WO2020178987A1 - 装着品又はスポーツ用品用の防滑部材、装着品及びスポーツ用品 - Google Patents
装着品又はスポーツ用品用の防滑部材、装着品及びスポーツ用品 Download PDFInfo
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- WO2020178987A1 WO2020178987A1 PCT/JP2019/008674 JP2019008674W WO2020178987A1 WO 2020178987 A1 WO2020178987 A1 WO 2020178987A1 JP 2019008674 W JP2019008674 W JP 2019008674W WO 2020178987 A1 WO2020178987 A1 WO 2020178987A1
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- hydrogel
- elastic body
- slip member
- friction coefficient
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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
- A43B13/22—Soles made slip-preventing or wear-resisting, e.g. by impregnation or spreading a wear-resisting layer
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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
- A43B13/12—Soles with several layers of different materials
- A43B13/122—Soles with several layers of different materials characterised by the outsole or external layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B2400/00—Functions or special features of shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
- A41B2400/80—Friction or grip reinforcement
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/0015—Sports garments other than provided for in groups A41D13/0007 - A41D13/088
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2102/00—Application of clubs, bats, rackets or the like to the sporting activity ; particular sports involving the use of balls and clubs, bats, rackets, or the like
- A63B2102/02—Tennis
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2102/00—Application of clubs, bats, rackets or the like to the sporting activity ; particular sports involving the use of balls and clubs, bats, rackets, or the like
- A63B2102/18—Baseball, rounders or similar games
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2102/00—Application of clubs, bats, rackets or the like to the sporting activity ; particular sports involving the use of balls and clubs, bats, rackets, or the like
- A63B2102/32—Golf
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2209/00—Characteristics of used materials
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2225/00—Miscellaneous features of sport apparatus, devices or equipment
- A63B2225/60—Apparatus used in water
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B53/00—Golf clubs
- A63B53/14—Handles
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B60/00—Details or accessories of golf clubs, bats, rackets or the like
- A63B60/06—Handles
- A63B60/08—Handles characterised by the material
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B60/00—Details or accessories of golf clubs, bats, rackets or the like
- A63B60/06—Handles
- A63B60/14—Coverings specially adapted for handles, e.g. sleeves or ribbons
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
- A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
- A63B71/14—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves
- A63B71/141—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves in the form of gloves
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
- A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
- A63B71/14—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves
- A63B71/141—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves in the form of gloves
- A63B71/143—Baseball or hockey gloves
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
- A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
- A63B71/14—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves
- A63B71/141—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves in the form of gloves
- A63B71/146—Golf gloves
Definitions
- the present invention relates to an anti-slip member for an attached product or sports equipment, an attached product and a sports product, and more specifically, an attached product having improved wet grip or an anti-slip member for sports equipment, and an attached product provided with the anti-slip member. And sports equipment.
- the player When playing sports, the player is equipped with various equipment or uses various sports equipment. Some such wear or sports equipment is expected to come into contact with wet ground, balls, or water-wet objects such as human hands. When such an article comes into contact with an object wet with water, water intervening between the article and the object prevents direct contact between the article and the object, resulting in slipperiness. Occurs.
- athletic shoes may be used after rain or on wet ground with water in the rain. Since wet ground is slippery, there is a risk that a wearer of sports shoes may slip and fall when acting on wet ground.
- the sweat generated by the player may occur or get in between the grip and the hand.
- the sweat present between the grip and the hand causes a slip between the grip and the hand, which prevents the player from firmly fixing the bat to the hand. In some cases, the sweat may cause the bat to slip out of the hand.
- Patent Document 1 discloses a foam for a shoe sole, in which an abrasive cut product of leather is mixed with a foam for a shoe sole made of rubber and/or a resin.
- this foam for soles the wet cutability of the foam for soles is improved by the abrasive cut product of the blended leather having high water absorption, thereby improving the wet grip property.
- Patent Document 2 discloses an outsole formed of a viscoelastic body containing rubber.
- Patent Document 3 discloses an outer sole formed from a composition containing a thermoplastic elastomer. By increasing the surface free energy of the composition, the outer sole is prevented from forming a liquid film between the surface of the composition and the road surface, thereby improving wet grip properties. ing.
- anti-slip members as described above have been proposed, they are anti-slip members that can be widely applied to various attachments or sports equipment, and have further improved wet grip and wet grip. Wearable products and sports equipment are constantly being demanded.
- an object of the present invention to provide an anti-slip member for an attached product or sports equipment having improved wet grip, and an attached product and sports equipment provided with such an anti-slip member.
- Hydrogel is a material that is widely used as a biocompatible material such as artificial cartilage and is widely known as a material that is highly hydrophilic and is slippery with respect to an object wet with water.
- the anti-slip member for an accessory or sports equipment is composed of an elastic body provided with an elastomer and a hydrogel, and at least a part of the hydrogel is dispersed on the surface of the elastomer.
- the area occupied by the hydrogel is 1 to 25% of the entire surface of the elastic body.
- the hydrogel is a crosslinked body.
- the hydrogel contains a polyvinyl alcohol gel. More preferably, the degree of saponification of the polyvinyl alcohol gel is 80 to 100%.
- the hydrogel contains a silicone hydrogel.
- the anti-slip member for wearing articles or sports equipment according to the present invention further contains a silane coupling agent.
- the hydrogel is also dispersed inside the elastic body, and the anti-slip member is 1 to 10% by weight based on the elastomer. Contains the amount of the hydrogel.
- the worn article or sports article according to the present invention includes the above-mentioned anti-slip member.
- the wearing article according to the present invention is a shoe, and the anti-slip member is provided at a position where the shoe bottom of the shoe comes into contact with the ground. More preferably, the anti-slip member is provided at a position corresponding to at least one of the heel, the metatarsophalangeal joint, and the toes.
- FIG. 5 is a schematic view showing a state before the elastic body of FIG. 1 comes into contact with an object wet with water.
- FIG. 3 is a schematic view showing a shoe as a wearing article of an embodiment, in which a slip prevention member is provided at a position of the shoe sole that comes into contact with the ground.
- FIG. 6 is a bottom view of a shoe sole provided with a slip prevention member in the shoe of FIG.
- the top view of rugby wear as a wearing article of one embodiment.
- the top view of the glove as a wearing article of one embodiment.
- the figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example The figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example.
- the figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example The figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example.
- the figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example The figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example.
- the figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example The figure showing the static friction coefficient and the dynamic friction coefficient in the elastic body of an example and a comparative example.
- FIG. 1 is a schematic view showing the surface of an elastic body 10 constituting an anti-slip member for an accessory or sports equipment of the present embodiment.
- the elastic body 10 of the present embodiment includes an elastomer 11 and a hydrogel 12, and at least a part of the hydrogel 12 is dispersed on the surface of the elastic body 10.
- the attached item means an article worn or worn by the user at the time of use, and includes, for example, shoes for exercise, work, cold weather or daily use, wear, gloves, eyeglasses and the like.
- sports equipment refers to equipment that is used when the user exercises (particularly, is gripped by the user), and is not included in the above-described wearing article,
- the bat, racket, golf club, etc. the anti-slip member of the present invention is mainly provided on these grip portions), grips provided for them, grip tape, and the like are included.
- exercise used in the present specification generally refers to all physical activities performed by a person moving the body, and includes physical activities performed for sports, athletics, exercise, recreation, and the like.
- surface refers to a surface on which an elastomer and an elastic body come into contact with an object when the anti-slip member is provided on sports equipment.
- the surface of the elastomer and the elastic body means the surface where the elastomer and the elastic body come into contact with the ground. Does not include the surface that is adhered to and that does not come into contact with the ground.
- FIG. 2 is a schematic view showing a state before the elastic body 10 constituting the slip prevention member of this embodiment is in contact with the object G wet with water W
- FIG. 3 is a slip prevention member of this embodiment. It is the schematic which showed the state after the elastic body 10 which comprises is contacted with the target object G wet with the water W.
- the object G is represented as the ground wet with the water W.
- the hydrogel 12 has a higher affinity with the water W than the elastomer 11. Therefore, with such a configuration, when the surface of the elastic body 10 comes into contact with the object G wet with the water W, the water W that wets the object G and the hydrogel 12 provided on the surface are dispersed. As shown in FIG.
- the elastic body 10 of the present embodiment can exhibit a high grip property even for the object G wet with the water W, and therefore the wet grip property is improved.
- the hydrogel 12 is dispersed almost uniformly over the entire surface of the elastic body 10.
