WO2022113234A1

WO2022113234A1 - Shoe member manufacturing method and shoe member

Info

Publication number: WO2022113234A1
Application number: PCT/JP2020/044008
Authority: WO
Inventors: 貴士山出
Original assignee: 株式会社アシックス
Priority date: 2020-11-26
Filing date: 2020-11-26
Publication date: 2022-06-02

Abstract

Provided are: a shoe member manufacturing method comprising a step for preparing an uncrosslinked rubber member, a step for placing, on one surface of the uncrosslinked rubber member, a metal oxide having a relative permittivity of 30 or more, a step for producing a first member having the metal oxide bound to one surface thereof by crosslinking said uncrosslinked rubber member on which the metal oxide is placed, while having pressure applied on the rubber member, a step for irradiating the first member with microwaves, and a step for placing a second member, which is different from the first member, on said one surface of the first member, and adhering the second member to the first member; and a shoe member in which a first member made of a crosslinked rubber and a second member different from the first member are adhered and which includes a metal oxide having a relative permittivity of 30 or more at an adhesion interface between the first member and the second member.

Description

Manufacturing method of shoe parts and shoe parts

The present invention relates to a method for manufacturing a shoe member using microwave irradiation, and a shoe member that can be manufactured by the manufacturing method.

The process of manufacturing a shoe member often involves adhering a crosslinked rubber member to another member. When adhering such a crosslinked rubber member, an adhering method using a solvent-based treatment agent is generally used.
However, in recent years, efforts have been made to reduce the burden on the environment at the manufacturing site of shoe members, and as a part of this, there is a demand for an adhesive technique that does not use a solvent-based treatment agent.

As a method of adhering the crosslinked rubber member without using a solvent-based treatment agent, for example, a method of adhering the crosslinked rubber member to another member by using an aqueous treatment agent can be considered.
However, it is known that it is difficult to bond the crosslinked rubber member with high strength by bonding using such an aqueous treatment agent.

Examples of the method for improving the adhesive strength in the adhesion of the crosslinked rubber member using the water-based treatment agent include the method described in Patent Document 1. Patent Document 1 describes a step of applying an aqueous adhesive to the surface of a first base material and treating it with an electromagnetic wave (microwave) having a frequency band of 2.45 ± 0.02 GHz, and a step of treating the surface of the second base material with an electromagnetic wave (microwave). The process of applying and drying the water-based adhesive, and the surface coated with the water-based adhesive of the first base material treated with electromagnetic waves and the surface coated with the water-based adhesive of the dried second base material are pasted. A method for manufacturing a laminated structure including a step of combining is disclosed.

However, when the crosslinked rubber member is heat-treated by microwaves as in the method of Patent Document 1, if the heat treatment is excessively performed, the crosslinked rubber member of the base material is adversely affected by excessive heat, and the manufactured product is manufactured. The quality may deteriorate.
Therefore, when the adhesive surface of the crosslinked rubber member is heated by the microwave, the base material can be efficiently heated so as not to receive excessive heat more than necessary, thereby further strengthening the crosslinked rubber member and another member. There is a need for a method that can be adhered to.

Japanese Patent Application Laid-Open No. 2013-151141

The present invention is a method for manufacturing a shoe member capable of firmly adhering a crosslinked rubber member and another member while suppressing an adverse effect due to heat on the crosslinked rubber member, and the members are firmly adhered to each other. It is an object of the present invention to provide a member for shoes made.

The present invention
Steps where uncrosslinked rubber members are prepared,
A step in which a metal oxide having a relative permittivity of 30 or more is arranged on one surface of the uncrosslinked rubber member.
A step of producing a first member having the metal oxide fixed on one surface by cross-linking the uncrosslinked rubber member to which the metal oxide is arranged under pressure.
The step of irradiating the first member with microwaves and
A step in which a second member different from the first member is arranged on the one surface of the first member and the first member and the second member are adhered to each other.
Provided is a method for manufacturing a member for shoes.

Further, the present invention
A shoe member to which a first member made of crosslinked rubber and a second member different from the first member are adhered.
Provided is a shoe member containing a metal oxide having a relative permittivity of 30 or more at an adhesive interface between the first member and the second member.

