WO2013179455A1 - 発泡成形品、発泡ソール、及びシューズ - Google Patents
発泡成形品、発泡ソール、及びシューズ Download PDFInfo
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- WO2013179455A1 WO2013179455A1 PCT/JP2012/064153 JP2012064153W WO2013179455A1 WO 2013179455 A1 WO2013179455 A1 WO 2013179455A1 JP 2012064153 W JP2012064153 W JP 2012064153W WO 2013179455 A1 WO2013179455 A1 WO 2013179455A1
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- foam
- sole
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- hardness
- shoe
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
- A43B13/18—Resilient soles
- A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/26—Elastomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Definitions
- the present invention relates to a foam molded article, a sole and the shoe using the foam molded article.
- Various shoes such as sports shoes have a sole.
- the sole can be broadly classified into a non-foamed sole made of a non-foamed molded product formed in a predetermined shape and a foamed sole made of a foamed molded product formed in a predetermined shape.
- the shoe provided with the foamed sole is lighter and more comfortable to use than the shoe provided with the non-foamed sole.
- Patent Document 1 discloses a copolymer composed only of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, has a vinyl group content of 0.06 to 1, and MFR10 / MFR2.16 is 8.5.
- An ethylene copolymer having the following density and a density of 0.850 to 0.910 g / cm 3 is disclosed.
- Patent Document 1 describes that a foamed sole obtained by foaming this ethylene copolymer has a low specific gravity and a low compression set.
- the foamed sole is generally a member provided in a shoe in order to mitigate the impact on the user during walking. That is, it can be said that the foamed sole is a member that affects the feeling of use (the comfort of the shoes felt by the user).
- the softness of the foamed sole is an important factor.
- the conventional foamed sole foam molded product
- the softness can also change greatly. That is, the hardness of the conventional foamed sole varies greatly according to various loads.
- a first object of the present invention is to provide a foamed molded article having moderate softness and small hardness change under compression deformation, and a foamed sole and shoes using the same.
- the second object of the present invention is to provide a foam molded article that is relatively lightweight and suitable as a member for shoes, and a foamed sole and shoes using the same.
- the inventors of the present invention have thought that a foam molded article having a small compression set can maintain an elastic force and have a small change in hardness over a long period of time. Although this idea itself is not wrong, the present inventors have noticed that, while considering various foamed soles, the feeling of softness is different for each shoe user. That is, even a foamed sole made of a foamed molded product having a small compression set may feel soft for some users and hard for other users.
- one type of shoe having a foamed sole is usually mass-produced industrially and distributed on the market.
- Various people use the one kind of shoes.
- general adult males are heavier than children.
- the present inventors for example, when a person with heavy weight wears shoes and exercises, the user tends to feel that the sole is soft.
- a person with a light weight wears and exercises a shoe having the same foamed sole as the shoe worn by the heavy person the user tends to feel that the sole is hard.
- the present inventors have intensively studied that the elastic modulus of the foamed sole is not uniform when it is compressed and deformed (for example, when it is actually used by general adult men and children). It is thought to be caused.
- FIG. 4 is a graph showing a stress-strain curve of a conventional foamed sole (manufactured by ASICS, Inc., a midsole used in a shoe of the product name “Sorty @ Japan Light”).
- the conventional foamed sole has a large elastic modulus when the strain is small, such as 0% to 5%, while it has elasticity when the strain is large, such as 40% to 45%. The coefficient is small. From this, the conventional foamed sole becomes hard when the strain is small (elastic coefficient is large), and soft when the strain is large (elastic coefficient is small).
- the foamed molded article of the present invention has a foam obtained by foaming a forming material containing a resin component, and the Asker C hardness of the foam is 10 or more.
- the elastic modulus of the foam at 0% strain (The ratio (E40 / E0) of the elastic modulus (E40) at a strain of 40% to E0) is 0.5 or more.
- E0 is the elastic modulus of the foam at a strain of 0%
- E40 is the elastic modulus of the foam at a strain of 40%.
- the foamed molded product has a foam having an Asker C hardness of 10 or more and a ratio (E40 / E0) of 0.5 or more.
- Such foam-molded products have moderate softness, and their hardness change is small under various compression deformations. According to a shoe provided with such a foam-molded product as a foamed sole, it is difficult for a user who wears the shoe to feel softness.
- the foam has an Asker C hardness of 60 or less.
- the storage modulus of the forming material at a frequency of 10 Hz and 23 ° C. is 15 MPa or less.
- the foam has a specific gravity of 0.7 or less.
- a foamed sole is provided.
- the foamed sole has any one of the above foam molded articles.
- a shoe is provided. This shoe has the foamed sole.
- the foamed molded product of the present invention has moderate softness, and further has a small change in hardness under compression deformation.
- a foam-molded article is used as, for example, a foamed sole, it is possible to give a good feeling to various users.
- FIG. 2 is an enlarged cross-sectional view taken along the line II-II in FIG.
- the foamed molded article of the present invention has a foam containing a forming material containing a resin component, the Asker C hardness of the foam is 10 or more, and the elastic modulus (E0) of the foam at a strain of 0%.
- the ratio E (40 / E0) of the elastic modulus (E40) at a strain of 40% with respect to is 0.5 or more.
- the foam molded article, foam sole and shoes of the present invention will be described in detail.
- the notation “XXX to YYY” means “from XXX to YYY”.
- the elastic modulus at a strain of 0% is simply “E0”
- the elastic modulus at a strain of 40% simply “E40”
- the ratio of the elastic modulus at a strain of 40% to the elastic modulus at a strain of 0% are simply abbreviated as “E40 / E0”.
- the foamed molded product of the present invention can be used for any application.
- Applications of the foamed molded article of the present invention include, for example, components of shoes such as soles; components of sports equipment such as grips, supporters, protectors, etc. of striking devices such as tennis rackets.
- the foamed molded article of the present invention is used as a constituent member of a shoe.
- the constituent members of the shoes include soles such as outsole, midsole and insole; shoe bodies such as uppers; reinforcing parts such as shanks.
- the foamed molded product of the present invention may be a part of a shoe component.
- the foamed molded product is preferably used for a shoe portion to which a large load is applied.
- the foam-molded product is preferably used for a forefoot portion of the sole (eg, directly below the main ball) or a heel portion of the sole.
- the said foam molded product can also be used in combination with another material.
- the foam molded product is suitably used as a laminated structure with other materials (one or more foam molded products are included in the structure).
- the foamed molded article of the present invention is used as a foamed sole.
- the foamed sole of the present invention is used, for example, as an outer sole of a shoe and is provided on the lower surface of the shoe body.
- the foamed sole of the present invention is used as a midsole of shoes, and is disposed, for example, between a shoe body and an outer sole.
- the foamed sole of the present invention is provided on the entire lower surface of the shoe body.
- the foamed sole may be provided on a part of the lower surface of the shoe body.
- the foamed sole of the present invention is not limited to the case where it is used as an outer sole or a midsole as described above, and can be used as a reinforcing portion such as a shoe shank.
- the shank is a bottom member disposed on the arch.
- the foamed sole is formed in an arbitrary shape.
