EP3248495A1 - Semelle d'usure et chaussures - Google Patents

Semelle d'usure et chaussures Download PDF

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Publication number
EP3248495A1
EP3248495A1 EP15859126.3A EP15859126A EP3248495A1 EP 3248495 A1 EP3248495 A1 EP 3248495A1 EP 15859126 A EP15859126 A EP 15859126A EP 3248495 A1 EP3248495 A1 EP 3248495A1
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EP
European Patent Office
Prior art keywords
outer sole
based elastomer
elastomer
shoe
free energy
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EP15859126.3A
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German (de)
English (en)
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EP3248495A4 (fr
EP3248495B1 (fr
Inventor
Toshiaki NISHI
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Asics Corp
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Asics Corp
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Publication of EP3248495A4 publication Critical patent/EP3248495A4/fr
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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
    • A43B13/02—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
    • 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
    • A43B5/00—Footwear for sporting purposes
    • A43B5/02—Football boots or shoes, i.e. for soccer, football or rugby
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B5/00—Footwear for sporting purposes
    • A43B5/06—Running shoes; Track shoes

Definitions

  • the present invention relates to an outer sole of a shoe and a shoe having the same.
  • Various shoes including sports shoes are composed of a shoe body and an outer sole attached to the bottom side of the shoe body.
  • Typical shoes are required to have a grip performance on a road surface.
  • the term "grip performance” herein refers to the slip resistance.
  • the term "road surface” herein refers to any surface on which a person wearing shoes walks or runs, including the surface of a road such as a sidewalk, the surface of a floor in a building such as a gymnasium, and the surface of unpaved ground.
  • outer soles with the improved grip performance include an outer sole produced by using a polymer material having a relatively high glass transition temperature and an outer sole produced by using a short fiber (Patent Document 1).
  • the level of grip performance exhibited by conventional outer soles is not high enough.
  • the level of grip performance exhibited by conventional outer soles on a wet road surface is not enough due to the presence of liquid between the wet road surface and the outer sole surface.
  • the term "outer sole surface” herein refers to one of the surfaces of an outer sole that comes into contact with a road surface.
  • the term "liquid” herein refers to water or oil, for example, present on a road surface.
  • An object of the present invention is to provide an outer sole having an excellent grip performance and a shoe having the same.
  • the outer sole of the present invention includes a thermoplastic elastomer and has a surface free energy of 12 mJ/m 2 or higher.
  • the outer sole of the present invention has an arithmetic mean roughness, Ra, of 1000 ⁇ m or lower.
  • the thermoplastic elastomer contains at least one elastomer selected from a chlorinated polyethylene-based elastomer, a chlorosulfonated polyethylene-based elastomer, a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, and a urethane-based elastomer.
  • the thermoplastic elastomer contains at least one of a chlorinated polyethylene-based elastomer and a chlorosulfonated polyethylene-based elastomer.
  • a shoe is provided.
  • the shoe of the present invention includes any one of the outer sole mentioned above.
  • An outer sole of the present invention has an excellent grip performance, particularly on a wet road surface.
  • a shoe having this outer sole has a slip resistance to be exhibited during walking on a dry road surface and even on a wet road surface.
  • An outer sole of the present invention is produced by using a composition containing a thermoplastic elastomer, and has a surface free energy of 12 mJ/m 2 or higher.
  • a shoe having the outer sole produced by using the thermoplastic elastomer and having a surface free energy of 12 mJ/m 2 or higher has an excellent grip performance, particularly on a wet road surface.
  • liquid While a person is walking on a wet road surface with shoes on, liquid is typically present between the outer sole surface of each shoe and the road surface, in a form of a thin film of liquid.
  • the presence of the film of liquid prevents the outer sole surface from coming into direct contact with the road surface, and thereby the shoe easily slips on the road surface.
  • the film of liquid present between the outer sole surface and the road surface is called a "liquid film”.
  • the inventor of the present invention conjectured that an outer sole capable of inhibiting formation of the liquid film can readily come into direct contact with a road surface and thereby have an improved grip performance on a wet road surface.
