US20230119951A1 - Shoe sole and shoe - Google Patents

Shoe sole and shoe Download PDF

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Publication number
US20230119951A1
US20230119951A1 US17/905,460 US202017905460A US2023119951A1 US 20230119951 A1 US20230119951 A1 US 20230119951A1 US 202017905460 A US202017905460 A US 202017905460A US 2023119951 A1 US2023119951 A1 US 2023119951A1
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Prior art keywords
rubber
mass
parts
rubber composition
shoe sole
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Pending
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US17/905,460
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English (en)
Inventor
Toshiaki NISHI
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Asics Corp
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Asics Corp
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Publication of US20230119951A1 publication Critical patent/US20230119951A1/en
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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
    • 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
    • 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
    • A43B13/223—Profiled soles

Definitions

  • the present invention relates to a shoe sole and a shoe.
  • Shoes are sometimes used on the ground wet by water during or after rain.
  • the ground wet by water is likely to cause slippage and may cause the wearer of the shoes to slip on the ground when the wearer moves on the ground.
  • Patent Literature 1 WO/2007-007412 A
  • a shoe sole according to the present invention is composed of a rubber composition including rubber and activated carbon.
  • a shoe according to the present invention includes the aforementioned shoe sole.
  • FIG. 1 is a schematic view showing a surface of an elastic body forming a shoe sole according to one embodiment.
  • FIG. 2 is a schematic view showing the elastic body of FIG. 1 before it makes contact with an object wet by water.
  • FIG. 3 is a schematic view showing the elastic body of FIG. 1 after it makes contact with the object wet by water.
  • FIG. 4 is a schematic view showing a shoe as a wearable equipment of one embodiment, which has an anti-slip member provided at a ground engaging position of a shoe sole.
  • FIG. 5 is a schematic view showing an apparatus for observing and imaging a contact portion between rubber and a flat plate shaped glass by performing a friction test in a preliminary study of examples.
  • FIG. 6 is a photograph showing contact portions between the flat plate shaped glass and the rubber after the flat plate shaped glass is slid 5 mm on the rubber having a smooth surface at an apex in contact with the glass, in the preliminary examination of examples.
  • FIG. 7 is a photograph showing contacting portions between the flat plate shaped glass and the rubber after the flat plate shaped glass is slid 5 mm on the rubber having pores of about 100 ⁇ m 3 formed at the apex in contact with the glass, in the preliminary study of examples.
  • FIG. 8 is a graph representing the areas of the contact portions between the flat plate shaped glass and the rubber after the flat plate shaped glass is slid 5 mm on the rubber in the preliminary study of examples.
  • FIG. 9 is a graph showing the static friction coefficients between the flat plate shaped glass and the rubber after the flat plate shaped glass is slid 5 mm on the rubber in the preliminary study of examples.
  • FIG. 1 is a schematic view showing a surface of an elastic body 10 of this embodiment.
  • the elastic body 10 of this embodiment includes rubber 11 and activated carbon 12 , and at least part of particles of the activated carbon 12 is exposed on the surface of the elastic body 10 .
  • the present inventors have found that, in a shoe sole composed of a rubber composition, inclusion of particles having pores into which water hardly enters in the shoe sole can solve the above problem. And the present inventors have found that activated carbon is suitable as such particles.
  • activated carbon Since activated carbon has high hydrophobicity and the size of the pores open to the surface is generally about 1 ⁇ m, water hardly enters the pores even when water is in contact with the pores.
  • the present inventors have found that when activated carbon having pores which have been considered unsuitable for the purpose of absorbing water is disposed on a shoe sole, air is released from the pores of activated carbon due to strain of the shoe sole at the time of the contact of the shoe sole with the ground via a water film, and a region in which the shoe sole and the ground are in direct contact with each other is formed, thereby have completed the present invention.
  • FIG. 2 is a schematic view showing the elastic body 10 composed of the same composition as the composition of the shoe sole of this embodiment before it makes contact with an object G wet by water W.
  • FIG. 3 is a schematic view showing the elastic body 10 after it makes contact with the object G wet by the water W.
  • the object G is herein represented as the ground wet by the water W.
  • FIG. 3 shows the state in which strain is being applied to the interface between the ground and the elastic body 10 by the strain applied to the elastic body 10 in the direction of the arrow.
