rubber composition, the first sole member 11 and the second sole member 12 can be more strongly adhered via the adhesive layer 13 containing polyurethane resin.

The material of the second shoe sole member 12 included in the shoe sole member 10 of the present embodiment is, for example, rubber, but is not particularly limited. The second sole member 12 is formed of, for example, a crosslinked foam based on ethylene-vinyl acetate copolymer resin or olefin resin, natural leather, artificial leather, polyester resin such as polyethylene terephthalate resin, or polyamide resin. ing.

The adhesive layer 13 arranged between the first sole member 11 and the second sole member 12 in the shoe sole member 10 contains a polyurethane resin. The adhesive layer 13 is formed by curing a commonly used urethane resin adhesive. The urethane resin-based adhesive may be in a solution state in which a urethane resin is dissolved in an organic solvent, or in an emulsion state in which a urethane resin is dispersed in a liquid containing water. In this embodiment, the adhesive layer 13 does not contain a crosslinked rubber component such as that contained in the first sole member 11 .

The above rubber composition may further contain components other than the components described above within a range in which the effects of the present invention are not significantly impaired. The rubber composition includes, for example, hardness modifiers such as paraffinic or naphthenic process oils, tackifiers such as terpene resins, antioxidants, processing aids, inorganic fillers, antibacterial agents, fragrances, and the like. may be included as appropriate.

In the shoe sole member 10 of the present embodiment, the first shoe sole member 11, which is the crosslinked rubber composition described above, is bonded to the second shoe sole member 12 via the adhesive layer 13 containing the polyurethane resin. It has a configuration that The adhesive that forms the adhesive layer 13 is a generally used adhesive containing polyurethane resin. Since the component of this adhesive has a relatively high affinity with the first sole member 11, it is thought that the first sole member 11 and the second sole member 12 can be bonded relatively strongly.

Next, a method for manufacturing the shoe sole member of the present embodiment will be described.

The method of manufacturing a shoe sole member according to the present embodiment comprises a first shoe sole member arranged on the sole of a shoe, and a second shoe sole member arranged on the sole of the wearer's foot rather than the first sole member. A method for manufacturing a shoe sole member comprising
a step of producing the first sole member by subjecting a rubber composition containing at least styrene-butadiene rubber and dry silica to a cross-linking treatment (cross-linking treatment step);
and a step of adhering the first sole member and the second sole member with an adhesive containing polyurethane resin (adhesion step).

Specifically, the method for manufacturing the shoe sole member of the present embodiment includes:
(a) a step of mixing raw materials such as styrene-butadiene rubber, butadiene rubber, dry silica, and a silane coupling agent (mixing step);
(b) A step of adding a cross-linking agent to the admixture prepared by the above mixing and further mixing the rubber composition into a sheet to prepare a preformed sheet 11' of the first sole member in an uncrosslinked state (sheet conversion process) and
(c) a step of applying a compressive force to the preformed sheet 11′ of the first sole member and subjecting it to heat treatment to produce the first sole member 11, which is a crosslinked body of the rubber composition (crosslinking treatment step); ,
(d) If necessary, a step of pre-treating one surface of the manufactured first sole member 11 that is to be adhered to the second sole member 12 (pre-treatment step);
(e) Disposing an adhesive containing a polyurethane resin between the manufactured first sole member 11 and the second sole member 12 prepared in advance, and attaching the first sole member 11 a step of applying a compressive force in the thickness direction to the laminate with the second sole member 12 to bond the two members together (adhesion step).

(a) In the mixing step, the raw materials described above are kneaded at a temperature of about 110° C. to 150° C. using a kneading device such as a Banbury mixer or a pressure kneader.

In the (b) sheet forming step, for example, the rubber composition is supplied to calender rolls or the like, and the rubber composition is further kneaded by the calender rolls. Then, the kneaded rubber composition is formed into a sheet using a calender roll or the like to prepare an uncrosslinked preformed sheet.

(c) In the cross-linking treatment step, for example, the preformed sheet 11' of the first sole member placed in the mold is hot-pressed by a hot press machine equipped with the mold. This forms a preformed sheet of desired shape in the mold. At the same time, the rubber composition of the preformed sheet 11' of the first sole member is subjected to a cross-linking treatment by hot pressing to produce the first sole member 11 made of a cross-linked body (cross-linked rubber).