  • an outer sole containing a thermoplastic elastomer and having a surface free energy of 12 mJ/m 2 or higher induces spontaneous discharge of liquid from the gap between the outer sole surface and a road surface.
  • the outer sole having a surface free energy of 12 mJ/m 2 or higher readily comes into direct contact with the road surface and therefore exhibits an excellent grip performance, particularly on a wet road surface.
  • the present invention is based on preliminary findings conducted by the inventor of the present invention. First, the preliminary findings are described below.
  • the inventor of the present invention has conducted friction testing.
  • various floorings and lubricants with different levels of the surface free energy were tested on one type of rubber material.
  • the "rubber material” in the [Preliminary findings] section corresponds to the outer sole in the present specification.
  • the "flooring” in the [Preliminary findings] section corresponds to the road surface in the present specification.
  • the “lubricant” in the [Preliminary findings] section corresponds to the liquid in the present specification.
  • PTFE polytetrafluoroethylene
  • PP polypropylene
  • PMMA polymethylmethacrylate
  • PET polyethylene terephthalate
  • Reference table (A) in Fig. 5 shows the values of arithmetic mean roughness (surface roughness), Ra, and the root-mean-square roughness, Rq, of the rubber material and each flooring.
  • Rq R and Rq S each denote the root-mean-square roughness of the rubber material and the root-mean-square roughness of a flooring, respectively.
  • the arithmetic mean roughness, Ra was measured with an atomic force microscope (Environmental Control Unit E-sweep, manufactured by Hitachi High-Tech Science Corporation), equipped with a cantilever, SI-DF20, manufactured by Hitachi High-Tech Science Corporation.
  • Reference table (A) has proven that the values of composite roughness, ⁇ , of all the floorings are similar to each other.
  • the inventors of the present invention determined that the arithmetic mean roughness (surface roughness), Ra, has not much influence on the friction testing.
  • lubricant water or a mixture of water and ethanol (ethanol concentration of 10 vol%, 30 vol%, and 90 vol%) were used.
  • Reference table (B) in Fig. 6 shows the viscosity of each lubricant.
  • water ion-exchanged water purified with REP343RB manufactured by Advantec was used.
  • ethanol a Wako 1st Grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • the value of viscosity of each lubricant was from a document ( Kagaku Binran, Kiso Hen (Handbook of Chemistry, Basic Version), 2nd Revision, P.574 (1975), published by Maruzen Publishing, Co., Ltd. ).
  • FIG. 7 shows an outline of a friction tester (HEIDON14 manufactured by Shinto Scientific Co., Ltd.).
  • a friction tester HIDON14 manufactured by Shinto Scientific Co., Ltd.
  • a hemispherical crosslinked isoprene rubber having an initial modulus of elasticity of 3.28 MPa was used (the hemisphere corresponded to a half of a sphere having a diameter of 25 mm).
  • a rubber material was brought into contact with a smooth flooring that had been thoroughly immersed in a lubricant. Then, the rubber material was linearly moved at a rate of 1.67 mm/second for 2.0 seconds or longer with a vertical load of 1.96 N being applied, while the friction force was being measured.
  • the friction force measured when the rubber material started to slide was used to calculate the coefficient of static friction.
  • Reference table (D) in Fig. 8 shows the values of the surface free energy of the rubber material, the floorings, and the lubricants.
  • the values of the surface free energy of the rubber material and the floorings were calculated according to the Kaelble-Uy's theory, based on the contact angles against 1.0 ⁇ L of ion-exchanged water and diiodomethane (Wako 1st Grade reagent manufactured by Wako Pure Chemical Industries, Ltd.), respectively, measured 10 seconds after dropping of each liquid.
  • the contact angle was measured with a contact angle meter (DM-510Hi manufactured by Kyowa Interface Science Co., Ltd.).
  • the values of the surface free energy of water and diiodomethane were from a document (D. H.
  • ⁇ SL , ⁇ RL , and ⁇ RS each denote the interfacial free energy between a flooring and a lubricant, the interfacial free energy between the rubber material and a lubricant, and the interfacial free energy between the rubber material and a flooring, respectively.