- the foamed sole is formed in a substantially plate shape, a substantially convex shape (for example, a truncated cone shape, etc.), a plate shape having a concavo-convex shape, or the like.
- the foamed sole of the present invention can be obtained by forming the foamed molded product into a predetermined shape according to the use such as the above-described midsole, outer sole, or shank.
- the foamed sole is fixedly attached to the shoe body using attachment means such as an adhesive.
- the adhesive is not particularly limited, and includes conventionally known solvent-type adhesives, emulsion-type adhesives, laser adhesives, heat-sensitive adhesives, and the like.
- the solvent-type adhesive is an adhesive in which a binder resin is dissolved or dispersed in an organic solvent
- the emulsion-type adhesive is an adhesive in which a binder resin is dispersed in water.
- the laser adhesive is an adhesive that exhibits adhesiveness when irradiated with laser light.
- the heat-sensitive adhesive is an adhesive that exhibits adhesiveness when heated.
- the foamed sole is not limited to a case where the foamed sole is attached to the shoe body using an attaching means.
- a part of the foamed sole may be laser-melted to exert an adhesive force, and the foamed sole may be attached to the shoe body by the adhesive force of the foamed sole itself.
- the foamed sole is not limited to being fixedly attached.
- the foamed sole may be detachably attached to the shoe body by forming the foamed sole into a predetermined shape and fitting it into the shoe body.
- the shoe 1a includes a shoe body 2a, a midsole 3a provided on the lower surface of the shoe body 2a, and an outer sole 5a disposed on the lower surface of the midsole 3a.
- the midsole 3a is formed in substantially the same shape as the lower surface shape of the shoe body 2a
- the outer sole 5a is formed in substantially the same shape as the lower surface shape of the midsole 3a. Desired irregularities are formed on the lower surface of the outer sole 5a as shown in FIG. But the lower surface of the outer sole 5a may be formed flat (not shown).
- the upper surface of the midsole 3a is bonded to the lower surface of the shoe body 2a using an adhesive or the like, and the upper surface of the outer sole 5a is bonded to the lower surface of the midsole 3a using an adhesive or the like (the adhesive is Not shown).
- the lower surface of the outsole 5a is in contact with the ground.
- the foamed sole of the present invention is used as the outer sole 5a of the shoe 1a.
- the foamed sole of the present invention is used as the midsole 3a of the shoe 1a.
- the foamed sole of the present invention is used as each of the midsole 3a and the outer sole 5a of the shoe 1a.
- FIG. 3 shows a second embodiment of the shoe of the present invention.
- the shoe 1b is disposed at the rear of the lower surface of the shoe body 2b, the midsole 3b provided on the lower surface of the shoe body 2b, the first outer sole 51b disposed in front of the lower surface of the midsole 3b, and the midsole 3b.
- a second outer sole 52b is formed in substantially the same shape as the bottom surface of the shoe body 2b, and the first outer sole 51b and the second outer sole 52b are each formed in a shape smaller than the bottom surface of the midsole 3b.
- the upper surface of the midsole 3b is bonded to the lower surface of the shoe body 2b using an adhesive or the like, and the upper surfaces of the first and second outer soles 51b and 52b are bonded to the lower surface of the midsole 3b using an adhesive or the like. (Adhesive is not shown).
- the lower surfaces of the first and second outsole 51b, 52b can be in contact with the ground, and a part of the lower surface of the midsole 3b can be in contact with the ground.
- the foamed sole of the present invention is used as the first outer sole 51b and / or the second outer sole 52b of the shoe 1b.
- the foamed sole of the present invention is used as the midsole 3b of the shoe 1b.
- the foamed sole of the present invention is used as each of the midsole 3b and the first and second outer soles 51b and 52b of the shoe 1b.
- each thickness of the midsole 3a and 3b is not particularly limited. In order to impart appropriate cushioning properties to the shoe, each thickness of the midsole 3a and 3b is, for example, 2 mm or more, and preferably 2 mm to 10 mm. The thicknesses of the outsole 5a, the first outer sole 51b, and the second outer sole 52b are not particularly limited. In order to impart appropriate cushioning properties to the shoe, each thickness of the outsole 5a, the first outer sole 51b, and the second outer sole 52b is, for example, 2 mm or more, and preferably 2 mm to 20 mm. As shown in the figure, the shoe of the present invention is not limited to a structure in which the shoe body protects almost the entire instep, but a structure in which the shoe body protects a part of the instep (for example, sandals) )
- the use of the shoe of the present invention is not particularly limited.
- the shoes of the present invention are used for, for example, various ball shoes such as soccer shoes and rugby shoes; running shoes such as jogging shoes and marathon shoes; athletic shoes; general athletic shoes; walking shoes; be able to.
- a foamed sole having a relatively small specific gravity that is, a lightweight foamed sole
- the shoe of the present invention having such a foamed sole is suitable as a ball game shoe, a running shoe, an athletics shoe or a walking shoe.
- the foam-molded article of the present invention is obtained by forming a foam obtained by foaming a forming material containing a resin component into a predetermined shape.
- the foam has an Asker C hardness of 10 or more, and a ratio (E40 / E0) of an elastic modulus (E40) at a strain of 40% to an elastic modulus (E0) at a strain of 0% is 0.5 or more.
- the foam has an Asker C hardness of 60 or less.
- the foam has a specific gravity of 0.7 or less.
- the storage elastic modulus at a frequency of 10 Hz and 23 ° C. of the forming material containing the resin component is preferably 15 MPa or less.
- the elastic coefficients (E0) and (E40) can be calculated from the stress-strain curve of the foam.
- the stress-strain curve of a foam is obtained by compressing a sample piece obtained by forming a foam to be measured into a cylindrical shape having a diameter of 10 mm and a height of 10 mm at a strain rate of 0.01 mm / sec. Can do.
- the Asker C hardness can be measured at 23 ° C. in accordance with JIS K 7312.
- the specific gravity can be measured at 23 ° C. in accordance with JIS K 7311.
- the storage elastic modulus at the frequency of 10 Hz and 23 ° C. can be measured according to JIS K 7244-4. See the examples below for specific measurement methods.
- the storage elastic modulus of the forming material at a frequency of 10 Hz and 23 ° C. is preferably 13 MPa or less, and more preferably 10 MPa or less.
- the lower limit value of the storage elastic modulus of the forming material is theoretically zero. However, in reality, the storage elastic modulus exceeds zero.
- Forming materials that are actually available on the market have a storage modulus of 0.01 MPa or more, for example.
- the foam of the present invention has an elastic modulus ratio (E40 / E0) of 0.5 or more, preferably an elastic modulus ratio (E40 / E0) of 0.5 to 3.5, and more Preferably, the ratio is 0.5 to 3.0, and particularly preferably, the ratio is 0.5 to 2.7.
- a strain of 0% corresponds to the initial strain amount of compressive deformation.
- the strain of 40% corresponds to the amount of compressive deformation assumed during actual use.
- the elastic modulus ratio (E40 / E0) is indicative of the change between the initial elastic modulus and the actual elastic modulus.