  • the activated carbon 12 has a large number of pores.
  • the activated carbon 12 When the pore distribution is measured by the mercury intrusion method, the activated carbon 12 usually exhibits a peak in any portion of the ranges of 0.5 ⁇ m or more and 3 ⁇ m or less. In other words, the activated carbon 12 has a large number of pores having a diameter of 0.5 ⁇ m to 3 ⁇ m centered on a diameter of about 1 ⁇ m.
  • the activated carbon 12 is usually less hydrophilic (more hydrophobic) than porous particles such as silica or zeolite. For the activated carbon 12 having high hydrophobicity, water hardly enters the pores having a small diameter as described above because the contact angle increases.
  • the activated carbon 12 exposed on the surface of the elastic body 10 in which strain is applied to the interface with the ground releases air A from the pores.
  • the amount of the air A released at this time is small, a gap is hardly formed between the elastic body 10 having low elasticity and the ground, so that the air A can be spread over a relatively wide range.
  • a driving force that minimizes the sum of the surface free energies is exerted so that water is expelled between the elastic body 10 and the ground in the region where the air A is interposed, thereby allowing the surface of the elastic body 10 to be in direct contact with the ground. In this way, a large number of portions where the elastic body 10 and the ground come into direct contact with each other without water interposed therebetween are formed, so that the elastic body 10 exhibits high grip performance.
  • the elastic body 10 of this embodiment exhibits the above-described characteristics by including a specific component such as activated carbon in the rubber composition. It is preferable that the rubber composition have specific physical property value in order for the elastic body 10 to exhibit the above-described characteristics.
  • the content of the activated carbon in the rubber composition is preferably 0.1% by mass or more because excellent wet-grip performance can be imparted to the elastic body 10 .
  • the content of the activated carbon is more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more.
  • the content of the activated carbon is preferably 10% by mass or less because excellent strength can be imparted to the elastic body 10 .
  • the content of the activated carbon is more preferably 5% by mass or less, still more preferably 3% by mass or less.
  • the activated carbon can be made of a plant such as coconut shell, wood, or bamboo as a raw material, or can be made of peat, coal, plastic, or the like as a raw material.
  • the activated carbon is obtained from a plant raw material in that it has a large number of pores as described above.
  • the activated carbon is preferably powdered activated carbon. It is preferable that the powdered activated carbon have a particle diameter in which a passing ratio of 150 ⁇ m mesh is 90% by mass or more. It is more preferable that the powdered activated carbon have a particle diameter in which a passing ratio of 75 ⁇ m mesh is 90% by mass or more.
  • the activated carbon is not limited to powdered activated carbon, and can be granular activated carbon.
  • an elastomer generally used for forming a shoe sole is used.
  • the elastomer include a vulcanized rubber such as an isoprene rubber (IR), a natural rubber (NR), a butadiene rubber (BR), a styrene butadiene rubber (SBR), a chloroprene rubber (CR), an acrylonitrile butadiene rubber (NBR), a butyl rubber (IIR), or a silicone rubber (Si); and a thermoplastic elastomer such as a styrene-based elastomer (TPS), an olefin-based elastomer (TPO), a urethane-based elastomer (TPU), a polyester-based elastomer (TPEE), polyamide-based elastomer (TPA), polyvinyl chloride (PVC), or an ethylene-vinyl acetate copoly
  • a vulcanized rubber such as an is
  • the rubber composition can further include an inorganic filler such as silica, alumina, calcium carbonate, magnesium carbonate, carbon black, graphite, talc, or clay.
  • an inorganic filler having excellent hydrophilicity is suitably included in the rubber composition.
  • Silica having a large number of silanol groups (—Si—OH) which are hydrophilic functional groups on the particle surface is suitably selected for the inorganic filler included in the rubber composition.
  • the silica can be wet silica or dry silica.
  • the wet silica can be precipitated silica, gel silica, or colloidal silica.
  • the dry silica can be flame silica or arc method silica. It is preferable that the silica be wet silica. It is preferable that the wet silica include aggregated particles in which a plurality of primary particles of about 20 ⁇ m are aggregated. Precipitated silica is suitable because it includes a large amount of aggregated particles which are easily decomposed into primary particles, is easy to handle, and is excellent in dispersibility of primary particles in rubber.