FIG. 1 is a diagram showing the temperature of the adhesive surface of the crosslinked rubber member with respect to the 1520 W microwave irradiation time in Examples and Comparative Examples. FIG. 2 is a diagram showing the temperature of the adhesive surface of the crosslinked rubber member with respect to the 1520 W microwave irradiation time in Examples and Comparative Examples. FIG. 3 is a diagram showing the temperature of the adhesive surface of the crosslinked rubber member with respect to the 570 W microwave irradiation time in Examples and Comparative Examples. FIG. 4 is a diagram showing the temperature of the adhesive surface of the crosslinked rubber member with respect to the 570 W microwave irradiation time in Examples and Comparative Examples. FIG. 5 is a diagram showing the peel strength of the adhesive interface between the crosslinked rubber member and the TPU member with respect to the 1520 W microwave irradiation time in Examples and Comparative Examples. FIG. 6 is a diagram showing the peel strength of the adhesive interface between the crosslinked rubber member and the TPU member with respect to the 1520 W microwave irradiation time in Examples and Comparative Examples. FIG. 7 is a diagram showing the peel strength of the adhesive interface between the crosslinked rubber member and the TPU member with respect to the 570 W microwave irradiation time in Examples and Comparative Examples. FIG. 8 is a diagram showing the peel strength of the adhesive interface between the crosslinked rubber member and the TPU member with respect to the 570 W microwave irradiation time in Examples and Comparative Examples.

Hereinafter, the manufacturing method of the shoe member and the shoe according to the embodiment of the present invention will be described with reference to the drawings. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

Further, in each drawing referred to in the embodiment and the like, members having substantially the same function are referred to by the same reference numeral. Further, the drawings referred to in the embodiment are schematically described, and the ratio of the dimensions of the object depicted in the drawing may be different from the ratio of the dimensions of the actual object.

(Manufacturing method of shoe parts)
The method for manufacturing a shoe member of the present embodiment includes at least the following steps.
(1) Steps where uncrosslinked rubber members are prepared,
(2) A step in which a metal oxide having a relative permittivity of 30 or more is arranged on one surface of an uncrosslinked rubber member.
(3) A step in which an uncrosslinked rubber member on which a metal oxide is arranged is crosslinked under pressure to produce a first member in which the metal oxide is fixed on one surface.
(4) Steps in which microwaves are applied to the first member, and
(5) A step in which a second member different from the first member is arranged on the one surface of the first member, and the first member and the second member are adhered to each other.

The shoe member manufactured by the manufacturing method of the present embodiment is manufactured by adhering the first member and the second member described above, and may be any shoe member used for shoes. .. Such shoe members include one or more combinations of other sole sole members such as midsole, outsole, sockliner, shoe reinforcement members such as heel counters and shanks, uppers, decorative materials and the like. Can be mentioned. For example, the shoe member manufactured in the present manufacturing method may be a sole member to which a first member which is an outsole and a second member which is a midsole are bonded.
Further, the shoe member manufactured in the manufacturing method of the present embodiment may be the shoe itself in which a plurality of shoe members are combined.

The first member is made of crosslinked rubber crosslinked from a rubber raw material in the present manufacturing method. Examples of such crosslinked rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and butyl rubber ( Examples thereof include crosslinked rubber such as IIR) and silicone rubber (Si).
For example, when the first member is a member provided on a ground surface such as an outsole, BR, SBR, NR, and IR having excellent tensile strength, tear strength, and wear resistance are preferably selected as the first member. Will be done.

The second member can be any member having a surface to be adhered to the first member made of crosslinked rubber. That is, the second member may be made of one or more members made of any material such as resin, cloth, metal, fiber, etc. as long as it has such a surface to be adhered.
For example, when the second member is a resin, the second member is a polyolefin resin such as polyethylene (PE) resin or polypropylene (PP) resin, a thermoplastic polyurethane (TPU) resin, a polystyrene (PS) resin, or ethylene-. Thermoplastic resin including propylene rubber (EPDM), polyether blockamide (PEBA) resin, polyester (PEs) resin, ethylene vinyl acetate (EVA) resin, polyamide (PA) resin, etc., thermosetting polyurethane elastomer, acrylic It may contain a thermoplastic resin containing a based elastomer, a crosslinked rubber, a silicone based elastomer, a fluoropolymer and the like.
Further, when the second member is a member provided other than the ground contact surface such as a midsole, a resin foam having excellent cushioning properties and light weight is preferably selected as the second member.

The metal oxide used in the production method of the present embodiment is a material that can be heated with high efficiency by microwave heating during the production method, and is characterized by having a relative permittivity of 30 or more. Examples of such metal oxides include titanium oxide (TiO ₂ ) known to have a relative permittivity of approximately 83 to 183.
The metal oxide may consist of a single type or may be a combination of a plurality of types of metal oxides. When a combination of a plurality of types of metal oxides is used, the proportion of titanium oxide contained in the entire metal oxide used is preferably at least 30%, more preferably 50% or more. preferable

It is known that the relative permittivity of metal oxides has a very small frequency dependence. Therefore, if the metal oxide used in the present embodiment has a relative permittivity of 30 or more at an arbitrary frequency, it is ensured that the metal oxide is heated with high efficiency by the microwave heating performed in the manufacturing method. .. If necessary, a microwave frequency of 300 MHz to 300 GHz, for example, 2.45 GHz, is referred to as a frequency for designating the relative permittivity of the metal oxide.