- the foam has an Asker C hardness of 10 or more, preferably 10 to 60, more preferably 15 to 60, particularly when no load is applied. Has an Asker C hardness of 20-50. Since the above-mentioned foam has an Asker C hardness of 10 or more, it has an appropriate softness (not too soft). In particular, a foam having an Asker C hardness of 10 to 60 has a suitable softness as a foamed sole of shoes. A foam having an Asker C hardness of 10 or more and an elastic modulus ratio (E40 / E0) of 0.5 or more has moderate softness, and the change in softness during use is small. By using such a foam as a foamed sole, it is possible to provide a shoe that can give a good feeling to the user.
- the present inventors have developed an elastic coefficient (E0) corresponding to the amount of strain at no load and an elastic coefficient (E40) corresponding to the amount of strain when a large load assumed during use is applied. ).
- the change in hardness of the foam does not become small only by the ratio of the elastic modulus. This is because innumerable bubbles (cells) are present inside the foam, and when a load is applied to the foam, the cells are crushed. The foam in which the cells are crushed loses its elasticity and increases its hardness. From these matters, the present inventors set the E40 / E0 of the foam to 0.5 or more, and the Asker C hardness of the foam at the time of no load to 10 or more. I found that it would not grow. Furthermore, a foam having an Asker C hardness of 60 or less at no load can constitute a foam having moderate softness and small change in hardness. A foam-molded article having such a foam can be suitably used as a shoe sole.
- the foamed molded product (foamed sole) of the present invention can be obtained by foam-molding a forming material containing the resin component.
- the material for forming the foam molded product of the present invention is not particularly limited as long as it contains the resin component and has foamability.
- the storage elastic modulus of the forming material is 15 MPa or less. When the storage elastic modulus of the forming material is 15 MPa or less, it becomes easy to control the ratio (E40 / E0) of the elastic modulus of the foam to 0.5 or more.
- the said forming material contains a resin component and arbitrary appropriate other components as needed.
- the resin component include thermoplastic elastomers, thermoplastic resins, and rubbers.
- thermoplastic elastomer examples include styrene elastomers such as styrene ethylene butylene styrene block copolymer (SEBS); ethylene-vinyl acetate copolymer elastomers; olefin elastomers; styrene butadiene styrene copolymers (SBS). , Urethane elastomers; ester elastomers; fluorine elastomers; silicone elastomers; polyamide elastomers; A thermoplastic elastomer in which an arbitrary part is hydrogenated may be used. These can be used alone or in combination of two or more.
- SEBS styrene ethylene butylene styrene block copolymer
- SBS ethylene-vinyl acetate copolymer elastomers
- olefin elastomers styrene butadiene sty
- thermoplastic resin examples include vinyl acetate resins such as ethylene-vinyl acetate copolymer (EVA); polystyrene, styrene butadiene resin, acrylonitrile styrene resin (AS resin), and acrylonitrile butadiene styrene resin (ABS resin).
- Styrenic resins such as: Olefin resins such as low density polyethylene, high density polyethylene, and polypropylene; ⁇ olefin resins such as ethylene- ⁇ olefin copolymers and ethylene-butene copolymers; polyethylene terephthalate, polybutylene terephthalate, etc.
- thermoplastic resin in which an arbitrary part is hydrogenated may be used. These thermoplastic resins can be used alone or in combination of two or more.
- the rubber examples include synthetic rubbers such as butadiene rubber (BR), isoprene rubber (IR), and chloroprene (CR); natural rubber (NR); styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), And copolymer rubbers such as butyl rubber (IIR). These rubbers can be used alone or in combination of two or more.
- synthetic rubbers such as butadiene rubber (BR), isoprene rubber (IR), and chloroprene (CR); natural rubber (NR); styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), And copolymer rubbers such as butyl rubber (IIR). These rubbers can be used alone or in combination of two or more.
- the compounding amount of the resin component is, for example, 30 parts by mass to 99 parts by mass, preferably 50 parts by mass to 99 parts by mass, when the total amount of the forming material is 100 parts by mass. If the amount of the resin component is too small, there is a possibility that a foam molded product having a strength that can withstand actual use cannot be obtained.
- a softening agent can be added to the resin component.
- the softening agent is not particularly limited, and conventionally known softening agents for resins or rubbers can be used.
- the softening agent include mineral oils such as naphthenic process oil and paraffinic process oil; castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, pine Vegetable oils such as oil and olive oil; and the like. These softeners can be used alone or in combination of two or more. These mineral oils and vegetable oils preferably have an average molecular weight of about 500 to 5,000.
- the blending amount of the softener is not particularly limited, but when the total amount of the forming material is 100 parts by mass, for example, it is more than 0 and less than 70 parts by mass, preferably 0 mass Part and less than 50 parts by weight. If the amount of the softening agent is too large, the softening agent may bleed, and the amount of the resin component is relatively reduced, so that there is a possibility that a foamed molded product having a strength that can withstand actual use may not be obtained.
- a foaming agent As other components of the forming material, a foaming agent, a foaming assistant, a crosslinking agent, various additives, and the like may be added.
- a foaming agent By cross-linking the resin component with the cross-linking agent, it is possible to obtain a foamed molded article having an appropriate flexibility and excellent mechanical strength.
- the method for obtaining the foamed molded product of the present invention is not particularly limited, and a known method can be used. Among them, it is preferable to use an extrusion foaming method, a press foaming method, or an injection foaming method because a foamed molded article having high mechanical strength can be formed. When these methods are adopted, if necessary, after foaming, the molded product may be compressed by a hot press or the like so as to have a predetermined specific gravity.
- Examples of the inorganic foaming agent include sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compound, sodium borohydride, metal powder, and the like.
- Examples of the organic foaming agent include azodicarbonamide (ADCA), azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine (DNPT), N, N′— Examples thereof include dinitroso-N, N′-dimethylterephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p, p′-oxybisbenzenesulfonyl hydrazide (OBSH), p-toluenesulfonyl semicarbazide and the like.
- ADCA azodicarbonamide
- DNPT N′-
- Examples of the physical blowing agent include hydrocarbons such as pentane, butane and hexane; halogenated hydrocarbons such as methyl chloride and methylene chloride; gases such as nitrogen and air; trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, And fluorinated hydrocarbons such as chlorodifluoroethane and hydrofluorocarbon. These foaming agents may be used alone or in combination of two or more.
- an appropriate hollow filler or a thermally expandable microballoon may be included in the molding material, or the molding material is kneaded with gas. Also good.
- a foaming aid may be used together with the foaming agent.
- the foaming aid include urea and urea derivatives.
- the compounding quantity of the said foaming agent is not specifically limited, It designs suitably.
- the blending amount of the foaming agent is, for example, 0.1 to 10 parts by mass when the total amount of the forming material is 100 parts by mass.
- the crosslinking agent is not particularly limited, and conventionally known crosslinking agents can be used.
- the crosslinking agent include organic peroxides; sulfur; compounds that generate sulfur by heating such as disulfides; and metal oxides such as magnesium oxide.
- an organic peroxide is used.