- the water W present between the elastomer 11 exposed on the surface of the elastic body 10 and the object G on the entire surface of the elastic body 10 is effectively transferred to the bottom of the hydrogel 12.
- the wet grip property can be more effectively enhanced on the entire surface of the elastic body 10.
- the hydrogel 12 does not necessarily have to be dispersed over the entire surface of the elastic body as described above. Even if the hydrogel 12 forms a hydrogel dispersion portion unevenly distributed in a specific region on the surface of the elastic body 10, the wet grip property of the elastic body 10 is enhanced.
- the area occupied by the hydrogel 12 dispersed on the surface of the elastic body 10 is not particularly limited, but is, for example, 1 to 25% of the entire surface area of the elastic body 10, and 5 to 25%. Preferably, the range of 5 to 20% is more preferable.
- the hydrogel 12 dispersed on the surface of the elastic body 10 is substantially uniformly dispersed in the state of small particles.
- the average particle diameter of the hydrogel 12 is preferably 0.01 to 1000 ⁇ m, more preferably 0.01 to 100 ⁇ m.
- FIG. 1 shows that the hydrogel 12 is dispersed on the surface of the elastic body 10, in the elastic body 10 of the present embodiment, the hydrogel 12 is also dispersed inside the elastic body 10. May be. In that case, even if the surface of the elastic body 10 is worn and the exposed hydrogel 12 is lost, the hydrogel 12 that has been dispersed inside the elastic body 10 is newly exposed on the surface of the elastic body 10. Since the gel 12 is exposed again, the wet grip property of the elastic body 10 hardly deteriorates with time, and the durability of the elastic body 10 can be improved.
- the amount of the hydrogel 12 dispersed in the elastic body 10 is not particularly limited, but should be set to an appropriate amount while considering the influence on the compression elastic modulus and hardness of the elastic body 10 forming the anti-slip member. Is preferred.
- the amount of the hydrogel 12 dispersed inside the elastic body 10 is preferably 1 to 15% by weight, more preferably 5 to 10% by weight, based on the elastomer 11.
- the particle size of the hydrogel 12 dispersed inside is preferably small in order to suppress a decrease in the mechanical strength of the elastic body 10 constituting the anti-slip member.
- the average particle size of the hydrogel 12 is preferably 0.01 to 1000 ⁇ m, more preferably 0.01 to 100 ⁇ m.
- the hardness of the elastic body 10 of the present embodiment can be appropriately set according to the use of the anti-slip member.
- the hardness of the elastic body 10 is preferably in the range of 55 to 75 for the hardness of the type A durometer based on JIS K 6253-3: 2012.
- the hardness of the elastic body 10 is preferably in the range of 40 to 60 for the hardness of the type A durometer. ..
- the average particle size of the hydrogel 12 dispersed on the surface of the elastic body 10 is 10 to 20 particles of the hydrogel 12 found on the surface of the elastic body 10 randomly selected. , The major axis diameters of those particles are individually measured, and the measured values obtained for each are arithmetically averaged. Further, regarding the average particle size of the hydrogel 12 dispersed inside the elastic body 10, the same measurement is performed on each of two or more cross sections of the elastic body 10, and the measured values obtained for each cross section are arithmetically averaged. It can be obtained by.
- an elastomer that is generally used as a slip resistant material and that can exhibit a sufficient grip property with respect to a contacting object is used.
- examples of such an elastomer include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), butyl rubber (IIR).
- vulcanized rubber such as silicone rubber (Si), or styrene elastomer (TPS), olefin elastomer (TPO), urethane elastomer (TPU), polyester elastomer (TPEE), polyamide elastomer (TPA) poly.
- vulcanized rubber such as silicone rubber (Si), or styrene elastomer (TPS), olefin elastomer (TPO), urethane elastomer (TPU), polyester elastomer (TPEE), polyamide elastomer (TPA) poly.
- PVC vinyl chloride
- EVA ethylene-vinyl acetate copolymer
- the elastomer 11 is appropriately selected according to the properties required for a fitting or sports equipment in which the anti-slip member is used.
- BR, SBR, NR and IR having excellent tensile strength, tear strength and abrasion resistance are preferably selected as the elastomer 11.
- the elastomer 11 preferably has high water repellency.
- the contact angle of the elastomer 11 is preferably 80° or more, more preferably 100° or more.
- the hydrogel 12 is a gel formed by dispersing a hydrogel material in water as a dispersion medium.
- Such hydrogels include, for example, polyvinyl alcohol gel, acrylic polymer gel, urethane gel, polyethylene glycol gel, polyethylene oxide gel, silicone gel and the like. These may contain only 1 type and may contain multiple types.
- the amount of the dispersion medium contained in the hydrogel 12 is not particularly limited, but is, for example, 1 to 99% by weight, preferably 5 to 20% by weight of the entire hydrogel 12.
- the dispersion medium of the hydrogel may further contain a hydrophilic organic solvent in addition to water. Examples of such a hydrophilic organic solvent include an organic solvent having a hydroxyl group, an amino group or an amide group.
- the hydrogel 12 may be a crosslinked body or a non-crosslinked body. However, since the hydrogel 12 needs to be stably present on the surface of the elastic body 10 when the anti-slip member including the elastic body 10 is used, the hydrogel 12 is preferably a more stable crosslinked body.
- the hydrogel 12 is preferably a crosslinked body that is chemically crosslinked by adding a crosslinking agent. This is because the chemically crosslinked crosslinked product has high stability because it is irreversibly crosslinked. However, if the crosslinked state of the hydrogel 12 is not substantially disrupted by the temperature or mechanical impact during use and manufacture of the elastic body 10 and the anti-slip member provided with the elastic body 10, the hydrogel 12 is frozen and thawed. It may be a crosslinked body physically crosslinked by a method or the like.
- the hydrogel 12 may further contain a crosslinking agent.
- the crosslinking agent include boron compounds such as borax, titanium lactate, titanium aminoethylaminoethanolate, organic titanium compounds such as titanium triethanolaminate, and organic zirconium compounds such as zirconyl chloride.
- the cross-linking agent is preferably an organotitanium compound from the viewpoint of wear resistance, and particularly titanium triethanolaminate having a very high cross-linking efficiency is preferable.
- the amount of the crosslinking agent contained in the chemically crosslinked hydrogel 12 is not particularly limited as long as the hydrogel 12 is sufficiently crosslinked, and may be 1 to 10% by weight with respect to the entire hydrogel 12.
- the hydrogel 12 is sufficiently cross-linked if the cross-linking agent is contained in the hydrogel 12 in an amount of 1 to 2% by weight. it is conceivable that.
- the hydrogel 12 is preferably a hydrogel containing a polyvinyl alcohol gel. This is because the polyvinyl alcohol gel has relatively high hydrophilicity and further has very high stability when a crosslinked body is formed.
- the saponification degree is preferably high in order to increase the hydrophilicity of the polyvinyl alcohol gel.
- the saponification degree of polyvinyl alcohol is preferably 80 to 100%, more preferably 88 to 100%, and most preferably 98 to 100%.
- a hydrogel containing a silicone hydrogel is preferable. This is because the silicone hydrogel contains water, has relatively high hydrophilicity, and has low elasticity.
- hydrogel 12 examples include acrylic polymer gel such as polyacrylamide gel, sodium polyacrylate, gel polyacrylonitrile gel, and urethane gel. These gels are also known for their relatively high hydrophilicity.
- the molecular weight of the hydrogel 12 is not particularly limited.
- the molecular weight of the hydrogel 12 can be appropriately selected from the viewpoint of handleability at the time of manufacturing the elastic body 10, for example.
- the hydrogel 12 is preferably highly hydrophilic.
- the contact angle of the hydrogel 12 is, for example, preferably 90° or less, more preferably 50° or less. Further, it is preferable that the difference between the hydrophilicity of the hydrogel 12 and the hydrophilicity of the elastomer 11 is large, and for example, the difference between them is preferably 10° or more, and the difference is 50° or more. Is more preferable.
- the hydrogel 12 preferably has a small compression elastic modulus. If the compressive elastic modulus of the hydrogel 12 is small, the water W collected at the position where the hydrogel 12 is provided is likely to be retained between the compressed and deformed hydrogel 12 and the object. From this viewpoint, the compression modulus of the hydrogel 12 is, for example, preferably 10 MPa or less, and more preferably 1 MPa or less. Further, it is preferable that the difference between the compressive elastic modulus of the hydrogel 12 and the compressive elastic modulus of the elastomer 11 is large, for example, there is a difference of 5 MPa or more between them, and a difference of 10 MPa or more. Is more preferable. When the hydrogel 12 is also dispersed inside the elastomer 11, the compression elastic modulus of the hydrogel 12 is set to an appropriate value while considering the influence on the compression elastic modulus and hardness of the elastic body 10. Preferably.