The form of the metal oxide is not particularly limited, and may be any form such as powder or mesh. Preferably, the metal oxide is used in powder form. In that case, the average particle size of the primary particles of the powdered metal oxide is preferably in the range of 0.05 to 0.5 μm.
In the present specification, the average particle size of the primary particles of the metal oxide can be determined based on the measurement method using a transmission electron microscope of JIS Z 8901: 2006.

Hereinafter, each step included in the manufacturing method of the present embodiment will be described.

(1) Step in which an uncrosslinked rubber member is prepared In the method for manufacturing a shoe member of the present embodiment, first, an uncrosslinked (pre-crosslinked) rubber member is prepared by using any conventionally known method.
The uncrosslinked rubber member can be made of any rubber raw material that becomes the first member made of the crosslinked rubber described above by being crosslinked in a later step. For example, when the rubber member is crosslinked by vulcanization in a later step, the rubber raw material is an uncrosslinked resin which is the same type as the resin contained in the crosslinked rubber of the first member and the uncrosslinked resin. It may contain about 1 to 3 parts by weight of sulfur with respect to 100 parts by weight.

The form of the rubber member is not particularly limited, but it is preferable that the rubber member is prepared in a form corresponding to the first member after crosslinking.

(2) Step in which a metal oxide having a relative permittivity of 30 or more is arranged on one surface of the uncrosslinked rubber member Next, a predetermined surface of the uncrosslinked rubber member prepared in step (1). Above, the above-mentioned metal oxide having a relative permittivity of 30 or more is arranged.
One surface of the rubber member in this step is a surface (in other words, the rubber) that becomes one surface of the first member that comes into contact with the second member after the rubber member is crosslinked to become the first member in a later step. At least a part of the surface of the member), and the region of one surface of the rubber member on which the metal oxide is arranged in this step becomes the adhesive surface of the first member to be adhered to the adhered surface of the second member.

The amount of the metal oxide arranged on the adhesive surface of the rubber member is not necessarily limited to the following, but the surface treatment amount for the adhesive surface is preferably in the range of 0.3 to 1.0 mg / cm ² , and 0. The range of 4 to 0.8 mg / cm ² is more preferable. When the surface treatment amount of the metal oxide is 0.3 mg / cm ² or more, the adhesive surface of the first member after cross-linking can be heated more efficiently by microwave heating, whereby the said. The bonded surface can be heated to a sufficiently high temperature in a short time. In addition, since the surface treatment amount of the metal oxide is 1.0 mg / cm ² or less, the crosslinked rubber constituting the first member and the bonded surface of the second member are adhered to the bonded surface of the first member after cross-linking. It is possible to secure a sufficient area for direct adhesion (or via a treatment agent described later) without sandwiching the metal oxide with the exposed material, whereby the first member and the first member can be bonded to each other. It is possible to relatively increase the adhesive strength (peeling strength) of the adhesion with the two members.

The metal oxide is preferably arranged on the entire surface of the rubber member. In that case, the entire surface of the first member that comes into contact with the second member after the rubber member is crosslinked to become the first member in a later step can function as an adhesive surface.
In that case, the metal oxide can be distributed substantially uniformly (eg, with a surface treatment amount in the range of 0.3 to 1.0 mg / cm ² ) over the entire surface of the rubber member, for example. By doing so, the first member and the second member can be evenly adhered to each other, so that the adhesive strength (peeling strength) can be further increased.

On the other hand, a suitable amount and relative permittivity of the metal oxide is arranged only in the peripheral region of the one surface of the rubber member (that is, the surface that comes into contact with the second member after being crosslinked to become the first member). You may. For example, a metal oxide in the range of 0.3 to 1.0 mg / cm ² as a surface treatment amount is arranged in the peripheral region of the one surface of the rubber member, and a smaller amount of metal is arranged in the inner region thereof. Oxides may be arranged. Alternatively, the metal oxide arranged in the peripheral region of the one surface of the rubber member is a metal oxide having a relatively high relative permittivity such as titanium oxide, and the metal oxide arranged in the region inside the metal oxide is used. It may be a metal oxide having a lower relative permittivity. Further, a metal oxide having a relative permittivity of less than 30 may be arranged in a region inside the peripheral region of the one surface of the rubber member, or a metal oxide may not be arranged at all.
In these cases, the amount of metal oxide used can be reduced while effectively suppressing the adhesion between the first member and the second member from the peripheral edge portion. Such a method is useful when the shoe member to be manufactured is expected to be used in a relatively mild environment.

In the present specification, the peripheral region of the one surface of the rubber member means a region including the peripheral edge of the one surface and its vicinity, for example, a region having a width of 10 mm inward from the peripheral edge of the one surface.