  • the content of the silica in the rubber composition is preferably 10 parts by mass or more based on 100 parts by mass of the rubber.
  • the content of the silica is more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more.
  • the content of the silica in the rubber composition is preferably 100 parts by mass or less based on 100 parts by mass of the rubber.
  • the content of the silica is more preferably 90 parts by mass or less, still more preferably 80 parts by mass or more.
  • the rubber composition include a silane coupling agent together with silica.
  • the silane coupling agent in this embodiment has a hydrolyzable functional group at the end of the molecular chain, and can further have an organic functional group other than the hydrolyzable functional group.
  • the hydrolyzable functional group can be an alkoxy group, a phenoxy group, a carboxyl group, an alkenyloxy group, or the like.
  • the organic functional group can be an epoxy group, a vinyl group, an acryloyl group, a methacryloyl group, an amino group, a sulfide group, a mercapto group, or the like.
  • the silane coupling agent in this embodiment preferably has a sulfide group.
  • the silane coupling agent in this embodiment is preferably a sulfide-based silane coupling agent.
  • the sulfide-based silane coupling agent can be a monosulfide-based silane coupling agent or a polysulfide-based silane coupling agent.
  • sulfide-based silane coupling agent examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl-tetrasulfide, and 3-octanoylthio-1-propyltriethoxys
  • a polysulfide-based silane coupling agent is preferred.
  • the polysulfide-based silane coupling agent also works effectively in crosslinking of rubber. Among them, bis(3-triethoxysilylpropyl)tetrasulfide is preferred.
  • the silane coupling agent can be included in the rubber composition at a ratio of 1 part by mass or more when the content of silica in the rubber composition is set to 100 parts by mass.
  • the content of the silane coupling agent is preferably 6 parts by mass or more, more preferably 7 parts by mass or more, based on 100 parts by mass of the silica.
  • the content of the silane coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the silica.
  • the rubber composition can further include a compound having excellent hydrophilicity such as polyethylene glycol.
  • the polyethylene glycol preferably has a mass average molecular weight of 2000 or more and 5000 or less.
  • the mass average molecular weight is determined as a value in terms of polystyrene by the GPC method.
  • the content of the polyethylene glycol in the rubber composition is preferably 0.1 parts by mass or more based on 100 parts by mass of the rubber.
  • the content of the polyethylene glycol is more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more.
  • the content of the polyethylene glycol is more preferably 10 parts by mass or less, still more preferably 2 parts by mass or less.
  • the rubber composition can include a plasticizer such as paraffin oil (liquid paraffin). It is preferable that the content of a highly hydrophobic plasticizer such as paraffin oil be 30 parts by mass or less based on 100 parts by mass of the rubber.
  • the rubber composition of this embodiment can further include other optional components such as a vulcanizing agent, a vulcanization accelerator, a crosslinking accelerator, a filler, an antioxidant, or an ultraviolet absorber.
  • a vulcanizing agent such as a vulcanizing agent, a vulcanization accelerator, a crosslinking accelerator, a filler, an antioxidant, or an ultraviolet absorber.
  • the hardness of the rubber composition is preferably set to 50 or more and 80 or less as measured by a Type A durometer based on JIS K 6253-3:2012.
  • the tensile elastic modulus of the rubber composition is preferably 12 MPa or less.
  • the tensile elastic modulus of the rubber composition is more preferably 10 MPa or less, still more preferably 8 MPa or less.
  • the tensile elastic modulus is preferably 1 MPa or more.
  • the rubber composition have a tensile strength of 15 MPa or more measured on the basis of JIS K6251:2017 “Rubber, vulcanized or thermoplastic-Determination of tensile stress-strain properties” in terms of exhibiting properties required for a shoe sole. It is preferable that the rubber composition have a tensile elongation at break of 350% or more measured based on the same JIS.
  • the tear strength determined on the basis of JIS K6252-1:2015 “Rubber, vulcanized or thermoplastic—Determination of tear strength—Part 1: Trouser, angle and crescent test pieces” is preferably 40 N/mm or more. The tear strength can be measured using an angle-shaped test piece (without notches).
  • the tensile strength of the rubber composition is more preferably 18 MPa or more, still more preferably 20 MPa or more.
  • the tensile strength is usually 50 MPa or less.
  • the tensile elongation at break of the rubber composition is 400% or more, still more preferably 500% or more.