  • the interfacial free energy was calculated according to the Kaelble-Uy's theory, by Formula (3).
  • the spreading coefficient, S provides the following interpretation: the formation of a liquid film at the point of contact between the rubber material, the selected flooring, and the selected lubricant is inhibited when the spreading coefficient, S, is negative, and the formation is facilitated when the spreading coefficient, S, is positive.
  • ⁇ i and ⁇ j each denote the surface free energy of substance i and the surface free energy of substance j, respectively; ⁇ ij denotes the interfacial free energy between substance i and substance j; and ⁇ d and ⁇ p each denote the dispersion component and the polar component of the surface free energy, respectively.
  • the amount of work required for detaching the rubber material from contact with each flooring is expressed as a work of adhesion, W.
  • the work of adhesion, W is calculated by Formula (4).
  • ⁇ S and ⁇ R each denote the surface free energy of a flooring and the surface free energy of the rubber material, respectively.
  • a solid-solid interface, a solid surface, and a liquid surface are all thermodynamically unstable compared to a bulk of solid or liquid.
  • the amount of work required for detaching the rubber material from each flooring can be obtained by calculating the work of adhesion, W.
  • Reference figure (H) shows that there were fluctuations in the coefficients of static friction and dynamic friction of the rubber material depending on the surface free energy of each flooring, but reference figure (H) does not show any correlation between the surface free energy of each flooring and the coefficients of static friction and dynamic friction of the rubber material.
  • the spreading coefficient, S is an index of tendency of a lubricant to spread on a mating material.
  • the spreading coefficient, S, at the point of contact between the rubber material, each flooring, and a lubricant indicates the tendency of the lubricant to penetrate the interface between the rubber material and the flooring, providing the following interpretation: the formation of a liquid film at the point of contact is inhibited when the spreading coefficient, S, is negative, and the formation is facilitated when the spreading coefficient, S, is positive.
  • the relationship between the ethanol concentration in a lubricant and the spreading coefficient is shown in reference figure (J) in Fig. 14 .
  • Reference figure (J) shows that the spreading coefficient on each flooring increased as the ethanol concentration increased.
  • the spreading coefficient on marble flooring was always higher than those of other floorings regardless of the ethanol concentration. This phenomenon occurred because the polar component, ⁇ p , of the surface free energy of marble is higher than those of other floorings.
  • the interface of contact between the rubber material and a flooring has an interfacial free energy, ⁇ RS , and the action of external energy causes detachment of the rubber material from contact with the flooring.
  • the energy required for this detachment is expressed as work of adhesion, W.
  • the relationship between the work of adhesion and either of the coefficients of static friction and dynamic friction of the rubber material is shown in reference figure (L) in Fig. 16 .
  • Reference figure (L) shows that the coefficients of static friction and dynamic friction of the rubber material on any lubricant tended to increase as the work of adhesion increased.
  • the coefficients of static friction and dynamic friction of the rubber material at a certain level of work of adhesion tended to decrease as the ethanol concentration in the lubricant increased.
  • the inventor of the present invention has found the followings: as the surface free energy increases, the work required for detaching an outer sole surface from contact with a road surface increases and thereby the coefficients of static friction and dynamic friction of the outer sole on the road surface increases; and as the surface free energy increases, removal of a liquid film from the gap between the outer sole surface and the road surface is facilitated by thermodynamics, making the outer sole readily coming into direct contact with the road surface and thereby increasing the coefficients of static friction and dynamic friction of the outer sole on the road surface.
  • the outer sole of the present invention is produced by using a composition containing a thermoplastic elastomer, and has a surface free energy of 12 mJ/m 2 or higher.
  • the surface free energy of the outer sole be 15 mJ/m 2 or higher, more preferably 20 mJ/m 2 or higher, further preferably 25 mJ/m 2 or higher, particularly preferably 30 mJ/m 2 or higher. It is preferable for the surface free energy of the outer sole to be as high as possible, with no upper limit. Practically, the upper limit to the surface free energy of the outer sole produced by using the composition containing the thermoplastic elastomer is 73 mJ/m 2 or lower, for example.