(d) In the pretreatment step, the surface of the first sole member 11 or the surface of the second sole member 12 to be adhered is optionally treated in order to further increase the adhesive strength after adhesion. At least one of them is subjected to pretreatment. As the pretreatment, for example, a treatment of polishing the surface or a treatment of applying a pretreatment liquid containing an organic solvent is adopted.

(e) In the bonding step, for example, an adhesive is applied to one surface of the first sole member 11 . Next, while facing the surface coated with the adhesive and one side of the sheet-like second sole member 12, a thickness is applied to the laminate of the first sole member 11 and the second sole member 12. Apply compressive force in the direction In this way, the first sole member 11 and the second sole member 12 are adhered together with an adhesive containing polyurethane resin.

In addition, the material for manufacturing the second sole member 12 is not particularly limited, and for example, the materials described above are adopted.

The adhesive used in the adhesion process is a general urethane resin adhesive. The urethane resin adhesive includes a solution type in which a urethane resin is dissolved in an organic solvent, and an emulsion type in which particles containing a urethane resin are dispersed in a liquid containing water. In general, when the adhesion process is performed using the emulsion type adhesive, the first sole member 11 is more likely to be attached than when the solution type adhesive is used. The bonding strength with the second sole member 12 becomes smaller. This is probably because, in the emulsion type adhesive, the urethane resin, which is an adhesive component, is not uniformly dissolved in the adhesive, but is dispersed.

However, since the solution type adhesive contains an organic solvent, the organic solvent volatilized during the manufacturing process is released into the air. Therefore, from the viewpoint of safety to the human body, fire prevention, and protection of the global environment, it is necessary to suppress the use of the solution type adhesive.
Therefore, there is a demand for a manufacturing method that can exhibit good adhesive strength between the first shoe sole member 11 and the second shoe sole member 12 even when the emulsion type adhesive is used. there is

In the manufacturing method of the present embodiment, when the emulsion type adhesive is used, in order to increase the adhesive strength between the first sole member 11 and the second sole member 12, for example, method can be adopted.
In such a method, the pretreatment steps described above are performed. In the pretreatment step, for example, as shown in FIG. 4, a pretreatment liquid A containing an organic solvent is applied to one surface of the first sole member 11 which is to be adhered to the second sole member 12 later. (See (4-2) in FIG. 4). This pretreatment liquid A can increase the adhesive strength with the second sole member 12 .
Next, in the pretreatment process, the organic solvent contained in the pretreatment liquid A is volatilized by heating, for example, to about 60° C. (see (4-3) in FIG. 4).
Subsequently, the emulsion type adhesive B is applied to the surface to which the pretreatment liquid A has been applied (see (4-4) in FIG. 4).
Furthermore, by heating, for example, to about 60° C., the liquid such as water contained in the emulsion type adhesive B is volatilized (see (4-5) in FIG. 4).
Then, one side of the second sole member 12 is superimposed on the surface to which the adhesive is applied, and the first sole member 11 and the second sole member 12 are adhered ((4-6 in FIG. 4). )).

According to the production method shown in FIG. 4, a relatively high adhesive strength can be exhibited, but since an organic solvent is used, it is not so desirable from the viewpoint of global environmental protection. Thus, even when using an emulsion type adhesive that does not contain an organic solvent, the use of a pretreatment liquid containing an organic solvent as in the pretreatment step described above is avoided as much as possible. need to refrain.

In contrast to the manufacturing method shown in FIG. 4 described above, even in the following manufacturing method shown in FIG. The bonding strength between the sole member 11 and the second sole member 12 can be increased. Specifically, a manufacturing method can be implemented in which the operation of applying the pretreatment liquid is removed from the method shown in FIG.

More specifically, in the manufacturing method of this embodiment, for example, as shown in FIG. The emulsion type adhesive B is applied without applying the pretreatment liquid containing the adhesive (see (5-2) in FIG. 5).
Next, by heating to, for example, about 60° C., liquid such as water contained in the emulsion type adhesive B is volatilized (see (5-3) in FIG. 5).
Then, one side of the second sole member 12 is superimposed on the surface coated with the adhesive, and the first sole member 11 and the second sole member 12 are adhered ((5-4) in FIG. 5). ).

When the shoe sole member 10 is manufactured by the manufacturing method shown in FIG. expected to be lower. However, in the manufacturing method of the present embodiment, since the first shoe sole member 11 is formed of the crosslinked rubber composition having the specific composition described above, the above-mentioned emulsion type adhesive is used to form the adhesive as shown in FIG. Even if the sole member 10 is manufactured by the method, the adhesive strength between the first sole member 11 and the second sole member 12 is sufficiently increased. In this embodiment, even if the sole member 10 is manufactured using a solution type adhesive, the adhesive strength between the first sole member 11 and the second sole member 12 is sufficiently high. growing.