- organic peroxide examples include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 2 , 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, dialkyl peroxides such as t-butylcumyl peroxide; 1,1-di-t-butylperoxy-3,3,5 -Peroxyketals such as trimethylcyclohexane and 4,4-di-t-butylperoxyvaleric acid-n-butyl ester; diacyl peroxides such as benzoyl peroxide; Furthermore, in order to promote crosslinking, a known crosslinking accelerator may be added together with the crosslinking agent.
- the compounding quantity of a crosslinking agent is not specifically limited, It designs suitably.
- the additive examples include a heat stabilizer, a light stabilizer, an antioxidant, an ultraviolet absorber, a colorant, a plasticizer, an antistatic agent, a thickener, a filler, and stearic acid.
- the forming material containing the resin component is foam-molded. Specifically, the resin component and, if necessary, the softener, the foaming agent, the cross-linking agent, and the additive are blended in a predetermined amount, and while mixing this with heating to 100 ° C. to 150 ° C., a mixing roll, Kneading using a pressure kneader or an extruder.
- the forming material sufficiently kneaded is filled in a press mold and, for example, is pressurized for a predetermined time while being heated to 150 ° C. to 170 ° C., thereby vulcanizing the resin component and foaming the foaming agent.
- the expansion ratio is not particularly limited, but is, for example, 1.2 times to 10 times, and preferably 1.5 times to 7 times.
- a foam is obtained by foaming the forming material.
- the obtained foam has an Asker C hardness of preferably 60 or less, and more preferably 55 or less.
- the foamed molded article having such hardness is soft and excellent in the feeling of use.
- the specific gravity of the foam is preferably 0.7 or less, more preferably 0.6 or less, and further preferably 0.55 or less.
- the lower limit of the specific gravity of the foam is preferably as small as possible.
- the specific gravity of the foam theoretically exceeds 0. In general, the specific gravity of the foam is 0.1 or more, preferably 0.2 or more.
- the foam foamed as described above may be directly used as the foam molded product of the present invention, or the foam may be molded into a desired shape and used as the foam molded product of the present invention.
- the foamed sole of the present invention can be obtained by subjecting the foamed molded product of the present invention to secondary processing so as to conform to the shape of the outer sole or the like.
- the shape of the foam molded product matches the shape of the foamed sole (for example, when the shape of the mold is a shape of an outer sole or the like)
- the foamed molded product is directly used as the foam of the present invention. Can be used as a sole.
- the foamed sole is bonded to the shoe body using an adhesive or the like.
- an adhesive or the like When a solvent-type adhesive or an emulsion-type adhesive is used as the adhesive, the adhesive is dried by exposure to hot air at 60 ° C. to 80 ° C., for example.
- a laser adhesive or a heat-sensitive adhesive is used as the adhesive, the foamed sole is bonded to the shoe body in a state where the adhesive is heated and melted by a laser or a heating device.
- the foamed sole is not limited to the case where the foamed sole is adhered to a shoe body, and can be used as a removable shoe member.
- the foamed sole may be used as an insole of a shoe, and the foam seal may be fitted into the shoe body. In this way, the shoe of the present invention can be obtained.
- SBBS Styrene-butadiene-butylene-styrene copolymer elastomer (manufactured by Asahi Kasei Chemicals Corporation, trade name “Tuftec MP10”). Styrene content 30% by mass, butadiene and butylene content 70% by mass.
- Mineral oil Paraffin oil (manufactured by Idemitsu Kosan Co., Ltd., trade name “PW90”). Processing aid: stearic acid.
- Foaming agent azodicarbonamide.
- Foaming aid Zinc oxide.
- Crosslinking agent dicumyl peroxide.
- Example 1 Resin components, mineral oil, processing aids, foaming agents, foaming aids and crosslinking agents were blended in the proportions shown in Table 1. These materials are kneaded using a pressure kneader and a mixing roll, filled in a press mold, and pressed for a predetermined time while being heated to about 160 ° C., thereby having a length of 200 mm, a width of 200 mm, and a height of 10 mm. A rectangular parallelepiped foam was produced. However, each numerical value of Table 1 is a mass part display.
- Example 2 to Example 19 A foam was produced in the same manner as in Example 1 except that each material was blended at the ratio shown in Table 1.
- the specific gravity of the foam was measured at 23 ° C. using an electronic hydrometer (manufactured by Alpha Mirage Co., Ltd., product name “MD-300S”) in accordance with JIS K 7311.
- a material obtained by removing the foaming agent from the foam forming material of each example (that is, resin component, mineral oil, processing aid, foaming aid and cross-linking agent) was blended in the proportions shown in Table 1.
- Each of these materials was kneaded using a pressure kneader and a mixing roll, and press molded for 30 minutes while heating at 150 ° C. to 180 ° C. to prepare a resin sheet having a thickness of about 2 mm. This resin sheet was cut into the following sample shape.
- the storage elastic modulus of this resin sheet was calculated by measuring dynamic viscoelasticity under the following conditions in accordance with JIS K 7244-4.
- the storage elastic modulus of the resin sheet was adopted as the storage elastic modulus of the foam forming material.
- Measuring instrument Dynamic viscoelasticity measuring device Rheogel-E4000 manufactured by UBM Co., Ltd. Sample shape: strip shape of length 33 ⁇ 3 mm, width 5 ⁇ 0.3 mm, thickness 2 ⁇ 0.3 mm. Measurement mode: Tension mode of sinusoidal distortion. Distance between chucks: 20 ⁇ 0.2 mm. Temperature: 23 ° C. Frequency: 10Hz. Load: Automatic static load. Dynamic strain: 3-5 ⁇ m.
- the elastic modulus (E0) at 0% strain and the elastic modulus (E40) at 40% strain are the slope of the tangent at the point corresponding to 0% strain after obtaining the stress-strain curve of the foam. And the slope of the tangent at the point corresponding to 40% of the distortion of the curve.
- E40 / E0 was calculated from E40 / E0 and rounded off to the fourth decimal place.
- the stress-strain curve of the foam was obtained by cutting the foam into a columnar shape having a diameter of 10 mm and a height of 10 mm, and using an autograph precision universal testing machine (manufactured by Shimadzu Corporation, product name “AG- 50 kNIS MS type ”) and compressed at 23 ° C. at a strain rate of 0.01 mm / sec.
- Asker C hardness of the foam was measured at 23 ° C. in accordance with JIS K 7312 using a C-type hardness meter (Polymer Keiki Co., Ltd., product name “Asker rubber hardness meter C type”).
- the measurement sample was a rectangular parallelepiped foam (without cutting the foam).
- This measurement of Asker C hardness is a measurement of the hardness of the foamed product under no load, and the measured value is H0 in Table 2.
- the hardness was measured by applying a load of 0.1 MPa to the foams (assumed to be the soles of the shoes) produced in the above Examples and Comparative Examples. Specifically, the foam was cut into the same area (height 10 mm) as the pressing surface of the C-type hardness meter to obtain a sample piece. A pressure surface of a C-type hardness meter (Polymer Keiki Co., Ltd., product name “Asker rubber hardness meter C-type”) is placed on the sample piece, and 0.1 MPa (about 1 kgf / cm 2 ) is placed on the entire sample piece. This was compressed by applying a load of. The Asker C hardness of the sample piece at the time of compression was measured at 23 ° C. using the C-type hardness meter. The results are shown in Table 2. In addition, H1 of Table 2 shows Asker C hardness at the time of the said compression.