- the elastic body 10 of the present embodiment may further contain a silane coupling agent in order to prevent the hydrogel 12 from detaching from the surface of the elastomer 11 when the anti-slip member is used.
- a silane coupling agent examples include alkylsilane, vinylsilane, aminosilane, mercaptosilane, bis (3-triethoxysilylpropyl) tetrasulfide (Si69), and bis (3-triethoxysilylpropyl) tetrasulfide. It is preferably used. These may be used alone or in combination of two or more.
- the content of the silane coupling agent in the elastic body 10 may be 0.1 to 10% by weight, preferably 0.2 to 5% by weight, and 0.5 to 1% by weight, based on the entire elastic body 10. % Is more preferable.
- the content of the silane coupling agent in the elastic body 10 is 0.5 to 1% by weight, surprisingly, the abrasion resistance of the elastic body 10 is deteriorated due to the incorporation of the hydrogel. It has been found that the effect of being significantly suppressed or the wear resistance of the elastic body 10 is improved is produced.
- a vulcanizing agent in addition to the above components, a vulcanizing agent, a vulcanization accelerator, a cross-linking accelerator, a filler, a plasticizer, an antioxidant, an ultraviolet absorber, and any other optional one. It may contain an ingredient.
- the elastic body 10 of the present embodiment is formed by kneading each of the above components, that is, an elastomer 11 material, a hydrogel 12 material, and optionally a silane coupling agent, by any method usually performed by those skilled in the art. It can be manufactured.
- a kneading method a method of kneading each of the above components by a rotary such as an open roll or a kneader, for example, an A kneading or a B kneading step can be used.
- kneading with a kneader is more preferable because the hydrogel 12 can be dispersed in the elastomer 11 in the form of smaller particles.
- the temperature for kneading the above components is not particularly limited, and may be, for example, 80 to 200° C., preferably 100 to 180° C. At this time, when the above components are kneaded at a high temperature of 100 to 180° C., excess water contained in the hydrogel 12 material is removed. The defective portion that may occur in the above is miniaturized, whereby the mechanical strength of the obtained elastic body 10 becomes relatively high.
- the attached product or sports equipment of the present invention includes an anti-slip member (hereinafter, also referred to as an anti-slip member 10) composed of the elastic body 10.
- the wearing article or sports article of the present invention is not particularly limited as long as it is an article worn or worn by the user at the time of use, or an article used when the user exercises, for example, shoes, It may be wear, gloves, glasses, a bat, a racket, a golf club, or the like.
- FIG. 4 is a schematic view showing a shoe 20 as a wearing article of one embodiment, in which the slip prevention member 10 is provided at a position where the shoe sole 23 comes into contact with the ground.
- the shoe 20 has an upper material 21 that covers the upper surface of the foot, and a midsole 22 and an outer sole 23 as soles that are arranged under the upper material 21. More specifically, the shoe 20 has an outer sole 23 arranged at a position in contact with the ground and provided with the anti-slip member 10, and a midsole 22 arranged between the upper member 21 and the outer sole 23. doing.
- the shoe 20 includes both the midsole 22 and the outer sole 23, but the shoe 20 does not necessarily have to include both of them. That is, the shoe 20 may include only the outer sole 23 provided with the anti-slip member 10 as the sole, and may not include the midsole 22. In this case, the outer sole 23 may be formed of foam in order to ensure the cushioning property required for the midsole.
- FIG. 5 is a bottom view of the shoe sole (outer sole) 23 provided with the anti-slip member 10 in the shoe 20.
- the length of the shoe sole 23 is the lengthwise position. Region within the range of 0% to 60% position (hereinafter also referred to as the front region of the shoe sole 23) and region within the range of 70% to 100% position of the shoe sole 23 in the length direction (hereinafter, The anti-slip member 10 may be provided on the rear region of the shoe sole 23).
- the anti-slip member 10 is provided in an area that occupies 5 to 100% of the entire front area of the shoe sole 23, an area that occupies 5 to 100% of the entire posterior area of the shoe sole 23, or both.
- the region within the range of 0% to 60% position in the length direction of the shoe sole 23 is the point at the 60% position on the lengthwise straight line passing through the toe side end and the heel side end.
- the region within the range of 70% to 100% positions in the length direction of the shoe sole 23 refers to the region of the shoe sole 23 on the heel side of the 70% position width direction straight line which is similarly defined. Further, these areas are designated by the areas when the bottom surface of the shoe sole 23 is viewed from the front as shown in FIG.
- the shoe sole 23 is provided with the slip prevention member 10 at a position corresponding to the heel, metatarsophalangeal joint and toe of the wearer.
- the contact with the ground is large and the contact area is relatively large. Therefore, by disposing the anti-slip member 10 at these positions on the shoe sole 23, the wet grip property of the shoe 20 can be more effectively enhanced.
- the position where the anti-slip member 10 is provided in the sole 23 of the shoe 20 of the present invention is not particularly limited.
- the anti-slip member 10 may be provided at a position corresponding to at least one position of the heel, the metatarsophalangeal joint, or the toe of the shoe sole 23, and may be provided at a position different from those positions. May be good.
- the anti-slip member 10 may be provided only in the front region of the shoe sole 23, or may be provided only in the rear region.
- the anti-slip member 10 may be provided on the entire surface of the shoe sole 23, or the entire sole 23 may be formed by the anti-slip member 10.
- the antislip member 10 provided on the shoe sole 23 when in contact with the ground, makes contact with the ground on the widest possible surface of the antislip member 10. .. Therefore, unlike the conventionally known anti-slip members for shoe soles, the anti-slip member 10 provided on the shoe sole 23 preferably does not have large irregularities on the surface, and has a flat surface. More preferred.
- the shoe 20 of the present embodiment has enhanced wet grip on various grounds including unpaved surfaces by the anti-slip member 10 provided on the sole 23, and among them, it is paved with concrete, asphalt, or the like. Wet grip on the road is particularly enhanced. On the contrary, it should be noted that the shoe 20 of the present embodiment can hardly be expected to have improved wet grip on frozen ground or ice due to the mechanism of improving wet blip.
- the anti-slip member 10 of the present embodiment is composed of an elastic body 10 in which hydrogel is dispersed on the surface, but the anti-slip member has such an elastic body 10 and hydrogel not dispersed on the surface. , It may be a combination with a conventional elastic body having anti-slip unevenness on the surface. Further, such an anti-slip member may be integrally molded as an elastic body having both a surface on which the hydrogel is dispersed and a surface on which the hydrogel is not dispersed.
- FIG. 6 shows a rugby wear 30 as an embodiment of the wearing article of the present invention.
- the anti-slip member 10 may be provided near the chest of the front body and on the shoulders and the sides.
- the vicinity of the chest and the sides of the front body are the parts that come into contact with the ball as an object when holding the ball during a rugby game. Therefore, a rugby player who wears the rugby wear 30 provided with the anti-slip member 10 at these portions can obtain an effect that it is difficult for the sweat-wet ball to slip off.
- the shoulder is a part that comes into contact with the shoulders of the opponent players when forming a scrum during a rugby game. Therefore, a rugby player wearing the rugby wear 30 provided with the anti-slip member 10 at this portion has the effect of being less likely to slip when assembling a scrum.
- FIG. 7 shows a sports glove 40 as an embodiment of the wearing article of the present invention.
- the anti-slip member 10 may be provided between the joints of the phalanges and near the tip of the metacarpal bone. A player wearing a sports glove 40 provided with an anti-slip member 10 at these portions can obtain an effect that it is difficult to slip off an object wet with water or sweat that he / she is holding.
- the anti-slip member 10 may be provided on a grip portion of a sports equipment such as a bat, a racket or a golf club.
- a sports equipment such as a bat, a racket or a golf club.
- the grip portion is less likely to slip due to water or sweat, so that the user can easily hold the sporting goods stably.
- the anti-slip member for the wearing product or sports equipment of the present embodiment is composed of an elastic body provided with an elastomer and a hydrogel, and at least a part of the hydrogel covers the entire surface of the elastic body. Since it is dispersed, it is possible to exhibit high grip even on an object wet with water, and therefore, wet grip is improved. Moreover, since the wearing article or sports article of the present embodiment includes the anti-slip member, it is possible to provide the wearing article or sports article having improved wet grip properties.