The shoe 100 including the shoe sole member 10 manufactured as described above is used, for example, as a sports shoe. The shoe 100 described above may also be used in other applications, such as sneakers.

The shoe sole member, the shoe, and the method for manufacturing the shoe sole member of the present embodiment are as exemplified above. It is not limited to the manufacturing method.
That is, various forms used in a general method for manufacturing a shoe sole member, a shoe, or a shoe sole member can be employed as long as the effects of the present invention are not impaired.

Matters disclosed by this specification include the following.
(1)
A first sole member arranged on the sole of the shoe, and a second sole member arranged on the sole of the wearer's foot rather than the first sole member,
The first sole member and the second sole member are adhered via an adhesive layer containing a polyurethane resin,
A shoe sole member, wherein the first shoe sole member is a crosslinked rubber composition containing at least styrene-butadiene rubber and dry silica.
(2)
The shoe sole member according to (1) above, wherein the styrene-butadiene rubber accounts for half or more of the rubber component in the rubber composition.
(3)
The shoe sole member according to (1) or (2) above, wherein the rubber composition further contains butadiene rubber.
(4)
The shoe sole member according to any one of (1) to (3) above, wherein the rubber composition further contains at least one of a coupling agent and a cross-linking agent.
(5)
The sole member according to (4) above, wherein the rubber composition further contains the cross-linking agent, and the cross-linking agent is an organic peroxide or sulfur.
(6)
The shoe sole member according to any one of (1) to (5) above, wherein the rubber composition has a fatty acid content of less than 1% by mass.
(7)
The shoe sole member according to any one of (1) to (6) above, wherein the amount of isoprene rubber is less than 20 parts by mass out of 100 parts by mass of the rubber component in the rubber composition.
(8)
Of 100 parts by mass of the rubber component contained in the rubber composition, 20 parts by mass or more and 40 parts by mass or less is the styrene-butadiene rubber, and the rubber composition is 40 parts by mass with respect to 100 parts by mass of the rubber component. The shoe sole member according to any one of (1) to (7) above, containing the dry silica described above.
(9)
Of 100 parts by mass of the rubber component contained in the rubber composition, 60 parts by mass or more and 80 parts by mass or less is the styrene-butadiene rubber, and the rubber composition is 20 parts by mass with respect to 100 parts by mass of the rubber component. The shoe sole member according to any one of (1) to (7) above, containing the dry silica described above.
(10)
A shoe comprising the sole member according to any one of (1) to (9) above.
(11)
A method for manufacturing a shoe sole member comprising a first sole member arranged on the sole of a shoe and a second sole member arranged on the sole of the wearer's foot rather than the first sole member, the method comprising:
producing the first sole member by subjecting a rubber composition containing at least styrene-butadiene rubber and dry silica to a cross-linking treatment;
and a step of bonding the first sole member and the second sole member with an adhesive containing a polyurethane resin.
(12)
The method for manufacturing a shoe sole member according to (11) above, wherein the step of producing the first shoe sole member and the step of adhering are performed simultaneously.
(13)
The method for producing a shoe sole member according to (11) or (12) above, wherein the adhesive is an emulsion type adhesive in which the polyurethane resin is dispersed in a liquid containing water.

Next, the present invention will be described in more detail by way of experimental examples, but the present invention is not limited to these.

The first shoe sole member and the second shoe sole member were adhered with an adhesive in the following manner to manufacture a shoe sole member. Tables 1 to 4 show raw materials for manufacturing the shoe sole members of each example and each comparative example and the compounding composition of the rubber composition for forming the first shoe sole member.