- the hardness of the foam assumed when the child wears shoes corresponds to the Asker C hardness of the foam in an unloaded state.
- the Asker C hardness of the foam in this unloaded state is H0 in Table 2.
- the foams of Examples 1, 5 and 13 did not change greatly in hardness due to the difference in load.
- the foams of these examples have an Asker C hardness of more than 60 at both no load and load.
- the Asker C hardness under no load is preferably in the range of 10 to 60 as in the foams of Examples 2 to 4, 6 to 12 and 14 to 19.
- the foams of Comparative Examples 1 to 9 had H1-H0 outside the range of ⁇ 20, and these foams had a large change in hardness due to the difference in load. Since the foams of Comparative Examples 1 to 3, 8, and 9 had E40 / E0 of less than 0.5, a large change in hardness occurred.
- the foams of Comparative Examples 4 to 7 had E40 / E0 of 0.5 or more, but H0 was less than 10, so a large change in hardness occurred. This is presumed to be because the foam with H0 (Asker C hardness under no load) of less than 10 becomes hard due to the collapse of the cells in the foam when a load is applied. In addition, although data are not acquired about the foam whose E40 / E0 is less than 0.5 and H0 is less than 10, such a foam has the same result as the foam of Comparative Examples 1 to 9. It is estimated that
- the present inventors measured E0 and E40 of each Example and Comparative Example, and at the same time, the elastic modulus (E20) at 20% strain, the elastic modulus (E30) at 30% strain, and 50% strain. Measurements of elastic modulus (E50) were also obtained. And when E20 / E0 is 0.2 or more, E30 / E0 is 0.3 or more, and E50 / E0 is 0.8 or more, hardness (H1) when it is assumed that a person with a weight of 60 kg rides, The difference (H1 ⁇ H0) between the hardness (H0) and the hardness (H0) when it was assumed that a person with a weight of 20 kg got on was within ⁇ 20.
- the foamed molded product of the present invention can be used, for example, as a constituent member of shoes or a constituent member of exercise equipment.
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Abstract
Description
前記ソールは、所定形状に形成した非発泡成形品からなる非発泡ソールと、所定形状に形成した発泡成形品からなる発泡ソールと、に大別できる。
前記発泡ソールを備えるシューズは、非発泡ソールを備えるシューズに比して、軽量であり、使用感に優れている。
しかしながら、従来の発泡ソール(発泡成形品)においては、様々な荷重の負荷により圧縮変形量が変化すると、柔らかさも大きく変化し得る。つまり、従来の発泡ソールは、様々な荷重に応じて、その硬度が大きく変化する。
このような発泡ソールを有するシューズを、例えば一般成人男性と児童とがそれぞれ着用すると、その使用者毎に、柔らかさの感じ方が異なってしまうという問題点がある。
本発明の第2の課題は、比較的軽量で、シューズ用の部材として好適な発泡成形品、並びにそれを用いた発泡ソール及びシューズを提供することである。
つまり、圧縮永久ひずみが小さい発泡成形品からなる発泡ソールであっても、ある使用者は柔らかく感じ、他の使用者は硬く感じることがある。
本発明者らの研究によれば、例えば、体重の重い人がシューズを着用して運動したとき、その使用者はソールが柔らかいと感じる傾向にある。他方、前記体重の重い人が着用するシューズと同じ発泡ソールを有するシューズを、体重の軽い人が着用して運動したときには、その使用者はソールが硬いと感じる傾向にある。
この原因に関して、本発明者らは鋭意研究したところ、それは、圧縮変形したときの(例えば、一般成人男性と児童が実際に使用したときなどの)、発泡ソールの弾性係数が一様でないことに起因すると考えられる。
図4から明らかなように、従来の発泡ソールは、ひずみ0%~5%のようなひずみが小さいときには、弾性係数が大きく、一方、ひずみ40%~45%のようなひずみが大きいときには、弾性係数が小さい。このことから、従来の発泡ソールは、ひずみが小さいときには硬くなり(弾性係数が大きくなり)、ひずみが大きいときにはそれに比して柔らかくなる(弾性係数が小さくなる)。体重が軽い人が使用したときなどには、発泡ソールには、相対的に小さな荷重が加わる(ひずみが小さい)。体重が重い人が使用したときなどには、発泡ソールには、相対的に大きな荷重が加わる(ひずみが大きい)。
発泡ソールの弾性係数がひずみ量に応じて大きく変化することと、使用者の状況に応じたシューズの使用感とは、相関関係にある。このような点は、本発明者らが初めて見出した事項である。
本発明者らは、上記のような知見を得て、本発明を完成した。
ここで、前記E0は、ひずみ0%における発泡体の弾性係数であり、前記E40は、ひずみ40%における発泡体の弾性係数である。前記比は、E40/E0=E40÷E0、で求められる。
このような発泡成形品を発泡ソールとして備えるシューズによれば、それを着用する使用者の、柔らかさの感じ方のバラツキが生じ難くなる。