- the anti-slip member for the worn article or sports article, the worn article, and the sports article according to the present invention are not limited to the configurations of the above embodiments. Further, the anti-slip member for the worn article or sports article, the worn article, and the sports article according to the present invention are not limited by the above-described effects. Various modifications can be made to the anti-slip member for wearable goods or sports goods, wearable goods and sports goods according to the present invention without departing from the scope of the present invention.
- the anti-slip member for wearing articles or sports articles the wearing articles and sports articles.
- the present invention can be appropriately adopted in the present invention.
- polyvinyl alcohol gel As the hydrogel.
- -Polyvinyl alcohol 165-1795 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. Saponification degree 80 mol%) : 160-03055 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. Saponification degree 88 mol%) : 160-11485 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., saponification degree 98 mol%)
- -Plasticizer ion-exchanged water-Crosslinking agent: TC-400 (manufactured by Matsumoto Fine Chemical Co., Ltd. Titanium diisopropoxybis (triethanolaminate)) These materials were blended in the weight ratios shown in Table 1 below to prepare polyvinyl alcohol gels (a) to (g).
- silane coupling agent contained in the rubber raw material
- silane coupling agent for coupling the interface between the vulcanized rubber and the polyvinyl alcohol gel
- Si69 manufactured by Degussa Japan Ltd., bis[3-(triethoxysilyl)propyl]pertetrasulfide, for rubber/PVA gel interface
- Examples 1 to 15 Elastic bodies in which polyvinyl alcohol gel particles were dispersed on the surface and inside of the vulcanized rubber were prepared as follows. First, of all the above-mentioned vulcanized rubber raw material materials, except for the vulcanizing agent and vulcanization accelerator, a kneader (device name: DS3-10MWB, manufactured by Nippon Spindle Manufacturing Co., Ltd.) was used. The mixture was kneaded at 80 to 130 ° C. for 15 minutes. The rubber raw material thus obtained, the polyvinyl alcohol gel selected from Table 1 above, and optionally an additional silane coupling agent were compounded at the compounding ratio shown in Table 2 below to give the above vulcanizing agent.
- a kneader device name: DS3-10MWB, manufactured by Nippon Spindle Manufacturing Co., Ltd.
- a vulcanization accelerator with an open roll (device name: KD-M2-8, manufactured by KNEADER MACHINERY CO., LTD.) at 25 to 60° C. for 10 minutes. ..
- the elastic raw material thus obtained is introduced into a flat plate-shaped mold, and the device name: ram diameter 12 "150 tons (manufactured by Nimei Koki Co., Ltd.) is used for 5 minutes under 160 ° C. conditions.
- ram diameter 12 "150 tons manufactured by Nimei Koki Co., Ltd.
- an elastic body molded into a flat plate having a thickness of 2 mm was obtained, and the obtained elastic body was kneaded into fine particles on the surface of the vulcanized rubber by measuring the polyvinyl alcohol gel coverage described later. It was confirmed that the polyvinyl alcohol gel particles (average particle diameter: 100 to 200 ⁇ m) were dispersed.
- Comparative Example 1 By the same method as in Examples 1 to 15 except that the polyvinyl alcohol gel was not kneaded, a 2 mm-thick plate-shaped elastic body was obtained.
- the elastic bodies of Examples 1 to 15 were immersed in an aqueous solution containing 1 to 100 ppm of fluoroscein sodium salt for 1 hour. Subsequently, the elastic body was taken out from the aqueous solution, the aqueous solution adhering to the elastic body was wiped off using a non-woven fabric, and then the surface of the elastic body was irradiated with blue light in a dark room. On the surface, green fluorescence due to the polyvinyl alcohol gel was observed.
- the ratio of the area where the polyvinyl alcohol gel is exposed on the surface of the elastic body (polyvinyl alcohol gel coverage rate) can be determined. Calculated.
- Hardness Measurement The hardness of the elastic bodies of Examples 1 to 15 and Comparative Example 1 was measured using “Asker rubber hardness meter A type” manufactured by Kobunshi Keiki Co., Ltd. as Asker A type hardness meter. The results are shown in Table 2 below.
- Friction test 1 The static friction coefficient and the dynamic friction coefficient of the elastic bodies of Examples 1 to 15 and Comparative Example 1 were measured by sliding the probe on the elastic body wet with water. Specifically, under the conditions of an atmospheric temperature of 24 ° C. and a relative humidity of 75% RH, the surface of the elastic body molded into a flat surface is wetted with water, and cylindrical aluminum is placed on the surface of the elastic body wet with water. A probe (diameter: 10 mm, length: 6.0 mm) was placed so that the surface of the elastic body was in contact with the side surface of the cylinder.
- the cylinder is slid on the surface of the elastic body in a direction orthogonal to the length direction of the probe at a vertical load of 0.981 N and a sliding speed of 10.0 mm/s, and the static friction coefficient and the dynamic friction coefficient at that time are measured. It was measured.
- Friction test 2 Before performing the friction test, the elastic bodies of Examples 1 to 15 and Comparative Example 1 were previously placed in water having the same temperature as the ambient temperature and left as they were for 1 hour. Then, after taking out the elastic body from water, their static friction coefficient and dynamic friction coefficient were measured by the same method as in the friction test 1.
- FIG. 8 and FIG. 9 are diagrams showing the relationship between the static friction coefficient and the dynamic friction coefficient in the friction test 1 and the polyvinyl alcohol gel blending amount regarding the elastic bodies of Comparative Example 1 and Examples 1 to 6.
- the elastic bodies of Examples 1 to 6 in which the hydrogel particles are dispersed on the surface of the vulcanized rubber are more water-based than the elastic bodies of Comparative Example 1 containing no hydrogel. Both the coefficient of static friction and the coefficient of dynamic friction in the wet state are significantly increased.
- the elastic bodies of Examples 4 to 6 shown in FIG. 9 include an additional silane coupling agent for coupling the interface between the vulcanized rubber and the hydrogel, but do not include it. It can also be seen that it exhibits static friction coefficient and dynamic friction coefficient equivalent to those of the elastic bodies of Examples 1 to 3 shown in FIG.
- FIGS. 10 and 11 show static friction coefficient and dynamic friction in friction test 2 on the elastic bodies of Comparative Example 1 and Examples 1 to 6. It is a figure showing the relationship between a coefficient and polyvinyl alcohol gel compounding quantity.
- the elastic bodies of Examples 1 to 3 lose the effect of improving the static friction coefficient and the dynamic friction coefficient by the hydrogel when left in water for 1 hour. It is considered that this is because, in these elastic bodies, the hydrogel particles are detached from the surface of the vulcanized rubber when left in water for a long time.
- FIGS. 12 and 13 show static friction coefficient and dynamic friction coefficient in the friction tests 1 and 2 and the additional silane coupling agent for the elastic bodies of Examples 2, 4 and 7 to 9. It is a figure which shows the relationship with the compounding amount.
- FIG. 12 in these elastic bodies, even if the compounding amount of the additional coupling agent is changed, the effect of improving the static friction coefficient and the dynamic friction coefficient by the hydrogel is hardly affected.
- FIG. 13 it can be seen that when the compounding amount of the additional coupling agent is increased, the reduction of the static friction coefficient and the dynamic friction coefficient due to being left in water is effectively suppressed.
- FIG. 12 and 13 show static friction coefficient and dynamic friction coefficient in the friction tests 1 and 2 and the additional silane coupling agent for the elastic bodies of Examples 2, 4 and 7 to 9. It is a figure which shows the relationship with the compounding amount.
- FIG. 13 it can be seen that when the compounding amount of the additional coupling agent is increased, the reduction of the static friction coefficient and the dynamic friction coefficient due to being left in water is effectively suppress
- FIGS. 14 and 15 show static friction coefficient and kinetic friction coefficient in friction tests 1 and 2 and blending of crosslinking agent contained in polyvinyl alcohol gel for the elastic bodies of Examples 4 and 10 to 13. It is a figure which shows the relationship with a quantity.
- FIG. 14 in these elastic bodies, the effect of improving the static friction coefficient and the dynamic friction coefficient by the hydrogel does not significantly change depending on the crosslinking agent contained in the hydrogel.
- FIG. 15 as compared with the hydrogel containing no cross-linking agent, the use of the hydrogel containing the cross-linking agent causes a decrease in static friction coefficient and dynamic friction coefficient after being left in water.
- FIGS. 16 and 17 show the relationship between the static friction coefficient and dynamic friction coefficient in friction tests 1 and 2 and the saponification degree of the polyvinyl alcohol gel with respect to the elastic bodies of Examples 4, 14 and 15. It is a figure.