(3) A step in which an uncrosslinked rubber member on which a metal oxide is arranged is crosslinked under pressure to produce a first member in which the metal oxide is fixed on one surface (adhesive surface). In step (2), the uncrosslinked rubber member to which the metal oxide is arranged is crosslinked under pressure. As a result, the rubber member is crosslinked to become the first member, and the first member made of crosslinked rubber in which the metal oxide is fixed on one surface (adhesive surface) of the first member corresponding to the one surface of the rubber member is formed. can get.

Crosslinking of the rubber member can be carried out by any method performed under pressure, and in many cases, it is performed by vulcanizing the uncrosslinked resin contained in the rubber member. Vulcanization of the rubber member may be carried out, for example, by heating (heat pressing) the rubber member containing sulfur as described above under pressure. In that case, the rubber member can be vulcanized, for example, by maintaining it at 140 to 180 ° C. for 2 to 20 minutes under a predetermined pressure described below.
However, the cross-linking of the rubber member may be carried out by a method other than vulcanization, and may be cross-linked using, for example, an organic peroxide, bismaleimide or a quinoid.

The pressure applied in the pressurization at the time of crosslinking is not particularly limited as long as the metal oxide can be fixed on one surface of the first member. Preferably, the pressurization at the time of crosslinking is performed with a high pressure to such an extent that the metal oxide is embedded on the one surface of the first member. By embedding the metal oxide on the one surface of the first member, the metal oxide is more firmly fixed on the one surface, so that the adhesive strength (peeling) when the first member and the second member are adhered to each other. Strength) can be further increased. Further, by applying a relatively high pressure at the time of crosslinking, it is possible to obtain an effect that a part of the rubber is sponged at the time of crosslinking and the decrease in strength is suppressed.
Preferably, the pressure applied in the pressurization at the time of crosslinking is preferably 5 MPa or more.

(4) Step of irradiating the first member with microwaves Next, in step (3), the first member to which the metal oxide is fixed is irradiated with microwaves.
When the first member is irradiated with microwaves, the metal oxide fixed on the one surface (adhesive surface) of the first member absorbs the microwaves, whereby the metal oxide generates heat. As a result, the heat of the generated metal oxide is transferred to the entire surface of the first member to which the metal oxide is fixed, and the entire surface is heat-treated.

The frequency of the irradiated microwave is not particularly limited. As described above, since the relative permittivity of the metal oxide has a very small frequency dependence, the metal oxide having a relative permittivity of 30 or more used in the present embodiment is heated at an arbitrary frequency in the microwave frequency. It is possible. For example, 2.4 GHz is used as the frequency of the irradiated microwave.
However, when the first member contains a member that is easily affected by a predetermined frequency within the microwave frequency in addition to the metal oxide, in order to avoid the influence of microwave irradiation on other than the metal oxide. In addition, it is preferable to use microwaves having a frequency far from such a predetermined frequency.

The irradiation intensity and irradiation time of the microwave are not particularly limited, and the intensity and time can be set so that the metal oxide can be sufficiently heated to sufficiently heat-treat the one surface (adhesive surface) of the first member. However, if the heat treatment is excessively performed, the crosslinked rubber constituting the first member may be adversely affected by the excessive heat. Therefore, for example, the irradiation time of the microwave is preferably 240 seconds or less so that the heat treatment of the one surface (adhesive surface) of the first member can be performed efficiently and promptly, and the first member is irradiated with the microwave. It is preferable to adjust the irradiation intensity and irradiation time of the microwave so that the temperature of the one surface (adhesive surface) does not exceed 200 ° C.

In addition, after preparing the first member in which the metal oxide is fixed to the one surface (adhesive surface) in the step (3), and before the main step (4) of irradiating the microwave, the one surface of the first member. An additional step (3.5) may be provided in which the (adhesive surface) is coated with any treatment agent. In this case, examples of the treatment agent applied to the one surface (adhesive surface) of the first member include a chloroprene emulsion, a polyurethane emulsion, a vinyl acetate emulsion, an acrylic emulsion, an epoxy emulsion, and a styrene rubber emulsion. Can be mentioned.
The adhesive applied in the additional step (3.5) will be heated together with the above-mentioned one surface (adhesive eye) of the first member by the irradiation of the microwave in the step (4). At this time, the treatment agent can be dried by heating.

Further, after the microwave is irradiated in the step (4) and before the step (5) described later is performed, an arbitrary treatment agent is applied to the one surface (adhesive surface) of the first member. Another additional step (4.5) may be provided. In this case, examples of the treatment agent applied to the one surface (adhesive surface) of the first member include a water-based urethane adhesive, a solvent-based urethane adhesive, an epoxy-based adhesive, an acrylic-based adhesive, and a vinyl acetate-based adhesive. , Rubber-based adhesives can be mentioned.
Further, in the additional step (4.5), after the treatment agent is applied to the one surface (adhesive surface) of the first member, the first member may be heated by any method such as oven heating. At this time, the temperature at which the first member is heated may be such that the treatment agent can be dried by heating, and may be, for example, in the range of 50 to 100 ° C.
Only one of these additional steps (3.5) and the additional step (4.5) may be performed, or both may be performed. If both are done, the treatments applied in these additional steps may be of different types or of the same type. Further, in step (5) described later, if the first member and the second member can be adhered to each other, none of these additional steps may be performed.