  • the surface free energy of the outer sole can be determined according to the Kaelble-Uy's theory, in the same manner as in the [Preliminary findings] section.
  • the value of the surface free energy of the outer sole can be determined as follows: on the outer sole surface, 1 ⁇ L of ion-exchanged water and 1 ⁇ L of diiodomethane are dropped; 10 seconds later, the contact angles of the liquid drops are measured; the values of the contact angles are substituted into the simultaneous equations of Formulae (x1) and (x2); and the solutions, ⁇ d and ⁇ p , are substituted into Formula (y).
  • a Wako 1st Grade reagent manufactured by Wako Pure Chemical Industries, Ltd. may be used.
  • ⁇ d , ⁇ p , and ⁇ total each denote the dispersion component, the polar component, and the sum of the dispersion component and the polar component of the surface free energy, respectively;
  • ⁇ H2O and ⁇ CH3I each denote the surface free energy of water and the surface free energy of diiodomethane, respectively;
  • ⁇ H2O and ⁇ CH3I each denote the contact angle of water and the contact angle of diiodomethane, respectively.
  • the values of the surface free energy of water and diiodomethane are from a document ( D. H. Kaelble, The Journal of Adhesion, 2, 2 (1970) 66 .).
  • the arithmetic mean roughness, Ra, (indicative of the surface roughness) of the outer sole of the present invention is not particularly limited, but it is preferable that the arithmetic mean roughness, Ra, be 1000 ⁇ m or lower, more preferably from 5 ⁇ m to 100 ⁇ m, further preferably from 5 ⁇ m to 20 ⁇ m. With an arithmetic mean roughness, Ra, within this range, the outer sole has high levels of coefficients of static friction and dynamic friction on a road surface and, in particular, has an excellent grip performance.
  • the arithmetic mean roughness, Ra is the arithmetic mean roughness of the outer sole surface (which is one of the surfaces of the outer sole that comes into contact with a road surface), measured in accordance with JIS B0601-2001.
  • Examples of the method of obtaining the outer sole having an arithmetic mean roughness, Ra, within this range include (1) foaming the composition into a foam and (2) forming fine irregularities on the surface.
  • the composition may contain an additional component other than the thermoplastic elastomer.
  • additional component other than the thermoplastic elastomer include polymers other than the thermoplastic elastomer; and various additives, such as a foaming agent, a reinforcing agent, and a crosslinking agent.
  • thermoplastic elastomer refers to an elastomer that softens and becomes fluid upon heating and then returns to become rubber-like and elastic upon cooling.
  • thermoplastic elastomer is not particularly limited, and examples thereof include a chlorinated polyethylene-based elastomer, a chlorosulfonated polyethylene-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, a polystyrene-based elastomer, an olefin-based elastomer, a polyvinyl chloride elastomer, a urethane-based elastomer, a vinyl chloride-based elastomer, an acrylic-based elastomer, and a vinyl acetate-based elastomer.
  • a chlorinated polyethylene-based elastomer a chlorosulfonated polyethylene-based elastomer
  • polyester-based elastomer a polyamide-based elastomer
  • a polystyrene-based elastomer an olefin-based elastomer
  • thermoplastic elastomer consist of at least one type of elastomer selected from a chlorinated polyethylene-based elastomer, a chlorosulfonated polyethylene-based elastomer, a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, and a urethane-based elastomer.
  • thermoplastic elastomer examples include: (1) a chlorinated polyethylene-based elastomer alone, (2) a chlorosulfonated polyethylene-based elastomer alone, (3) at least a chlorinated polyethylene-based elastomer and an olefin-based elastomer, (4) a styrene-based elastomer alone, (5) a polyamide-based elastomer alone, (6) at least a styrene-based elastomer and a polyamide-based elastomer, (7) at least a styrene-based elastomer and a urethane-based elastomer, (8) at least a styrene-based elastomer and an olefin-based elastomer, (9) at least a styrene-based elastomer, an olefin-based elastomer, and
  • a chlorinated polyethylene-based elastomer, a chlorosulfonated polyethylene-based elastomer, a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, and a urethane-based elastomer are collectively called "first elastomers", and thermoplastic elastomers other than the first elastomers are collectively called "second elastomers”.