  • the tensile elongation at break is usually 1000% or less.
  • the tear strength of the rubber composition is more preferably 50 N/mm or more, still more preferably 60 N/mm or more.
  • the tensile strength is usually 120 N/mm or less.
  • the rubber composition of this embodiment can be produced by kneading the above components, that is, the rubber, the activated carbon, and, optionally, silica, the silane coupling agent, polyethylene glycol, and the like by any method generally carried out by a person skilled in the art.
  • a method of kneading the above components using an open roll or a kneader can be used as the kneading method.
  • the shoe sole of this embodiment exhibits high wet-grip performance by being composed of the rubber composition, as described above while exemplifying the aforementioned elastic body 10 .
  • FIG. 4 is a schematic view showing a shoe 20 of one embodiment, which has the rubber composition (elastic body) provided at a ground engaging position of a shoe sole 23 .
  • the shoe 20 includes an upper member 21 covering the upper surface of the foot, a midsole 22 arranged on the lower side of the upper member 21 , and an outer sole 23 in contact with the ground.
  • the shoe 20 includes both the midsole 22 and the outer sole 23 , but the shoe 20 does not necessarily include both of them. That is, the shoe 20 can be configured to include only the outer sole 23 as the shoe sole, and include no midsole 22 .
  • the shoe sole according to this embodiment is composed of a rubber composition including rubber and activated carbon, high wet-grip performance can be exhibited.
  • the rubber composition of the shoe sole according to this embodiment has a tensile elastic modulus of 10 MPa or less. Therefore, the wet-grip performance of the shoe sole can be effectively enhanced in such a case.
  • the shoe sole according to this embodiment has a content of the activated carbon in the rubber composition being 0.1% by mass or more and 5% by mass or less. In such a case, excellent wet-grip performance and excellent strength can be imparted to the rubber composition.
  • the rubber composition further includes silica, and the content of the silica in the rubber composition is 10 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the rubber.
  • the hydrophilicity of the rubber composition can be suitably enhanced.
  • the rubber composition further includes polyethylene glycol, and the content of the polyethylene glycol in the rubber composition is 0.1 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the rubber.
  • the hydrophilicity of the rubber composition can be suitably enhanced.
  • the shoe according to the present invention includes the above-described shoe sole, high wet-grip performance can be exhibited.
  • All of the rubbers used in the friction test were hemispherical silicone rubbers having a radius of curvature of 7.6 mm, one of which was a rubber SP 1 having a smooth surface on which a recess or the like was not provided at an apex, and the other was a rubber SP 2 having a recess (pore) of about 100 ⁇ m 3 formed at an apex in contact with the glass. Fluorescent particles were kneaded into these rubbers in order to facilitate observation of the contact state with the flat plate shaped glass during the friction test.
  • the true contact part of the rubber SP 1 ,SP 2 and the flat plate shaped glass GL was continued to be observed using the device shown in FIG. 5 .
  • the true contact part was imaged.
  • the device includes a light source LS for illuminating the true contact part and a CCD device CD for imaging the true contact part. The true contact part was observed and imaged by combining the total reflection method and the optical interference method.
  • FIG. 6 and FIG. 7 show photographs of the real contact parts respectively imaged under the non-lubricated conditions and the water lubricated conditions.
  • the black regions are the true contact parts
  • the white regions are the regions where the flat plate shaped glass GL is not in contact with the rubber SP 1 ,SP 2 .
  • the gray region is a part where the flat plate shaped glass GL is in contact with water (is wet)
  • the white region is a part where the flat plate-shaped glass GL is not in contact with any of water and the rubber SP 1 ,SP 2 (air is present).
  • FIG. 9 shows the measured static friction coefficient.
  • the area of the true contact part between the rubber SP 2 and the flat plate shaped glass GL after the flat plate shaped glass GL is slid 5.0 mm is increased by about 38% compared with the rubber SP 1 , and the friction coefficient is also increased by about 27%.
  • the friction coefficient is improved in the water-lubricated conditions compared with the non-lubricated conditions. From this result, it can be seen that in the rubber in which pores are formed on the surface, the wet-grip performance in the water lubricated conditions is greatly improved so as to be able to exceed the non-lubricated conditions.