(5) A step in which a second member different from the first member is arranged on the one surface of the first member and the first member and the second member are adhered to each other. After that, the one surface (adhesive surface) of the first member. ) By arranging the second member on the surface, the adhesive surface of the first member and the adhered surface of the second member are bonded to each other, thereby adhering the first member and the second member.
In this step, after the adhesive surface of the first member and the adhered surface of the second member are bonded together, the first member and the second member are adhered by curing for a predetermined time (for example, 48 hours) or more. Is completed, whereby the desired shoe member can be manufactured.

The adhesion between the first member and the second member is, for example, the adhesion applied on the adhesive surface of the first member in one or both of the above-mentioned additional step (3.5) and additional step (4.5). This can be done by adhering the adhesive surface of the first member and the adhered surface of the second member via a treatment agent such as an agent. In the manufacturing method of the present embodiment, the adhesive surface is efficiently heated by the metal oxide fixed on the adhesive surface of the first member, so that the treatment agent is firmly fixed to the adhesive surface of the first member. Can be. Therefore, by adhering the first member and the second member via the treatment agent, the adhesive strength of these members can be effectively increased.

However, the adhesion between the first member and the second member is not limited to that performed via a treatment agent. For example, when the first member is a member made of a diene rubber, the double bond remaining in the first member is converted into a hydroxyl group when it is microwave-heated in the air, and the hydroxyl group is converted into a hydroxyl group. Adhesiveness based on the action of the above may be imparted to the adhesive surface of the first member. In such a case, the adhesion between the first member and the second member may be performed by directly adhering the adhesive surface of the first member and the adhered surface of the second member. In that case, since the adhered surface of the second member can be firmly fixed to the adhesive surface of the first member that has been efficiently heated, the adhesive strength of these members is effectively enhanced.

In this step, after the second member is arranged on the first member, the first member and the second member may be bonded under pressure. Thereby, the first member and the second member can be effectively adhered to each other at the time of bonding.

By performing each of the above steps, in the manufacturing method of the present embodiment, it is possible to manufacture a shoe member in which the first member and the second member are firmly adhered to each other.
For example, when the first member is an outsole and the second member is a midsole, the manufacturing method of the present embodiment manufactures a sole member to which these members are firmly adhered.

(Members for shoes)
The shoe member of the present embodiment is manufactured by the above-mentioned manufacturing method of the shoe member.
Specifically, in the shoe member of the present embodiment, the first member made of crosslinked rubber and the second member different from the first member are adhered to each other, and the first member and the second member are adhered to each other. A metal oxide having a relative permittivity of 30 or more is contained in the adhesive interface.
Here, the first member, the second member, and the metal oxide are the same as those described for the above-described embodiment of the method for manufacturing a shoe member.

The shoe member of the present embodiment preferably has a range of 0.3 to 1.0 mg / cm ² with respect to the adhesive interface to which the first member and the second member are adhered, more preferably 0.4. An amount of metal oxide in the range of ~ 0.8 mg / cm ² is contained in the adhesive interface. By including the metal oxide in such a range in the adhesive interface, the adhesive strength between the first member and the second member can be more effectively enhanced in the shoe member of the present embodiment.

The metal oxide may be contained in the entire contact surface where the first member and the second member are in contact (that is, the entire contact surface between the first member and the second member is an adhesive interface). It is preferable that the metal is generally evenly distributed over the entire bonding interface.
However, when it is assumed that the shoe member is used in a relatively non-harsh environment, the metal oxide is not always uniformly distributed over the entire contact surface between the first member and the second member. You may. In that case, in order to prevent the adhesion between the first member and the second member from peeling off from the peripheral edge portion, a suitable amount and relative permittivity are applied to the peripheral edge region of the contact surface between the first member and the second member. Metal oxide may be arranged.

Similar to the above-described embodiment of the method for manufacturing a shoe member, the shoe member of the present embodiment can be any shoe member used for shoes. For example, the shoe member manufactured in the present manufacturing method may be a sole member to which a first member which is an outsole and a second member which is a midsole are bonded. Further, the shoe member of the present embodiment may be a shoe itself in which a plurality of shoe members are combined.