- the higher the saponification degree of the polyvinyl alcohol gel the more effectively the static friction coefficient and the dynamic friction coefficient of these elastic bodies are increased.
- the higher the degree of saponification of the polyvinyl alcohol gel dispersed on the surface of the vulcanized rubber is, the higher the hydrophilicity of the polyvinyl alcohol gel is, so that the polyvinyl alcohol gel is between the surface of the elastic body and the cylinder sliding on the surface. It is considered that this is because the localization effect of water caused by attracting the intervening water to the position where the polyvinyl alcohol gel is present becomes more remarkable.
- the elastic bodies of Examples 1 to 15 in which the hydrogel particles are dispersed on the surface of the vulcanized rubber have a friction in a wet state as compared with the elastic bodies of Comparative Example 1 containing no hydrogel. It can be seen that the coefficient, that is, the wet grip property is significantly improved.
- thermosetting silicone rubber was used as the material of the elastomer.
- hydrogel material either the following polyvinyl alcohol gel material or silicone hydrogel material was used.
- Polyvinyl alcohol gel material Frozen pulverized particles (average particle diameter: 10 to 100 ⁇ m) obtained by freezing and pulverizing the polyvinyl alcohol gel (a) shown in Table 1 above at -196 ° C.
- Silicone hydrogel material Silicone hydrogel particles (average particle diameter: 1 mm) obtained by cutting commercially available contact lens comfilcon A (silicone hydrogel lens manufactured by Cooper Vision)
- Comparative example 2 On a concave hemispherical watch glass having a diameter of 142 mm and a radius of curvature of 71 mm, uncured silicone rubber was poured to fill the watch glass and heated at 80° C. for 90 minutes to cure the silicone rubber on the watch glass. .. After the silicone rubber was completely cured, an elastic body made of cured silicone gel and having a convex shape corresponding to the concave shape of the watch glass was taken out from the watch glass.
- Example 16 An elastic body was obtained in the same manner as in Comparative Example 2 except that frozen pulverized particles of polyvinyl alcohol gel were dispersedly arranged on the concave surface of the watch glass before pouring the uncured silicone rubber onto the watch glass. It was The resulting elastic body provided polyvinyl alcohol gel particles dispersed on a watch glass on the convex surface of the cured silicone rubber.
- Example 17 An elastic body was prepared in the same manner as in Comparative Example 2 except that a mixed solution of uncured silicone rubber and frozen pulverized particles of polyvinyl alcohol gel was poured into the watch glass instead of the uncured silicone rubber. Obtained. The obtained elastic body provided polyvinyl alcohol gel particles inside and on the surface of the cured silicone rubber.
- Example 18 An elastic body was obtained in the same manner as in Comparative Example 2 except that silicone hydrogel particles were dispersed and arranged on the concave surface of the watch glass instead of the frozen and pulverized particles of polyvinyl alcohol gel. The resulting elastic body provided silicone hydrogel particles dispersed on a watch glass on the convex surface of the cured silicone rubber.
- Friction test 3 The coefficient of static friction and the coefficient of dynamic friction of the elastic bodies of Examples 16 to 18 and Comparative Example 2 were measured by sliding these elastic bodies on a glass plate wet with water. Specifically, under the conditions of an atmospheric temperature of 24 ° C. and a relative humidity of 75% RH, the surface of the flat glass plate is wetted with water, and the convex surface of the elastic body is formed on the surface of the glass plate wet with water. The elastic body was arranged so as to come into contact with the glass plate. After that, the elastic body was slid on the surface of the glass plate at a vertical load of 0.981 N and a sliding speed of 10.0 mm/s, and the static friction coefficient and the dynamic friction coefficient at that time were measured.
- the above silicone rubber material was used as an elastomer, and the frozen pulverized particles of the above polyvinyl alcohol gel material (a) were used as a hydrogel.
- Comparative Example 3 Comparison except that instead of the watch glass, a shoe sole mold corresponding to the shape of the outer sole (foot length 27 cm) for shoes with a flat bottom surface that contacts the ground was used. An elastic body was obtained in the same manner as in Example 2.