本発明のさらに好ましい発泡成形品は、前記形成材料の、周波数10Hz、23℃における貯蔵弾性率が15MPa以下である。
本発明のさらに好ましい発泡成形品は、前記発泡体の比重が、0.7以下である。
この発泡ソールは、上記いずれかの発泡成形品を有する。
本発明の別の局面によれば、シューズが提供される。
このシューズは、上記発泡ソールを有する。
かかる発泡成形品を、例えば、発泡ソールとして使用した場合、様々な使用者に対して良好な使用感を与えることができる。
本発明によれば、使用感に優れたシューズを提供できる。
なお、本明細書において、「XXX~YYY」という表記は、「XXX以上YYY以下」を意味する。
また、本明細書において、ひずみ0%における弾性係数を、単に「E0」と、ひずみ40%における弾性係数を、単に「E40」と、ひずみ0%における弾性係数に対するひずみ40%における弾性係数の比を、単に「E40/E0」と、それぞれ略記する場合ある。
本発明の発泡成形品は、任意の用途に使用できる。
本発明の発泡成形品の用途としては、例えば、ソールなどのシューズの構成部材;テニスラケットなどの打撃具のグリップ、サポーター、プロテクターなどの運動用具の構成部材;などが挙げられる。
好ましくは、本発明の発泡成形品は、シューズの構成部材として使用される。シューズの構成部材としては、例えば、アウトソール、ミッドソール及びインソールなどのソール;アッパーなどのシューズ本体;シャンクなどの補強部などが挙げられる。
また、本発明の発泡成形品は、シューズの構成部材の一部分であってもよい。この場合、履き心地をコントロールできることから、前記発泡成形品を、大きな荷重が加わるシューズ部分に使用することが好ましい。例えば、前記発泡成形品は、ソールの前足部(母趾球直下部など)やソールの踵部などに好適に使用される。また、前記発泡成形品は、他の材料と組み合わせて使用することもできる。例えば、前記発泡成形品は、他の材料との積層構造(その構造中に発泡成形品が1層以上含まれる)として好適に使用される。
本発明の発泡ソールは、例えば、シューズのアウターソールとして使用され、シューズ本体の下面に設けられる。また、本発明の発泡ソールは、シューズのミッドソールとして使用され、例えば、シューズ本体とアウターソールの間に配置される。
本発明の発泡ソールは、シューズ本体の下面の全体的に設けられる。また、前記発泡ソールを、シューズ本体の下面の一部分に設けてもよい。
また、本発明の発泡ソールは、上述したようなアウターソールやミッドソールとして使用される場合に限られず、例えば、シューズのシャンクのような補強部として用いることも可能である。前記シャンクは、土踏まず部分に配置される底部材である。
接着剤としては、特に限定されず、従来公知の溶剤型接着剤、エマルジョン型接着剤、レーザー接着剤、感熱接着剤などが挙げられる。前記溶剤型接着剤は、有機溶剤中にバインダー樹脂を溶解又は分散させた接着剤であり、前記エマルジョン型接着剤は、水中にバインダー樹脂を分散させた接着剤である。レーザー接着剤は、レーザー光の照射によって接着性を発現する接着剤である。感熱接着剤は、加熱することによって接着性を発現する接着剤である。
また、前記発泡ソールは、固定的に取り付けられる場合に限られない。例えば、発泡ソールを所定形状に形成し、これをシューズ本体に嵌め込むことによって、発泡ソールがシューズ本体に着脱可能に取り付けられていてもよい。
図1及び図2は、本発明のシューズの第1の実施形態を示す。
このシューズ1aは、シューズ本体2aと、シューズ本体2aの下面に設けられたミッドソール3aと、ミッドソール3aの下面に配置されたアウターソール5aと、を備えている。ミッドソール3aは、シューズ本体2aの下面形状とほぼ同じ形状に形成され、アウターソール5aは、ミッドソール3aの下面形状とほぼ同じ形状に形成されている。アウターソール5aの下面には、図2に示すように、所望の凹凸が形成されている。もっとも、アウターソール5aの下面が平坦状に形成されていてもよい(図示せず)。
このシューズ1bは、シューズ本体2bと、シューズ本体2bの下面に設けられたミッドソール3bと、ミッドソール3bの下面前方に配置された第1アウターソール51bと、ミッドソール3bの下面後方に配置された第2アウターソール52bと、を備えている。ミッドソール3bは、シューズ本体2bの下面形状とほぼ同じ形状に形成され、第1アウターソール51b及び第2アウターソール52bは、それぞれミッドソール3bの下面形状よりも小さな形状に形成されている。
上記アウトソール5a、第1アウターソール51b及び第2アウターソール52bの各厚みは、特に限定されない。適切なクッション性をシューズに付与するために、アウトソール5a、第1アウターソール51b及び第2アウターソール52bの各厚みは、例えば、2mm以上であり、好ましくは2mm~20mmである。
なお、本発明のシューズは、図示したように、シューズ本体が足の甲のほぼ全体を保護する構造に限られず、シューズ本体が足の甲の一部を保護するような構造(例えば、サンダルなど)でもよい。
本発明によれば、比較的比重の小さい発泡ソール(つまり、軽量な発泡ソール)を提供できる。かかる発泡ソールを備える本発明のシューズは、球技用シューズ、ランニング用シューズ、陸上競技用シューズ又はウォーキング用シューズとして好適である。
本発明の発泡成形品は、樹脂成分を含む形成材料を発泡することによって得られた発泡体を、所定形状に形成することによって得られる。
前記発泡体は、アスカーC硬度が10以上で、且つ、ひずみ0%における弾性係数(E0)に対するひずみ40%における弾性係数(E40)の比(E40/E0)が、0.5以上である。
好ましくは、前記発泡体は、アスカーC硬度が60以下である。さらに、前記発泡体は、比重が0.7以下である。
また、前記樹脂成分を含む形成材料の、周波数10Hz、23℃における貯蔵弾性率は、好ましくは15MPa以下である。
前記アスカーC硬度は、JIS K 7312に準拠して、23℃下で測定できる。
前記比重は、JIS K 7311に準拠して、23℃下で測定できる。
前記周波数10Hz、23℃における貯蔵弾性率は、JIS K 7244-4に準拠して測定できる。
具体的な測定方法は、下記実施例を参照されたい。
前記形成材料の貯蔵弾性率の下限値は、理論上、零である。もっとも、現実的には、その貯蔵弾性率は0を超えている。実際に市場で入手できる形成材料は、その貯蔵弾性率が、例えば0.01MPa以上のものである。
ひずみ0%は、圧縮変形の初期ひずみ量に相当する。ひずみ40%は、実際の使用時に想定される、圧縮変形のひずみ量に相当する。弾性係数の比(E40/E0)は、初期時の弾性係数と、実際の使用時の弾性係数との変化を指標している。
上記発泡体は、アスカーC硬度が10以上なので、適度な柔らかさを有する(柔らか過ぎることがない)。特に、アスカーC硬度が10~60の発泡体は、シューズの発泡ソールとして適切な柔らかさを有する。
アスカーC硬度が10以上で且つ前記弾性係数の比(E40/E0)が0.5以上の発泡体は、適度な柔らかさを有し、その使用時における柔らかさの変化が小さい。かかる発泡体を発泡ソールとして用いることにより、使用者に良好な使用感を与えることができるシューズを提供できる。
理論上、あらゆるひずみ量に対応した各弾性係数が一定である発泡体は、硬度変化(柔らかさの変化)がないと言える。
しかしながら、一般的な発泡体は、図4に示すような、応力-ひずみ曲線を示し、ひずみ量に応じて弾性係数が様々に変化する。
理論的には可能としても、現実的に、あらゆるひずみ量における各弾性係数が一定である発泡体を製造することはできない。
このような事項から、本発明者らは、発泡体のE40/E0を0.5以上とし、無荷重時の発泡体のアスカーC硬度を10以上とすることにより、使用時において、硬度変化が大きくならないことを見出した。