As described above, the method for manufacturing a shoe member according to the embodiment described in the present specification has a step in which an uncrosslinked rubber member is prepared and a specific dielectric constant on one surface of the uncrosslinked rubber member. The metal oxide is fixed on one surface by the step in which 30 or more metal oxides are arranged and the uncrosslinked rubber member on which the metal oxide is arranged is crosslinked under pressure. A step in which one member is manufactured, a step in which the first member is irradiated with a microwave, and a second member different from the first member are arranged on the one surface of the first member. It includes a step in which the first member and the second member are adhered to each other.
According to the above embodiment, the adhesive interface to which the first member made of crosslinked rubber and the second member different from the first member are adhered can be heated remarkably more efficiently by microwaves than in the prior art. .. Therefore, in the method for manufacturing a shoe member of the present embodiment, the adhesive strength between the first member made of crosslinked rubber and the second member different from the first member is increased while suppressing the adverse effect of excessive heat. It can be greatly enhanced compared to the conventional technique.

Further, in the shoe member according to the embodiment described in the present specification, a first member made of crosslinked rubber and a second member different from the first member are adhered to the first member and the first member. The adhesive surface with the second member contains a metal oxide having a relative permittivity of 30 or more.
Therefore, in the shoe member of the above embodiment, the adhesive strength between the first member made of crosslinked rubber and the second member different from the first member is greatly increased as compared with the prior art.

In one aspect of the method for manufacturing a shoe member, a treatment agent is applied onto the surface of the first member after the step of being irradiated with the microwave and before the step of arranging the second member. It further comprises a step of being applied and then the first member being heated. In such an embodiment, since the treating agent can be firmly fixed to the first member, the adhesive strength in the adhesion between the first member and the second member using the treating agent is more effectively enhanced.

In the method for manufacturing a shoe member and one aspect of the shoe member, the metal oxide is titanium oxide (TiO ₂ ). Since titanium oxide has a very high relative permittivity of 83 to 183, the adhesive interface can be heated extremely efficiently in such an embodiment. Therefore, the adhesive strength between the first member and the second member can be increased more effectively.

In one aspect of the method for manufacturing a shoe member, the metal oxide is 0.3 to 1.0 mg / cm ² on one surface of the uncrosslinked rubber member in the step of arranging the metal oxide. Distributed in quantity. Further, in one aspect of the shoe member, the metal oxide is contained in the adhesive interface in an amount of 0.3 to 1.0 mg / cm ² . In such an embodiment, the adhesive interface can be heated extremely efficiently, and a sufficient adhesive area between the first member and the second member without sandwiching the metal oxide can be sufficiently secured. Therefore, the adhesive strength between the first member and the second member is more effectively enhanced.

In the method for manufacturing a shoe member and one aspect of the shoe member, the metal oxide is in the form of powder. In such an embodiment, the adhesive strength between the first member and the second member can be increased more effectively.

In the method for manufacturing a shoe member and one aspect of the shoe member, the first member is a shoe outsole member and the second member is a shoe midsole member.

The method for manufacturing the shoe member and the shoe member according to the present embodiment are not limited to the configuration of the above embodiment. Further, the method for manufacturing a shoe member and the shoe member according to the present invention are not limited by the above-mentioned effects. The method for manufacturing a shoe member and the shoe member according to the present invention can be variously modified without departing from the gist of the present invention.

Further, although no further detailed description will be given here, even if the matters are not directly described above, the technical matters conventionally known regarding the manufacturing method and the shoe member shall be described. It can also be appropriately adopted in the present invention.

Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

Adhesion test between the crosslinked rubber member and the TPU member was performed by the following methods of Examples 1 to 4 and Comparative Examples 1 to 3.

(Example 1 (A1))
First, as a raw material member for the crosslinked rubber member (first member) to be bonded in this embodiment, an uncrosslinked rubber member (butadiene rubber is used as a main material) formed into a plate having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm. The compound (containing 1.5 phr of rubber) was prepared.
Next, by applying powdery TiO ₂ (relative permittivity: approximately 83 to 183) to one surface of the uncrosslinked rubber member with a brush, the surface treatment amount on the surface is 0.2 mg / cm ² . It was arranged almost uniformly on the surface so as to be.
Then, using a hot press machine, the uncrosslinked rubber member was hot-pressed at 160 ° C. and 15 MPa for 5 minutes. The uncrosslinked rubber member was crosslinked by the hot press, and a crosslinked rubber member (first member) in which TiO ₂ was fixed on one surface (adhesive surface) was produced.

After cooling the crosslinked rubber member thus produced to room temperature, 0.2 g of Bond G17 (manufactured by Konishi Co., Ltd.), which is a chloroprene-based emulsion adhesive, is substantially uniformly applied to the adhesive surface of the crosslinked rubber member. The bonded surface was heated by irradiating the crosslinked rubber member with a microwave (frequency 2.45 GHz) of 1520 W for 40 seconds. At this time, the temperature of the adhesive surface after microwave irradiation was recorded.
After cooling the first member to room temperature again, 0.2 g of a water-based urethane adhesive as a treatment agent was subsequently uniformly applied to the adhesive surface of the crosslinked rubber member, and then in an oven at 60 ° C. 7 Heated for minutes.