- Example 19 Before pouring the uncured silicone rubber into the shoe sole mold, the same method as in Comparative Example 2 except that frozen and pulverized particles of polyvinyl alcohol gel were dispersed and arranged on the bottom surface of the shoe sole mold. Obtained an elastic body. The obtained elastic body was equipped with the polyvinyl alcohol gel particles dispersed in the shoe sole mold on the bottom surface of the outer sole.
- Friction test 4 The coefficient of static friction and the coefficient of dynamic friction of the elastic bodies of Example 19 and Comparative Example 4 were measured according to JIS T8101. Specifically, after fixing the elastic bodies of Example 19 and Comparative Example 4 to the soles of shoes having no outer sole, a flat iron plate is used under the conditions of an atmospheric temperature of 24 ° C. and a relative humidity of 75% RH. The surface of the above was wetted with water, and the shoe provided with the elastic body was placed on the surface of the iron plate wetted with water so that the bottom surface of the elastic body was in contact with the iron plate. Then, the elastic body was slid on the surface of the iron plate at a vertical load of 500 N and a sliding speed of 300 mm/s, and the static friction coefficient and the dynamic friction coefficient at that time were measured.
- the elastic body of Example 19 in which the hydrogel particles are dispersed on the surface of the silicone rubber has the outer sole shape which is the sole member of the shoe. Even when used as a sole, compared with the outer sole-shaped elastic body of Comparative Example 3 containing no hydrogel, the static friction coefficient and the dynamic friction coefficient in a wet state, that is, the wet grip property is significantly improved. Has been elevated.
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Abstract
Description
特許文献1には、ゴム及び/又は樹脂の靴底用発泡体に、皮革の研磨切削物が配合された靴底用発泡体が開示されている。この靴底用発泡体では、配合された吸水性の高い皮革の研磨切削物によって靴底用発泡体の水の濡れ性を向上させ、それによりウェットグリップ性が高められている。
特許文献2には、ゴムを含む粘弾性体から形成されたアウトソールが開示されている。このアウトソールでは、該粘弾性体の動的粘弾性測定における損失係数及び貯蔵弾性率、並びに引張応力を調整して、該粘弾性体を高粘性化することにより、ウェットグリップ性が高められている。
特許文献3には、熱可塑性エラストマーを含む組成物から形成されたアウターソールが開示されている。このアウターソールは、該組成物の表面自由エネルギーを高くすることにより、組成物の表面と路面との間に液膜が形成されることが抑制されており、それによって、ウェットグリップ性が高められている。
ハイドロゲルは、人工軟骨のような生体適合材料にも使用される、親水性が高いため水に濡れた対象物に対して滑りやすい材料として広く知られた材料である。本発明者らは、そのような特性を有するハイドロゲルをエラストマーの表面上に分散させることによって、驚くべきことに、エラストマー及びハイドロゲルを備えた防滑部材のウェットグリップ性が従来技術に比べて飛躍的に向上することを見出し、本発明を完成させた。
まず、本発明の装着品又はスポーツ用品用の防滑部材について、図1~3を参照して説明する。
図1は、本実施形態の装着品又はスポーツ用品用の防滑部材を構成する弾性体10の表面を示した概略図である。本実施形態の弾性体10は、エラストマー11と、ハイドロゲル12とを備えており、ハイドロゲル12の少なくとも一部が、弾性体10の表面に分散されている。
本明細書において、装着品とは、使用時において使用者に着用又は装着される物品をいい、例えば、運動用、作業用、防寒用又は日用の靴、ウェア、手袋、眼鏡等を含む。また、本明細書において、スポーツ用品とは、使用者が運動を行う際に(特に、使用者に把持されて)使用される用品であって、前述の装着品に含まれないものをいい、例えば、バット、ラケット、ゴルフクラブ等(本発明の防滑部材は、主にこれらのグリップ部に設けられる)や、それらに供されるグリップ、グリップテープ等を含む。なお、本明細書で使用される用語「運動」は、広く人間が体を動かして行う身体活動全般をいい、スポーツ、アスレチック、エクササイズ、レクリエーション等のために行う身体活動を含む。
また、本明細書で使用される用語「表面」は、防滑部材がスポーツ用品に備えられた際に、エラストマー及び弾性体が対象物と接触することになる面をいう。例えば、防滑部材が靴の靴底に設けられた場合には、エラストマー及び弾性体の表面とは、エラストマー及び弾性体が地面と接触することになる面のことをいい、エラストマー及び弾性体が靴と接着されている面であって地面と接触することのない面を含まない。
ハイドロゲル12は、エラストマー11に比べて、水Wとの親和性が高い。そのため、斯かる構成により、弾性体10の表面が水Wで濡れた対象物Gと接触する際に、対象物Gを濡らしている水Wは、表面に分散して設けられたハイドロゲル12と接触しようとする傾向を生じるため、図3に示すように、ハイドロゲル12の設けられた位置に集まる。これにより、弾性体10の表面に露出したエラストマー11と対象物Gとの間に介在する水Wが低減することになるため、エラストマー11と対象物Gとの接触面積が大きくなる。
したがって、本実施形態の弾性体10は、水Wで濡れた対象物Gに対しても高いグリップ性を発揮することができ、したがって、ウェットグリップ性が向上する。
もっとも、弾性体10では、必ずしも上述のようにハイドロゲル12が弾性体の表面全体にわたって分散されていなくてもよい。ハイドロゲル12が弾性体10の表面の特定の領域に偏在して分散したハイドロゲル分散部を形成していたとしても、弾性体10のウェットグリップ性は、高められる。
ここで、弾性体10の表面上に分散されたハイドロゲル12は、小さな粒子の状態で実質的に均一に分散されていることが好ましい。ハイドロゲル12が小さな粒子として均一に分散されていることにより、対象物を濡らしている水Wを、ハイドロゲル12が設けられた位置にさらに効率的に集めることができる。好ましくは、ハイドロゲル12の平均粒子径は、0.01~1000μmであり、より好ましくは、0.01~100μmである。
弾性体10の内部に分散されたハイドロゲル12の量は、特に限定されないが、防滑部材を構成する弾性体10の圧縮弾性率及び硬度への影響を考慮しつつ、適切な量に設定することが好ましい。好ましくは、弾性体10の内部に分散されたハイドロゲル12の量は、エラストマー11に対して1~15重量%が好ましく、5~10重量%がより好ましい。
また、内部に分散されたハイドロゲル12の粒子径は、防滑部材を構成する弾性体10の機械的強度の低下を抑制するため、小さいことが好ましい。この観点からも、ハイドロゲル12の平均粒子径は、0.01~1000μmであることが好ましく、0.01~100μmであることがより好ましい。
ハイドロゲル12が含有する分散媒の量は特に限定されないが、例えば、ハイドロゲル12全体の1~99重量%であり、好ましくは、5~20重量%である。
なお、ハイドロゲルの分散媒としては、水に加えて親水性有機溶媒をさらに含んでいてもよい。そのような親水性有機溶媒としては、例えば、水酸基、アミノ基又はアミド基を備えた有機溶媒が挙げられる。
化学架橋されたハイドロゲル12に含まれる架橋剤の量は、ハイドロゲル12が十分に架橋される限りにおいて特に限定されず、ハイドロゲル12全体に対して1~10重量%であってもよく、1~5重量%が好ましく、1~2重量%がより好ましい。特に、架橋剤が架橋効率の高いチタントリエタノールアミネートである場合には、架橋剤がハイドロゲル12全体に対して1~2重量%含まれていれば、ハイドロゲル12が十分に架橋されると考えられる。
ハイドロゲル12がポリビニルアルコールゲルである場合には、ポリビニルアルコールゲルの親水性を高めるため、けん化度が高いことが好ましい。具体的には、ポリビニルアルコールのけん化度は、80~100%が好ましく、88~100%がより好ましく、98~100%が最も好ましい。