<Raw material of the first sole member>
[Raw materials for the rubber composition of the first sole member]
(I) Rubber component S-SBR1: Styrene-butadiene rubber Product name “Asaprene 303” (manufactured by Asahi Kasei Corporation)
Percentage of styrene in the molecule: 46% by mass
・S-SBR2: Styrene-butadiene rubber Product name “JSR1502” (manufactured by JSR)
Percentage of styrene in the molecule: 23.5% by mass
・ BR: Butadiene rubber Product name “Nipol BR1220” (manufactured by Zeon Corporation)
・IR: Isoprene rubber Product name “Nipol IR2200” (manufactured by Zeon Corporation)
・EPDM: Ethylene propylene diene rubber Product name “EP21” (manufactured by JSR)
Percentage of diene in the molecule: 5.8% by mass
(II) Silica / dry silica: fumed silica Product name “Aerosil 200V” (manufactured by Nippon Aerosil Co., Ltd.)
Average particle size: 12 nm/BET specific surface area: 200 [m ² /g]
・Wet silica Product name “Ultrasil VN3” (manufactured by Degussa)
Average particle size: 18 nm/BET specific surface area: 170 [m ² /g]
(III) Coupling agent SiSH: Mercapto-based coupling agent Chemical name: 2-mercaptoethyltriethoxysilane Product name “NXT-Z-100” (manufactured by Momentive)
・SiMS: Monosulfide-based coupling agent Chemical name: 3-octanoylthio-1-propyltriethoxysilane Product name “NXT-Silane” (manufactured by Momentive)
・SiEP: Epoxy coupling agent Chemical name: Glycidoxypropyltrimethoxysilane Product name “A-187” (manufactured by Momentive)
・SiTS: Tetrasulfide-based coupling agent Chemical name: Bis[3-(triethoxysilyl)propyl]tetrasulfide Product name “Si-69” (manufactured by Degussa Japan)
(IV) Cross-linking agent CrPO: A cross-linking agent containing an organic peroxide, 1,1-bis(tert-butylperoxy)cyclohexane mixed with dry silica in a 1:1 mass ratio CrS: Sulfur Product name "Fine Sulfur 200 mesh” (manufactured by Hosoi Chemical Co., Ltd.)
(V) Cross-linking accelerator DM (thiazole-based cross-linking accelerator, chemical name: di-2-benzothiazolyl disulfide)
Product name "Noccellar DM-P" (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
・M (thiazole cross-linking accelerator, chemical name: 2-mercaptobenzothiazole)
Product name "Noccellar MP" (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
・ TS (thiuram-based cross-linking accelerator, chemical name: tetramethylthirium monosulfide)
Product name "Noccellar TS" (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
(VI) Fatty acid/stearic acid (VII) Process oil Product name “JOMO Process P200” (manufactured by JX Nippon Oil & Energy Corporation)
[Urethane resin adhesive (emulsion type)]
1-component water-based urethane adhesive (non-volatile content 49% by mass, pH about 7, viscosity about 7000 mPa s [BM type viscometer])

<Second Sole Member>
As the second shoe sole member, a sheet made of polyurethane resin (plate-shaped, thickness 2 mm, A hardness 95 conforming to JIS K7312) was prepared.

(Examples 1 to 24)
Each component was mixed according to each compounding composition shown in Tables 1 to 4 to prepare each rubber composition (unvulcanized state) for the first sole member. Next, the rubber composition was subjected to heat press treatment under conditions of 160° C. and 15 MPa for 10 minutes to obtain a crosslinked body, thereby producing a first shoe sole member (thickness: 2 mm).
Subsequently, the surface of the first sole member to be adhered to the second sole member was polished. An adhesive was applied to the polished surface and dried at 60° C. for 7 minutes.
Thereafter, while applying pressure, the coated surface was attached to the second sole member to manufacture each sole member.

(Comparative Examples 1 to 4)
A rubber composition was prepared in the same manner as in each of the above examples, using each compounding composition shown in Tables 1 to 4, and a shoe sole member was produced in the same manner.

The adhesion strength between the first sole member and the second sole member was evaluated in the following manner for each of the shoe sole members produced in Examples and Comparative Examples.

<Measurement of adhesive strength>
The adhesion strength between the first sole member and the second sole member was measured for test samples of the sole member manufactured in each example and each comparative example. The measurement conformed to "Adhesive-Peeling Bond Strength Test Method-Part 3: T-type Peeling (JIS K6854-3:1999)".
The measurement results are shown in Tables 1 to 4, respectively.

As can be seen from Tables 1 to 4, the shoe sole members of the examples have a higher adhesive strength between the first shoe sole member and the second shoe sole member than the shoe sole members of the comparative examples. It was good. The rubber composition contains both styrene-butadiene rubber and butadiene rubber, and the higher the content of styrene-butadiene rubber in the rubber component, the higher the adhesive strength between the first sole member and the second sole member. tended to be higher.