さらに、無荷重時のアスカーC硬度が60以下の発泡体は、適度な柔らかさを有し且つ硬度変化の小さい発泡体を構成できる。かかる発泡体を有する発泡成形品は、シューズのソールとして好適に利用できる。
本発明の発泡成形品(発泡ソール)は、前記樹脂成分を含む形成材料を発泡成形することよって得られる。
本発明の発泡成形品の形成材料は、前記樹脂成分を含み且つ発泡性を有するものであれば特に限定されない。好ましくは、前記形成材料の貯蔵弾性率は15MPa以下である。前記形成材料の貯蔵弾性率が15MPa以下である場合には、発泡体の弾性係数の比(E40/E0)を0.5以上に制御しやすくなる。
前記樹脂成分としては、例えば、熱可塑性エラストマー、熱可塑性樹脂、ゴムなどが挙げられる。
前記軟化剤は、特に限定されず、従来公知の樹脂用又はゴム用の軟化剤を用いることができる。軟化剤としては、例えば、ナフテン系のプロセス油、パラフィン系のプロセス油などの鉱物油;ひまし油、綿実油、あまみ油、なたね油、大豆油、パーム油、やし油、落花生油、木ろう、パインオイル、オリーブ油などの植物油;などが挙げられる。これらの軟化剤は、1種単独で、または2種以上を併用できる。
これらの鉱物油及び植物油は、その平均分子量が500~5,000程度であることが好ましい。
前記有機系発泡剤としては、アゾジカルボンアミド(ADCA)、アゾビスホルムアミド、アゾビスイソブチロニトリル、アゾジカルボン酸バリウム、N,N’-ジニトロソペンタメチレンテトラミン(DNPT)、N,N’-ジニトロソ-N,N’-ジメチルテレフタルアミド、ベンゼンスルホニルヒドラジド、p-トルエンスルホニルヒドラジド、p,p’-オキシビスベンゼンスルホニルヒドラジド(OBSH)、p-トルエンスルホニルセミカルバジドなどが挙げられる。
前記物理的発泡剤としては、ペンタン、ブタン、ヘキサンなどの炭化水素;塩化メチル、塩化メチレンなどのハロゲン化炭化水素;窒素、空気などのガス;トリクロロフルオロメタン、ジクロロジフルオロメタン、トリクロロトリフルオロエタン、クロロジフルオロエタン、ハイドロフルオロカーボンなどのフッ素化炭化水素;などが挙げられる。これらの発泡剤は、1種単独で又は2種以上を組み合わせて使用してもよい。
前記発泡剤の配合量は、特に限定されず、適宜設計される。前記発泡剤の配合量は、形成材料全量を100質量部とした場合、例えば、0.1質量部~10質量部である。
有機過酸化物としては、例えば、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン、ジクミルパーオキサイド、1,3-ビス(t-ブチルパーオキシイソプロピル)ベンゼン、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン-3、t-ブチルクミルパーオキサイドなどのジアルキルパーオキサイド類;1,1-ジーt-ブチルパーオキシ-3,3,5-トリメチルシクロヘキサン、4,4-ジ-tーブチルパーオキシバレリックアシッド-n-ブチルエステルなどのパーオキシケタール類;ベンゾイルパーオキサイドなどのジアシルパーオキサイド類;などが挙げられる。
さらに、架橋を促進するため、架橋剤と共に公知の架橋促進剤を添加してもよい。
架橋剤の配合量は、特に限定されず、適宜設計される。前記架橋剤の配合量は、形成材料全量を100質量部とした場合、例えば、0.1質量部~5質量部である。
前記樹脂成分を含む形成材料を、発泡成形する。
具体的には、前記樹脂成分、及び、必要に応じて、前記軟化剤、発泡剤、架橋剤、及び添加剤を所定量配合し、これを100℃~150℃に加熱しながら、ミキシングロール、加圧式ニーダー、押出機などを用いて混練する。
十分に混練した形成材料を、プレス金型内に充填し、例えば、150℃~170℃に加熱しながら所定時間加圧することにより、樹脂成分を加硫させ且つ発泡剤を発泡させる。
前記発泡倍率は、発泡倍率=形成材料の発泡前の密度÷形成材料の発泡後の密度、により求められる。
前記形成材料を発泡させることにより、発泡体が得られる。得られた発泡体のアスカーC硬度は、60以下が好ましく、さらに、55以下がより好ましい。このような硬度を有する発泡成形品は、柔らかく使用感に優れている。
軽量化の観点から、前記発泡体の比重は、好ましくは0.7以下であり、より好ましくは0.6以下であり、さらに好ましくは0.55以下である。また、発泡体の比重の下限は、出来るだけ小さいことが好ましい、発泡体の比重は、理論的には0を超える。一般的には、発泡体の比重は、0.1以上であり、好ましくは0.2以上である。
本発明の発泡成形品の形状を、アウターソールなどの形状に適合するように2次加工することにより、本発明の発泡ソールを得ることができる。
また、前記発泡成形品の形状が発泡ソールの形状に合致している場合には(例えば、前記金型の形状がアウターソールなどの形状である場合)、前記発泡成形品をそのまま本発明の発泡ソールとして使用できる。
接着剤として溶剤型接着剤又はエマルジョン型接着剤を用いた場合には、例えば、60℃~80℃の熱風に曝して、前記接着剤を乾燥する。接着剤としてレーザー接着剤又は感熱接着剤を用いた場合には、前記接着剤をレーザー又は加熱装置によって加熱溶融させた状態で発泡ソールをシューズ本体に接着する。
また、前記発泡ソールは、シューズ本体に接着して使用する場合に限られず、着脱可能なシューズ用の部材として使用することもできる。例えば、前記発泡ソールをシューズのインソールとして用い、この発泡シールをシューズ本体に嵌め入れてもよい。
このようにして、本発明のシューズを得ることができる。
SBBS:スチレン-ブタジエン-ブチレン-スチレン共重合体エラストマー(旭化成ケミカルズ(株)製、商品名「タフテック MP10」)。スチレン量30質量%、ブタジエン及びブチレン量70質量%。
EVA:エチレン-酢酸ビニル共重合体(東ソー(株)製、商品名「ウルトラセン634」)。MFR=4.3。
鉱油:パラフィンオイル(出光興産(株)製、商品名「PW90」)。
加工助剤:ステアリン酸。
発泡剤:アゾジカルボンアミド。
発泡助剤:酸化亜鉛。
架橋剤:ジクミルパーオキサイド。
表1に示す割合で、樹脂成分、鉱油、加工助剤、発泡剤、発泡助剤及び架橋剤を配合した。これらの各材料を、加圧ニーダー、ミキシングロールを用いて混練し、プレス金型内に充填し、約160℃に加熱しながら所定時間加圧することにより、縦200mm、横200mm、高さ10mmの直方体状の発泡体を作製した。
ただし、表1の各数値は、質量部表示である。
表1に示す割合で、各材料を配合したこと以外は、上記実施例1と同様にして、発泡体を作製した。
表1に示す割合で、各材料を配合したこと以外は、上記実施例1と同様にして、発泡体を作製した。
発泡体の比重は、JIS K 7311に準拠し、電子比重計(アルファーミラージュ(株)製、製品名「MD-300S」)を用いて、23℃下で測定した。
各例の発泡体の形成材料から発泡剤を除いたもの(つまり、樹脂成分、鉱油、加工助剤、発泡助剤及び架橋剤)を、表1に示す割合で配合した。これらの各材料を、加圧ニーダー、ミキシングロールを用いて混練し、150℃~180℃に加熱しながら30分間プレス成形し、約2mm厚の樹脂シートを作製した。この樹脂シートを、下記サンプル形状に裁断した。この樹脂シートの貯蔵弾性率を、JIS K 7244-4に準拠し、下記条件で動的粘弾性を測定することにより算出した。かかる樹脂シートは、発泡体の気泡壁と同等の材料物性を有すると考えられるので、その樹脂シートの貯蔵弾性率を発泡体の形成材料の貯蔵弾性率として採用した。
測定機器:(株)ユービーエム製、動的粘弾性測定装置 Rheogel-E4000。
サンプル形状:長さ33±3mm、幅5±0.3mm、厚さ2±0.3mmの短冊状。
測定モード:正弦波歪みの引張モード。
チャック間距離:20±0.2mm。