また、ハイドロゲル12の親水性と、エラストマー11の親水性との差が大きいことが好ましく、例えば、両者の間には10°以上の差があることが好ましく、50°以上の差があることがより好ましい。
また、ハイドロゲル12の圧縮弾性率と、エラストマー11の圧縮弾性率との差が大きいことが好ましく、例えば、両者の間には5MPa以上の差があることが好ましく、10MPa以上の差があることがより好ましい。
なお、ハイドロゲル12がエラストマー11の内部にも分散している場合には、弾性体10の圧縮弾性率及び硬度への影響を考慮しつつ、ハイドロゲル12の圧縮弾性率を適切な値に設定することが好ましい。
シランカップリング剤としては、例えば、アルキルシラン、ビニルシラン、アミノシラン、メルカプトシラン、ビス(3-トリエトキシシリルプロピル)テトラサルファイド(Si69)等が挙げられ、ビス(3-トリエトキシシリルプロピル)テトラサルファイドが好適に使用される。これらは単独で使用されてもよく、複数種を組み合わせて使用されてもよい。
例えば、混練方法としては、オープンロール又はニーダー等のロータリーにより、例えばA練り又はB練り工程により上記各成分を混練する方法を用いることができる。このとき、ニーダーを用いて混練すると、ハイドロゲル12をより小さい粒子状でエラストマー11中に分散させることができるため、より好ましい。
上記各成分を混練する際の温度は特に限定されず、例えば、80~200℃で混練してもよく、好ましくは、100~180℃で混練してもよい。このとき、上記各成分を100~180℃の高い温度で混練すると、ハイドロゲル12材料に含まれていた過剰な水分が除去されるため、混練時にハイドロゲル12材料に起因してエラストマー11の内部に生じ得る欠陥部が微細化され、それによって、得られる弾性体10の機械的強度が比較的高くなる。
本発明の装着品又はスポーツ用品は、上記弾性体10によって構成される防滑部材(以下、防滑部材10とも称する)を備えている。本発明の装着品又はスポーツ用品としては、使用時において使用者に着用若しくは装着される用品、又は、使用者が運動を行う際に使用される用品であれば特に限定されず、例えば、靴、ウェア、手袋、眼鏡、バット、ラケット、ゴルフクラブ等であってもよい。
該靴20は、足の上面を覆うアッパー材21と、アッパー材21の下側に配置されている靴底としてのミッドソール22及びアウターソール23とを有している。詳細には、該靴20は、地面と接する位置に配され、上記防滑部材10が設けられたアウターソール23と、アッパー材21とアウターソール23との間に配されたミッドソール22とを有している。
なお、本実施形態では、靴20はミッドソール22及びアウターソール23の両方を備えているが、靴20は、必ずしもこれらの両方を備えていなくてもよい。すなわち、靴20は、靴底として防滑部材10が設けられたアウターソール23のみを備え、ミッドソール22を備えていなくてもよい。この場合、アウターソール23は、ミッドソールに求められる緩衝性を確保するために、発泡体で形成されていてもよい。
靴底23では、図5に示されるように、靴底23の長さ方向における位置を、爪先側末端を0%位置、踵側末端を100%位置としたとき、靴底23の該長さ方向における0%~60%位置の範囲内の領域(以下、靴底23の前方領域とも称する)と、靴底23の該長さ方向における70%~100%位置の範囲内の領域(以下、靴底23の後方領域とも称する)とに、防滑部材10が設けられ得る。
好ましくは、防滑部材10は、靴底23の前方領域全体の5~100%を占める領域、靴底23の後方領域全体の5~100%を占める領域、又はその両方に設けられる。
なお、本明細書において、靴底23の長さ方向における0%~60%位置の範囲内の領域とは、爪先側末端及び踵側末端を通る長さ方向直線上において60%位置となる点を通り、該直線と垂直に交差する60%位置幅方向直線を規定し、該60%位置幅方向直線よりも爪先側における靴底23の領域をいう。同様に、靴底23の長さ方向における70%~100%位置の範囲内の領域とは、同様に規定される該70%位置幅方向直線よりも踵側における靴底23の領域をいう。また、これらの領域は、靴底23の底面を、図5のようにして正面から見た際の面積により指定される。
前身頃の胸部付近及び脇部は、ラグビーの試合時にボールを抱え込む際に対象物としてのボールに接触する部位である。そのため、これらの部位に防滑部材10が設けられたラグビーウェア30を着用したラグビープレイヤーは、汗で濡れたボールを滑り落としにくくなるという効果を得られる。
また、肩部は、ラグビーの試合時にスクラムを組む際に、対戦プレイヤーの肩と互いに接触する部位である。そのため、この部位に防滑部材10が設けられたラグビーウェア30を着用したラグビープレイヤーは、スクラムを組む際に滑りにくくなるという効果を得られる。
これらの部位に防滑部材10が設けられたスポーツ用手袋40を着用したプレイヤーは、把持している水や汗に濡れた対象物を滑り落としにくくなるという効果を得られる。
また、本実施形態の装着品又はスポーツ用品は、前記防滑部材を備えているため、ウェットグリップ性が向上した装着品又はスポーツ用品を提供することができる。
エラストマーとしての加硫ゴムの原料として、以下の材料を使用した。
・ポリマー:IR2200(日本ゼオン(株)製、イソプレンゴム) 100重量部
・加工助剤:ステアリン酸50S(新日本理化(株)製、ビーズ形状) 2重量部
・活性剤:活性亜鉛華No.2(本荘ケミカル(株)製) 5重量部
PEG#4000(日本油脂(株)製) 1重量部
・充填材:VN3(デグサジャパン(株)製、シリカ系無機充填材) 35重量部
・可塑剤:P-200(JTXG(株)製、プロセスオイル) 20重量部
・カップリング剤:Si69(デグサジャパン(株)製、ビス[3-(トリエトキシシリル)プロピル]ペルテトラスルフィド、ゴム/シリカ界面用) 3.5重量部
・老化防止剤:ノクラック200(大内新興化学工業(株)製、2,6-ジ-tert-ブチル-4-メチルフェノール) 1重量部
・加硫剤:硫黄#200(細井化学(株)製) 2重量部
・加硫促進剤:アクチングSL(三菱ケミカル(株)製、有機アミン) 1重量部
ノクセラーD(大内新興化学工業(株)製、DPG) 2重量部
ノクセラーDM(大内新興化学工業(株)製、MBTS) 2重量部
・ポリビニルアルコール:165-17915(富士フィルム和光純薬(株)製。けん化度80mol%)
:160-03055(富士フィルム和光純薬(株)製。けん化度88mol%)
:160-11485(富士フィルム和光純薬(株)製。けん化度98mol%)
・可塑剤:イオン交換水
・架橋剤:TC-400(マツモトファインケミカル(株)製。チタンジイソプロポキシビス(トリエタノールアミネート))
これらの材料を以下の表1に示される重量比により配合して、ポリビニルアルコールゲル(a)~(g)を調製した。
・カップリング剤:Si69(デグサジャパン(株)製、ビス[3-(トリエトキシシリル)プロピル]ペルテトラスルフィド、ゴム/PVAゲル界面用)
以下のようにして、加硫ゴムの表面及び内部にポリビニルアルコールゲル粒子が分散されている弾性体を、それぞれ作製した。
まず、上述の加硫ゴムの原料の各材料のうち、加硫剤、加硫促進剤を除いた全ての材料を、ニーダー(装置名:DS3-10MWB、日本スピンドル製造(株)製)を用いて80~130℃条件下で15分混練した。
これにより得られたゴム原料と、上記表1から選択されるポリビニルアルコールゲルと、場合により追加のシランカップリング剤とを、以下の表2に示される配合比率により配合して、上記加硫剤及び加硫促進剤と共に、オープンロール(装置名:KD-M2-8、利拿機械工業股フン有限公司(KNEADERMACHINERY CO., LTD.製)を用いて25~60℃条件下で10分混練した。
このようにして得られた弾性体原料を、平板状の金型内に導入し、装置名:ラム径12”150トン(二名工機(株)製)を用いて160℃条件下で5分間プレスすることによって、2mm厚の平板状に成型された弾性体を得た。得られた弾性体では、後述するポリビニルアルコールゲル被覆率の測定により、加硫ゴムの表面に、混練により微粒子化したポリビニルアルコールゲル粒子(平均粒子径:100~200μm)が分散されていることが確認された。
ポリビニルアルコールゲルを混練しないことを除いて、実施例1~15と同様の方法により、2mm厚の平板状に成型された弾性体を得た。
実施例1~15の弾性体を、フルオロセインナトリウム塩を1~100ppm含む水溶液中に1時間浸漬させた。続いて、該水溶液中から弾性体を取り出し、不織布を用いて弾性体に付着した水溶液を拭き取った後、暗室にて弾性体の表面に青色光を照射した。該表面では、ポリビニルアルコールゲルに起因する緑色の蛍光が見られた。
この蛍光を示している弾性体の表面をカメラにて撮像し、緑色の輝度分布を得ることにより、弾性体の表面にポリビニルアルコールゲルが露出している面積の比率(ポリビニルアルコールゲル被覆率)を算出した。
実施例1~15及び比較例1の弾性体の硬度を、アスカーA型硬度計として高分子計器(株)製「アスカーゴム硬度計A型」を用いて測定した。結果を以下の表2に示す。
実施例1~15及び比較例1の弾性体の静摩擦係数及び動摩擦係数を、水で濡らした弾性体上にプローブを滑らせることにより測定した。具体的には、雰囲気温度24℃、相対湿度75%RHの条件下、平面状に成型された弾性体の表面を水で濡らして、水で濡れた弾性体の表面上に、円柱状のアルミ製プローブ(直径10mm、長さ6.0mm)を、弾性体の該表面と該円柱の側面とが接触するように配置した。その後、該円柱を、垂直荷重0.981N、滑り速度10.0mm/sで、プローブの長さ方向に直交する方向に弾性体の表面上を滑らせて、その際の静摩擦係数及び動摩擦係数を測定した。
摩擦試験を行う前に、あらかじめ実施例1~15及び比較例1の弾性体を、雰囲気温度と同温の水中に配置し、そのまま1時間放置した。その後、該弾性体を水中より取り出した後、摩擦試験1と同様の方法によりそれらの静摩擦係数及び動摩擦係数を測定した。
上記摩擦試験に対する評価を、表2に示される結果に基づく図8~12を用いて以下に説明する。
図8及び図9は、比較例1及び実施例1~6の弾性体に関する、摩擦試験1における静摩擦係数及び動摩擦係数とポリビニルアルコールゲル配合量との関係を表す図である。
図8及び図9からわかるように、加硫ゴムの表面にハイドロゲル粒子が分散された実施例1~6の弾性体は、ハイドロゲルを含まない比較例1の弾性体に比べて、水に濡れた状態における静摩擦係数及び動摩擦係数の両方が大幅に高められている。