What is understood from the results shown in Tables 1 to 4 is described below.
If all the rubber components in the rubber composition are styrene-butadiene rubber, the adhesive strength is expected to be high. - It can be said that it is preferable to include a rubber component other than butadiene rubber (see Example 6). In Table 1, in Example 6, the viscosity of the rubber composition was too high, so kneading was difficult and the first sole member could not be produced, and the adhesive strength could not be measured.
There was a tendency that the higher the styrene content in the styrene-butadiene rubber molecule, the higher the adhesive strength.
When the rubber composition contains isoprene rubber, the adhesive strength tends to be low, but it is possible to blend a relatively small amount of isoprene rubber into the rubber composition.
Adhesion strength tended to increase as the amount of fumed silica in the rubber composition increased. Moreover, the rubber composition may contain both dry silica and wet silica as silica. Also, by setting the ratio of the styrene-butadiene rubber and the dry silica in the rubber composition to a specific ratio, the adhesive strength tends to be further improved.
Whether sulfur or an organic peroxide was used as the cross-linking agent had little effect on the adhesive strength.
Fatty acid (stearic acid), which is generally blended in rubber compositions when sulfur is used as a cross-linking agent, tends to lower the adhesive strength in the above examples. However, it is possible to incorporate relatively small amounts of fatty acid (stearic acid) into the rubber composition.
From the point of view of increasing the strength of the first sole member, it is preferable to mix a coupling agent with the rubber composition. The effect of the type of coupling agent on adhesive strength was small.

The adhesive strength is not very high in Example 7, but this is due to the relatively low content of fumed silica in the rubber composition. If the dry silica in Example 7 is replaced with wet silica to produce a shoe sole member in the same manner, the adhesive strength is expected to be even smaller than the adhesive strength in Example 7.
In Example 4, the adhesion strength was not so high, but the reason for this is that the content of isoprene rubber in the rubber composition is relatively large. As shown in Table 4, when a shoe sole member was produced in the same manner by replacing the dry silica in Example 4 with wet silica (Comparative Example 3), the adhesive strength was even lower than that of Example 4. .
In addition, although the adhesion strength is not so high in Examples 19 and 21, this is due to the relatively high content of fatty acid (stearic acid) in the rubber composition. If the dry-process silica in Examples 19 and 21 is replaced with wet-process silica to produce shoe sole members in the same manner, the adhesive strength of these is expected to be even smaller than the adhesive strength of Examples 19 and 21.
The adhesive strength is slightly high in Comparative Example 2, but the reason for this is that the amount ratio of the rubber component and dry silica in the rubber composition is appropriate. As shown in Table 2, in the example (Example 10) in which the wet silica in Comparative Example 2 was replaced with dry silica to produce a shoe sole member in the same manner, the adhesive strength was considerably increased.

The shoe sole member of the present invention is preferably used by being placed on the sole of a shoe. The shoe of the present invention is preferably used by being worn on each foot of the wearer. The shoe of the present invention is preferably used, for example, as a sports shoe.
The method for manufacturing a shoe sole member of the present invention is preferably used for manufacturing the above shoe sole member.

100: Shoes,
10: Sole member,
11: first sole member, 12: second sole member, 13: adhesive layer,
50: Upper material.

Claims (8)

A first sole member arranged on the sole of the shoe, and a second sole member arranged on the sole of the wearer's foot rather than the first sole member,
The first sole member and the second sole member are adhered via an adhesive layer containing a polyurethane resin,
A shoe sole member, wherein the first shoe sole member is a crosslinked rubber composition containing at least styrene-butadiene rubber and dry silica. 2. The sole member according to claim 1, wherein the styrene-butadiene rubber accounts for half or more of the rubber component in the rubber composition. The sole member according to claim 1 or 2, wherein the rubber composition further contains butadiene rubber. The sole member according to any one of claims 1 to 3, wherein the rubber composition further contains at least one of a coupling agent and a cross-linking agent. 5. The sole member according to claim 4, wherein said rubber composition further comprises said cross-linking agent, said cross-linking agent being an organic peroxide or sulfur. The shoe sole member according to any one of claims 1 to 5, wherein the rubber composition has a fatty acid content of less than 1% by mass. A shoe comprising the sole member according to any one of claims 1 to 6. A method for manufacturing a shoe sole member comprising a first sole member arranged on the sole of a shoe and a second sole member arranged on the sole of the wearer's foot rather than the first sole member, the method comprising:
producing the first sole member by subjecting a rubber composition containing at least styrene-butadiene rubber and dry silica to a cross-linking treatment;
and a step of bonding the first sole member and the second sole member with an adhesive containing a polyurethane resin.

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