温度:23℃。
周波数:10Hz。
荷重:自動静荷重。
動歪み:3~5μm。
発泡体のひずみ0%における弾性係数(E0)及びひずみ40%における弾性係数(E40)は、発泡体の応力-ひずみ曲線を得た後、その曲線のひずみ0%に対応する点における接線の傾き及びその曲線のひずみ40%に対応する点における接線の傾きから求めた。E40/E0は、E40÷E0から算出し、小数点4桁目を四捨五入した。
前記発泡体の応力-ひずみ曲線は、発泡体を直径10mm×高さ10mmの円柱形状に裁断し、そのサンプル片を、オートグラフ精密万能試験機((株)島津製作所製、製品名「AG-50kNIS MS型」)を用いて、23℃下で、ひずみ速度0.01mm/秒にて圧縮することによって得た。
発泡体のアスカーC硬度は、JIS K 7312に準拠し、C型硬度計(高分子計器(株)、製品名「アスカーゴム硬度計C型」)を用いて、23℃下で測定した。なお、測定サンプルは、(発泡体を裁断せず)直方体状の発泡体をそのまま用いた。このアスカーC硬度の測定は、無荷重時の発泡体の硬度の測定であり、その測定値は、表2のH0である。
一般に、シューズの履き心地は、着用時に使用者が足底に感じる硬さで指標できる。
シューズの使用者として、一般成人男性(体重60kg)と児童(体重20kg)を想定し、それらの使用者の体重がシューズのソールに加わった場合を考える。前記一般成人男性が静止して立った状態のときに、前記ソールに加わる最大圧縮応力は、体重を踵部の面積で除した値から約0.1MPa(約1kgf/cm2)である。一方、前記児童は、体重が軽いことに加えて、足底(土踏まず)が未発達であり、足底の接地面積が大きい。これらの理由から、前記児童が静止して立った状態のときには、シューズのソールに加わる最大圧縮応力は、前記一般成人男性に比べて極めて小さい(成人男性の1/10程度)。
具体的には、発泡体を、C型硬度計の加圧面と同面積(高さ10mm)に裁断して、サンプル片を得た。このサンプル片の上からC型硬度計(高分子計器(株)、製品名「アスカーゴム硬度計C型」)の加圧面を載せ、前記サンプル片の全体に0.1MPa(約1kgf/cm2)の荷重を加えてこれを圧縮した。その圧縮時のサンプル片のアスカーC硬度を、前記C型硬度計を用いて、23℃下で測定した。
その結果を表2に示す。なお、表2のH1は、前記圧縮時のアスカーC硬度を示す。
表2に、H1-H0の値を明示している。
H1-H0が±20の範囲内であれば、使用感が良好と判断した。つまり、体重60kgの人が乗ったと仮定したときの硬度(H1)と、体重20kgの人が乗ったと仮定したときの硬度(H0)と、の差(H1-H0)が、±20の範囲内であれば、大きな硬度変化ではない。このような発泡体をシューズのソールに使用したときには、各使用者のそれぞれの使用感に大きな差が生じないと言える。
実施例1乃至実施例19の発泡体は、H1-H0が±20の範囲内にあり、これらの発泡体は、荷重の相違によって大きな硬度変化が生じなかった。
なお、例えば、体重30kgの人や40kgの人を仮定した場合でも、実施例1乃至実施例19の発泡体は、同様に大きな硬度変化が生じないと推定できる。
比較例1乃至3、8及び9の発泡体は、E40/E0が0.5未満であるので、大きな硬度変化が生じた。
比較例4乃至7の発泡体は、E40/E0が0.5以上であるが、H0が10未満であるので、大きな硬度変化が生じた。これは、H0(無荷重時のアスカーC硬度)が10未満の発泡体は、荷重が加わったときに発泡体内のセルが潰れることによって、硬くなってしまうことが原因と推定される。
なお、E40/E0が0.5未満で且つH0が10未満である発泡体については、データを取得していないが、このような発泡体も比較例1乃至9の発泡体と同様な結果になると推定される。
そして、E20/E0が0.2以上、E30/E0が0.3以上及びE50/E0が0.8以上である場合に、体重60kgの人が乗ったと仮定したときの硬度(H1)と、体重20kgの人が乗ったと仮定したときの硬度(H0)と、の差(H1-H0)が、±20の範囲内であった。
このことからも、各ひずみ量における弾性係数の比とシューズの使用感には、所定の相関関係があることが判る。
それらの弾性係数の比の中で、本発明者らは、一般的な成人男性のシューズ実使用時にソールに生じるひずみ量である「ひずみ40%」を用いた弾性係数の比(E40/E0)を採用した。
2a,2b シューズ本体
3a,3b ミッドソール
5a,51b,52b アウターソール
Claims (6)
- 樹脂成分を含む形成材料を発泡させた発泡体を有し、
前記発泡体のアスカーC硬度が、10以上であり、
前記発泡体の、ひずみ0%における弾性係数E0に対するひずみ40%における弾性係数E40の比E40/E0が、0.5以上である、発泡成形品。 - 前記発泡体のアスカーC硬度が、60以下である、請求項1に記載の発泡成形品。
- 前記形成材料の、周波数10Hz、23℃における貯蔵弾性率が15MPa以下である、請求項1または2に記載の発泡成形品。
- 前記発泡体の比重が、0.7以下である、請求項1~3のいずれか一項に記載の発泡成形品。
- 請求項1~4のいずれか一項に記載の発泡成形品を有する発泡ソール。
- 請求項5に記載の発泡ソールを有するシューズ。
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AU2012381265A AU2012381265B2 (en) | 2012-05-31 | 2012-05-31 | Molded foam article, foamed sole, and shoe |
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US10113045B2 (en) | 2012-05-31 | 2018-10-30 | Asics Corporation | Molded foam article, foamed sole, and shoe |
WO2020105089A1 (ja) * | 2018-11-19 | 2020-05-28 | 株式会社アシックス | 靴底用部材、靴、及び、靴底用部材の製造方法 |
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JP5887463B2 (ja) * | 2013-03-15 | 2016-03-16 | 株式会社アシックス | 積層構造を持つミッドソール |
EP2992772B1 (en) | 2013-05-01 | 2020-07-22 | ASICS Corporation | Member for shoe sole |
US9867427B2 (en) | 2013-10-10 | 2018-01-16 | Asics Corporation | Shoe sole |
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JPWO2013179455A1 (ja) | 2016-01-14 |
EP2857444A1 (en) | 2015-04-08 |
US20150143723A1 (en) | 2015-05-28 |
JP5685343B2 (ja) | 2015-03-18 |
AU2012381265B2 (en) | 2015-02-12 |
AU2012381265A1 (en) | 2014-12-18 |
EP2857444B1 (en) | 2016-08-10 |
US10113045B2 (en) | 2018-10-30 |
EP2857444A4 (en) | 2015-06-03 |
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