また、図9に示される実施例4~6の弾性体は、加硫ゴムとハイドロゲルとの間の界面をカップリングするための追加のシランカップリング剤を含んでいるが、それを含まない図8に示される実施例1~3の弾性体と同等の静摩擦係数及び動摩擦係数を示すこともわかる。
図10及び図11は、比較例1及び実施例1~6の弾性体に関する、摩擦試験2における静摩擦係数及び動摩擦係数とポリビニルアルコールゲル配合量との関係を表す図である。
図10からわかるように、実施例1~3の弾性体は、水中に1時間放置されることにより、ハイドロゲルによる静摩擦係数及び動摩擦係数の向上効果が失われている。これは、これらの弾性体では、水中に長く放置されると、加硫ゴムの表面からハイドロゲルの粒子が脱離してしまうことに起因すると考えられる。
これに対し、図11に示される実施例4~6の弾性体は、水中に1時間放置された後であっても、ハイドロゲルによる静摩擦係数及び動摩擦係数の向上効果を保っていることがわかる。これは、加硫ゴムとハイドロゲルとの間の界面をカップリングするシランカップリング剤により、加硫ゴムの表面とハイドロゲルの粒子とが強固に結合されているため、加硫ゴムの表面からハイドロゲルの粒子が脱離し難いためと考えられる。
したがって、実施例4~6の弾性体は、実施例1~3の弾性体に比べて、水に濡れた状況下で使用される際における耐久性が大きく高められていることがわかる。
図12及び図13は、実施例2、4及び7~9の弾性体に関する、摩擦試験1及び2における静摩擦係数及び動摩擦係数と追加のシランカップリング剤配合量との関係を表す図である。
図12からわかるように、これらの弾性体では、追加のカップリング剤の配合量が変化していても、ハイドロゲルによる静摩擦係数及び動摩擦係数の向上効果にほぼ影響を与えない。一方で、図13によれば、追加のカップリング剤の配合量を増やすと、水中に放置されることによる静摩擦係数及び動摩擦係数の低下が効果的に抑制されていることがわかる。
なお、図13では、追加のシランカップリング剤の配合量が1%である実施例9の弾性体において静摩擦係数及び動摩擦係数の低下が十分に抑制されており、それ以上にシランカップリング剤が配合されても、静摩擦係数及び動摩擦係数への影響があまり見られない。そのため、実施例9の弾性体では、静摩擦係数及び動摩擦係数の低下が最も効率的に抑制されていることがわかる。
図14及び図15は、実施例4及び10~13の弾性体に関する、摩擦試験1及び2における静摩擦係数及び動摩擦係数とポリビニルアルコールゲルに含まれる架橋剤の配合量との関係を表す図である。
図14からわかるように、これらの弾性体では、ハイドロゲルに含まれる架橋剤によっては、ハイドロゲルによる静摩擦係数及び動摩擦係数の向上効果は大きく変わらない。一方で、図15によれば、架橋剤が含まれていないハイドロゲルに比べて、架橋剤が含まれているハイドロゲルを用いると、水中に放置された後の静摩擦係数及び動摩擦係数の低下が効果的に抑制されることがわかる。
なお、図15では、ハイドロゲルの架橋剤配合量が0.02%である実施例11の弾性体において静摩擦係数及び動摩擦係数の低下が十分に抑制されており、それ以上に架橋剤が含まれていても、静摩擦係数及び動摩擦係数を効果的に高めることが難しいことがわかる。そのため、実施例11の弾性体では、静摩擦係数及び動摩擦係数が最も効率的に高められていることがわかる。
図16及び図17は、実施例4、14及び15の弾性体に関する、摩擦試験1及び2における静摩擦係数及び動摩擦係数とポリビニルアルコールゲルのけん化度との関係を表す図である。
図16及び図17からわかるように、ポリビニルアルコールゲルのけん化度が高いほど、これらの弾性体の静摩擦係数及び動摩擦係数が効果的に高められていることがわかる。これは、加硫ゴムの表面上に分散されたポリビニルアルコールゲルのけん化度が高いほど、ポリビニルアルコールゲルの親水性がより高くなるため、弾性体の表面と該表面上を滑る円柱との間に介在する水がポリビニルアルコールゲルの存在する位置へと引き寄せられることによる生じる水の局在化効果がより顕著になることに起因すると考えられる。
エラストマーの材料として、熱硬化性シリコーンゴムを使用した。
・ポリビニルアルコールゲル材料:上記の表1に示されるポリビニルアルコールゲル(a)を-196℃にて冷凍して粉砕した冷凍粉砕粒子(平均粒子径:10~100μm)。
・シリコーンハイドロゲル材料:市販のコンタクトレンズであるcomfilcon A(クーパービジョン社製、シリコーンハイドロゲルレンズ)を裁断したシリコーンハイドロゲル粒子(平均粒子径:1mm)
直径142mm、曲率半径71mmの凹面半球形状の時計皿上に、未硬化のシリコーンゴムを注いで時計皿を満たし、80℃条件下にて90分加熱して時計皿上のシリコーンゴムを硬化させた。シリコーンゴムが完全に硬化した後、硬化したシリコーンゲルからなる、時計皿の凹面形状に対応する凸形状を備えた弾性体を時計皿から取り出した。
時計皿上に未硬化のシリコーンゴムを注ぐ前に、該時計皿の凹面上にポリビニルアルコールゲルの冷凍粉砕粒子を分散配置させたことを除いて、比較例2と同様の方法で弾性体を得た。得られた弾性体は、硬化したシリコーンゴムの凸状表面上に、時計皿上に分散されていたポリビニルアルコールゲル粒子を備えていた。
未硬化のシリコーンゴムの代わりに、未硬化のシリコーンゴムとポリビニルアルコールゲルの冷凍粉砕粒子とを混合した混合液を時計皿に注いだことを除いて、比較例2と同様の方法で弾性体を得た。得られた弾性体は、硬化したシリコーンゴムの内部及び表面上に、ポリビニルアルコールゲル粒子を備えていた。
ポリビニルアルコールゲルの冷凍粉砕粒子の代わりに、シリコーンハイドロゲル粒子を時計皿の凹面上に分散配置したことを除いて、比較例2と同様の方法で弾性体を得た。得られた弾性体は、硬化したシリコーンゴムの凸状表面上に、時計皿上に分散されていたシリコーンハイドロゲル粒子を備えていた。
実施例16~18及び比較例2の弾性体の静摩擦係数及び動摩擦係数を、水で濡らしたガラス板上にこれらの弾性体を滑らせることにより測定した。具体的には、雰囲気温度24℃、相対湿度75%RHの条件下、平面状のガラス板の表面を水で濡らして、水で濡れたガラス板の表面上に、弾性体の凸状表面とガラス板とが接触するように弾性体を配置した。その後、弾性体を、垂直荷重0.981N、滑り速度10.0mm/sでガラス板の表面上を滑らせて、その際の静摩擦係数及び動摩擦係数を測定した。
表3に示される結果からわかるように、シリコーンゴム表面上にハイドロゲル粒子が分散された実施例16~18の弾性体においても、ハイドロゲルを含まないシリコーンゴムのみからなる比較例2の弾性体に比べて、水に濡れた状態における静摩擦係数及び動摩擦係数、すなわち、ウェットグリップ性が大幅に高められている。
さらに、実施例16~18によれば、シリコーンゴム表面上にハイドロゲル粒子が分散されてさえいれば、ハイドロゲル粒子による静摩擦係数及び動摩擦係数の向上効果は、ハイドロゲル粒子がシリコーンゴムの内部にあってもなくても発揮されることがわかる。また、ハイドロゲルとしてポリビニルアルコールゲル又はシリコーンハイドロゲルのどちらを使用した際であっても、水に濡れた状態における静摩擦係数及び動摩擦係数が高められることがわかる。
エラストマーとして上述のシリコーンゴム材料を、ハイドロゲルとして上述のポリビニルアルコールゲル材料(a)の冷凍粉砕粒子を使用した。
時計皿の代わりに、地面と接触する面である底面が平坦な形状となった靴用のアウターソール(足長27cm)の形状に対応した靴底用金型を用いたことを除いて、比較例2と同様の方法で弾性体を得た。
靴底用金型内に未硬化のシリコーンゴムを注ぐ前に、靴底用金型内の底面にポリビニルアルコールゲルの冷凍粉砕粒子を分散配置させたことを除いて、比較例2と同様の方法で弾性体を得た。得られた弾性体は、アウターソールの底面側表面上に、靴底用金型内に分散されていたポリビニルアルコールゲル粒子を備えていた。
実施例19及び比較例4の弾性体の静摩擦係数及び動摩擦係数を、JIS T8101に準拠して測定した。具体的には、アウターソールを有さない靴の靴底に、実施例19及び比較例4の弾性体を固定した後、雰囲気温度24℃、相対湿度75%RHの条件下、平面状の鉄板の表面を水で濡らして、水で濡れた鉄板の表面上に、弾性体の底面と鉄板とが接触するように、弾性体を備えた靴を配置した。その後、弾性体を、垂直荷重500N、滑り速度300mm/sで鉄板の表面上を滑らせて、その際の静摩擦係数及び動摩擦係数を測定した。
表4に示される結果からわかるように、シリコーンゴム表面上にハイドロゲル粒子が分散された実施例19の弾性体は、靴用の靴底部材であるアウターソールの形状において、アウターソールとして使用される場合であっても、ハイドロゲルを含まない比較例3のアウターソール形状の弾性体に比べて、水に濡れた状態における静摩擦係数及び動摩擦係数、すなわち、ウェットグリップ性が大幅に高められている。
Claims (12)
- 装着品又はスポーツ用品用の防滑部材であって、
前記防滑部材が、エラストマーとハイドロゲルとを備えた弾性体により構成されており、
前記ハイドロゲルの少なくとも一部が、前記弾性体の表面に分散されている、防滑部材。 - 前記弾性体の表面において、前記ハイドロゲルの占める面積が、前記弾性体の表面全体の面積の1~25%である、請求項1に記載の防滑部材。
- 前記ハイドロゲルが、架橋体である、請求項1又は2に記載の防滑部材。
- 前記ハイドロゲルが、ポリビニルアルコールゲルを含んでいる、請求項3に記載の防滑部材。
- 前記ポリビニルアルコールゲルのけん化度が、80~100%である、請求項4に記載の防滑部材。
- 前記ハイドロゲルが、シリコーンハイドロゲルを含んでいる、請求項1~3のいずれか1項に記載の防滑部材。
- 前記弾性体が、さらにシランカップリング剤を含んでいる、請求項1~6のいずれか1項に記載の防滑部材。
- 前記ハイドロゲルが、前記弾性体の内部にも分散されており、
前記エラストマーに対して1~10重量%の量の前記ハイドロゲルを含んでいる、請求項1~7のいずれか1項に記載の防滑部材。 - 請求項1~8のいずれか1項に記載の防滑部材を備えた装着品。
- 前記装着品が靴であり、
前記防滑部材が、前記靴の靴底の地面に接触する位置に設けられている、請求項9に記載の装着品。 - 前記防滑部材が、かかと、中足指節関節又はつま先のうち少なくとも1箇所に対応する位置に設けられている、請求項10又は11に記載の装着品。
- 請求項1~8のいずれか1項に記載の防滑部材を備えたスポーツ用品。
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