Then, a plate-shaped TPU member having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm is placed on the adhesive surface of the crosslinked rubber member and pressed for 20 seconds under a pressure of 5 kgf / cm ² for cross-linking. The rubber member and the TPU member were bonded.

(Example 1 (A2) to (A4))
Examples 1 (A2) to (A4) were carried out in the same manner as in Example 1 (A1) except that the microwave irradiation times were set to 50 seconds, 60 seconds and 70 seconds, respectively.

(Example 1 (B1) to (B4))
Examples 1 (B1) to (B1) are the same as in Example 1 (A1) except that the intensity of the irradiated microwave is 570 W and the irradiation times are 120 seconds, 140 seconds, 180 seconds and 200 seconds, respectively. B4) was performed.

(Reference example 1)
Reference Example 1 was performed in the same manner as in Example 1 (A1) except that the microwave was not irradiated.

(Examples 2 (A1) to (A4), Examples 2 (B1) to (B4), Reference Example 2)
Examples 1 (A1) to (A4) except that the powdery TiO ₂ arranged on one surface of the uncrosslinked rubber member was arranged so that the surface treatment amount on the surface was 0.4 mg / cm ² . , Examples 1 (B1) to (B4), Examples 2 (A1) to (A4), Examples 2 (B1) to (B4), and Reference Example 2 were performed in the same manner as in Reference Example 1.

(Examples 3 (A1) to (A4), Examples 3 (B1) to (B4), Reference Example 3)
Examples 1 (A1) to (A4) except that the powdery TiO ₂ arranged on one surface of the uncrosslinked rubber member was arranged so that the surface treatment amount on the surface was 0.8 mg / cm ² . , Examples 1 (B1) to (B4), Examples 3 (A1) to (A4), Examples 3 (B1) to (B4), and Reference Example 3 were performed in the same manner as in Reference Example 1.

(Examples 4 (A1) to (A4), Examples 4 (B1) to (B4), Reference Example 4)
Examples 1 (A1) to (A4) except that the powdery TiO ₂ arranged on one surface of the uncrosslinked rubber member was arranged so that the surface treatment amount on the surface was 2.0 mg / cm ² . , Examples 1 (B1) to (B4), Examples 4 (A1) to (A4), Examples 4 (B1) to (B4), and Reference Example 4 were performed in the same manner as in Reference Example 1.

(Comparative Examples 1 (A1) to (A4), Comparative Examples 1 (B1) to (B4), Reference Example 5)
Similar to Examples 1 (A1) to (A4), Examples 1 (B1) to (B4), and Reference Example 1 except that powdered TiO ₂ was not arranged on one surface of the uncrosslinked rubber member. , Comparative Examples 1 (A1) to (A4), Comparative Examples 1 (B1) to (B4), and Reference Example 5.

(Comparative Examples 2 (A1) to (A4), Comparative Examples 2 (B1) to (B4), Reference Example 6)
Examples 3 (A1) to (A4), Example 3 except that CaCO ₃ (relative permittivity: 1.58) was arranged instead of the powdered TiO ₂ arranged on one surface of the uncrosslinked rubber member. Comparative Examples 2 (A1) to (A4), Comparative Examples 2 (B1) to (B4), and Reference Example 6 were performed in the same manner as in (B1) to (B4) and Reference Example 3.
(Comparative Examples 3 (A1) to (A4), Comparative Examples 3 (B1) to (B4), Reference Example 7)
Examples 3 (A1) to (A4), except that Al ₂ O ₃ (relative permittivity: 2.14) was arranged instead of the powdered TiO ₂ arranged on one surface of the unbridged rubber member. Comparative Examples 3 (A1) to (A4), Comparative Examples 3 (B1) to (B4), and Reference Example 7 were performed in the same manner as in Examples 3 (B1) to (B4) and Reference Example 3.

Table 1 below summarizes the types and amounts of metal oxides used in Examples 1 to 4 and Comparative Examples 1 to 3.

(Evaluation of heating efficiency)
The microwave irradiation time of 1520 W in Examples 1 (A) to 4 (A) and Comparative Examples 1 (A) to 3 (A) and the temperature of the adhesive surface of the crosslinked rubber member measured after the microwave irradiation. The relationship between the above is shown in FIGS. 1 and 2. Similarly, the microwave irradiation time of 570 W in Examples 1 (B) to 4 (B) and Comparative Examples 1 (B) to 3 (B) and the adhesive surface of the crosslinked rubber member measured after the microwave irradiation. The relationship with the temperature of is shown in FIGS. 3 and 4.