  • SiO 2 , PO, CA, St, and ZnO as materials for secondary kneading were blended by the blending ratios (mass ratios) shown in Table 1 below, and kneaded using a kneader (device name: DS3-10MWB, manufactured by Nippon Spindle Manufacturing Co., Ltd.) at 80 to 130° C. for 10 minutes to obtain a secondary kneading material.
  • a kneader device name: DS3-10MWB, manufactured by Nippon Spindle Manufacturing Co., Ltd.
  • OA, PEG, and AO as materials for tertiary kneading were blended by the blending ratios (mass ratios) shown in Table 1 below, and kneaded using an open roll (device name KD-M2-8, manufactured by KNEADER MACHINERY CO., LTD.) at 25 to 60° C. for 10 minutes to obtain rubbers (a) to (d).
  • the rubber thus prepared, the activated carbon, and the other materials were blended in the blending ratios (mass ratios) shown in Table 2 below, and kneaded at 25 to 60° C. for 10 minutes using an open roll (device name KD-M2-8, manufactured by KNEADER MACHINERY CO., LTD.). Thus, the rubber compositions were obtained.
  • Measuring mode Tensile mode of sine wave distortion
  • Test pieces each molded into a flat plate shape having a thickness of 2 mm were obtained by introducing the rubber composition of each of Comparative Examples 1 to 4 and Examples 1 to 10 into a flat plate shaped mold, followed by pressing at 160° C. for 8 to 12 minutes (a predetermined appropriate vulcanization time T90+2 minutes) using a device (name: Ram diameter of 12′′ 150 tons (manufactured by Nimei Koki Co., Ltd.)).
  • the static friction coefficient and the dynamic friction coefficient in the water lubricated conditions were measured by wetting these test pieces with water and sliding the probe on the test pieces. Specifically, at an ambient temperature of 24° C.
  • the rubber (a) alone according to Comparative Example 1 having a smaller content of the silane coupling agent than the rubber (b) is excellent in terms of the static friction coefficient and the dynamic friction coefficient, the mechanical strength such as hardness is greatly inferior to that of the rubber compositions of Examples 1 to 5. Therefore, it can be seen that the rubber compositions of Examples 1 to 5 have increased static friction coefficient and dynamic friction coefficient in the water lubricated conditions while maintaining sufficient mechanical strength.
  • the rubber compositions of Examples 1 to 3 in which the content of the activated carbon is 1 phr or less are excellent in terms of mechanical strength because the tensile strength is kept higher than that of the rubber compositions of Examples 4 and 5 in which the content of the activated carbon is 5 phr or more.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US17/905,460 2020-03-06 2020-03-06 Shoe sole and shoe Pending US20230119951A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2020/009680 WO2021176685A1 (ja) 2020-03-06 2020-03-06 靴底、及び、靴

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US (1) US20230119951A1 (de)
EP (1) EP4101332A4 (de)
JP (1) JPWO2021176685A1 (de)
CN (1) CN115209761A (de)
WO (1) WO2021176685A1 (de)

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
DE2536674C3 (de) * 1975-08-18 1979-09-27 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Vernetzbare Mischungen auf Basis von Kautschuk, Organosilanen und silikatischen Füllstoffen
JP3717260B2 (ja) * 1997-02-18 2005-11-16 横浜ゴム株式会社 スタッドレスタイヤ用ゴム組成物
JP4462396B2 (ja) * 2000-08-09 2010-05-12 青木安全靴製造株式会社 靴底用ゴム組成物及びそのゴム組成物を使用した靴底、並びに、靴
TWI386419B (zh) * 2004-12-20 2013-02-21 Ube Industries 聚丁二烯橡膠之製造方法及橡膠組合物
WO2007007412A1 (ja) 2005-07-14 2007-01-18 Moonstar Chemical Corporation 靴底用ゴム組成物
EP2045287A4 (de) * 2006-07-26 2010-03-03 Ube Industries Kautschukzusammensetzung für eine schuhsohle und kautschuk-schaumstoff-zusammensetzung
CN116138540A (zh) * 2018-06-04 2023-05-23 耐克创新有限合伙公司 两部分鞋底结构及其用途

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EP4101332A1 (de) 2022-12-14
CN115209761A (zh) 2022-10-18
EP4101332A4 (de) 2023-01-25
JPWO2021176685A1 (de) 2021-09-10

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