As is clear from FIGS. 1 to 4, in Examples 1 to 4 in which TiO ₂ having a relative permittivity of 30 or more is arranged on the adhesive surface and microwave heating is performed, the adhesive surface heated by microwave irradiation is performed. It can be seen that the temperature of the above is higher than that of Comparative Example 1 in which the metal oxide is not arranged on the adhesive surface.
Further, Example 3 in which TiO ₂ having a relative permittivity of 30 or more was arranged on the adhesive surface in an amount of 0.8 mg / cm ² , and CaCO ₃ and Al ₂ O ₃ having a relative permittivity of less than 30 on the adhesive surface. When comparing with Comparative Examples 2 and 3 containing the same amount of each, the temperature of the adhesive surface in Example 3 is higher than that of Comparative Examples 2 and 3 by 20 ° C. or more at any time point.
Therefore, it can be seen that the microwave heating efficiency on the adhesive surface of the crosslinked rubber member is surely enhanced by arranging TiO ₂ having a relative permittivity of 30 or more on the adhesive surface.

(Evaluation of peel strength)
In order to evaluate the adhesive strength between the crosslinked rubber member and the TPU member bonded in Examples 1 to 4, Comparative Examples 1 to 3 and Reference Examples 1 to 7, based on the T-shaped peeling test method based on JIS-K6854, A peeling test was carried out at a speed of 50 mm / min.
The peel strength measured in this way is shown in FIGS. 5 to 8.

As is clear from FIGS. 5 to 8, in Examples 1 to 4 in which TIO ₂ having a relative permittivity of 30 or more is arranged on the adhesive surface and microwave heating is performed, the crosslinked rubber member and the TPU member are peeled off. It can be seen that the strength is higher than that of Comparative Example 1 in which the metal oxide is not arranged on the adhesive surface.
Further, Example 3 in which TiO ₂ having a relative permittivity of 30 or more was arranged on the adhesive surface in an amount of 0.8 mg / cm ² , and CaCO ₃ and Al ₂ O ₃ having a relative permittivity of less than 30 on the adhesive surface. When comparing with Comparative Examples 2 and 3 containing the same amount of each, the peel strength in Example 3 is significantly higher than that of Comparative Examples 2 and 3.
Therefore, it can be seen that the adhesive strength between the crosslinked rubber member and the TPU member is surely increased by arranging TiO ₂ having a relative permittivity of 30 or more on the adhesive surface.

As shown in FIGS. 5 and 7, in Example 4 in which the amount of TiO ₂ arranged on the adhesive surface was relatively large at 2.0 mg / cm ² , when the microwave irradiation time was lengthened. The improvement of the peel strength is modest, and the peel strength is lower than that of Example 3 in which the amount of TiO ₂ is 0.8 mg / cm ² .
This means that if the amount of TiO ₂ arranged on the adhesive surface is increased too much, the portion where the crosslinked rubber member and the TPU member are bonded with the metal oxide such as TiO ₂ sandwiched between them increases. It is considered that the portion is caused by the lower adhesive strength than the portion bonded without sandwiching the metal oxide.

Claims

Steps where uncrosslinked rubber members are prepared,
A step in which a metal oxide having a relative permittivity of 30 or more is arranged on one surface of the uncrosslinked rubber member.
A step of producing a first member having the metal oxide fixed on one surface by cross-linking the uncrosslinked rubber member to which the metal oxide is arranged under pressure.
The step of irradiating the first member with microwaves and
A step in which a second member different from the first member is arranged on the one surface of the first member and the first member and the second member are adhered to each other.
A method for manufacturing a member for shoes.
After the step of being irradiated with the microwave and before the step of arranging the second member,
The method for manufacturing a shoe member according to claim 1, further comprising a step of applying a treatment agent on the one surface of the first member and then heating the first member.
The method for manufacturing a shoe member according to claim 1 or 2, wherein the metal oxide is TiO 2 .
13. Of claims 1 to 3, in the step of arranging the metal oxide, the metal oxide is arranged in an amount of 0.3 to 1.0 mg / cm 2 on the one surface of the uncrosslinked rubber member. The method for manufacturing a shoe member according to any one of the following items.
The method for manufacturing a shoe member according to any one of claims 1 to 4, wherein the metal oxide is in the form of powder.
The method for manufacturing a shoe member according to any one of claims 1 to 5, wherein the first member is a shoe outsole member and the second member is a shoe midsole member.
A shoe member to which a first member made of crosslinked rubber and a second member different from the first member are adhered.
A shoe member containing a metal oxide having a relative permittivity of 30 or more at the adhesive interface between the first member and the second member.
The shoe member according to claim 7, wherein the metal oxide is TiO 2 .
The shoe member according to claim 7 or 8, wherein the adhesive interface contains the metal oxide in an amount of 3 to 10 mg / cm 2 .
The shoe member according to any one of claims 7 to 9, wherein the metal oxide is in the form of powder.
The shoe member according to any one of claims 7 to 10, wherein the first member is a shoe outsole member and the second member is a shoe midsole member.