  • thermoplastic elastomer of the present invention consists of (a) at least one first elastomer, (b) at least one second elastomer, or (c) a combination of at least one first elastomer and at least one second elastomer. From the viewpoint to easily achieve a surface free energy of the outer sole of 12 mJ/m 2 or higher, it is preferable that the thermoplastic elastomer consists of at least a first elastomer, and it is more preferable that the first elastomer be at least one of a chlorinated polyethylene-based elastomer and a chlorosulfonated polyethylene-based elastomer.
  • the chlorinated polyethylene-based elastomer is a polymer in which some of or all of the hydrogen atoms of the polyethylene are substituted with chlorine atom(s). Provided that the chlorinated polyethylene-based elastomer contains a chloro group, a substituent or substituents other than chloro group may substitute the hydrogen atom or some of the hydrogen atoms of the polyethylene.
  • the chlorinated polyethylene-based elastomer may be obtained by chlorinating a polyethylene powder or particle in an aqueous suspension or by chlorinating a polyethylene dissolved in an organic solvent, for example.
  • the chlorine content in the chlorinated polyethylene-based elastomer ranges, for example, from 20% by mass to 50% by mass, preferably from 25% by mass to 45% by mass, in the whole chlorinated polyethylene. It is preferable that the chlorinated polyethylene-based elastomer be amorphous.
  • the chlorinated polyethylene-based elastomer include a chlorinated ethylene homopolymer and a copolymer of chlorinated ethylene with an ⁇ -olefin (preferably, an ⁇ -olefin containing 12 or less carbon atoms).
  • the copolymer contains the ⁇ -olefin in an amount of higher than 0% by mass and 10% by mass or lower in the whole chlorinated polyethylene, but it is not limited to the above-mentioned amount.
  • the density of the chlorinated polyethylene-based elastomer is not particularly limited but ranges from 1.07 g/cm 3 to 1.21 g/cm 3 , for example.
  • the molecular weight of the chlorinated polyethylene-based elastomer is not particularly limited but ranges from 50,000 to 700,000, for example.
  • the chlorinated polyethylene-based elastomer may be a crosslinked molecule or a non-crosslinked molecule.
  • chlorinated polyethylene-based elastomer a commercially available product may be used.
  • examples of the commercially available product include "Elaslen” (trade name) manufactured by Showa Denko K.K.
  • a copolymer herein may be any of a random copolymer, a block copolymer, and a graft copolymer.
  • the chlorosulfonated polyethylene-based elastomer is a polymer in which the hydrogen atom or some of the hydrogen atoms of the polyethylene is substituted with a chlorosulfonyl group.
  • the chlorosulfonated polyethylene-based elastomer contains a chlorosulfonyl group, a substituent or substituents other than chlorosulfonyl group may substitute some of the hydrogen atom or the hydrogen atoms of the polyethylene.
  • the chlorosulfonated polyethylene-based elastomer may be obtained by chlorosulfonating a polyethylene with chlorine and sulfurous acid gas, for example.
  • the chlorine content in the chlorosulfonated polyethylene-based elastomer ranges, for example, from 20% by mass to 50% by mass, preferably from 30% by mass to 40% by mass, in the whole chlorosulfonated polyethylene. It is preferable that the chlorosulfonated polyethylene-based elastomer be amorphous.
  • chlorosulfonated polyethylene-based elastomer examples include a chlorosulfonated ethylene homopolymer and a copolymer of chlorosulfonated ethylene with an ⁇ -olefin (preferably, an ⁇ -olefin containing 12 or less carbon atoms). It is preferable that the content of the ⁇ -olefin in the copolymer be higher than 0% by mass and 10% by mass or lower in the whole chlorosulfonated polyethylene, but it is not limited to the above-mentioned content.
  • the density of the chlorosulfonated polyethylene-based elastomer is not particularly limited but ranges from 1.10 g/cm 3 to 1.40 g/cm 3 , for example.
  • the chlorosulfonated polyethylene-based elastomer may be a crosslinked molecule or a non-crosslinked molecule.
  • chlorosulfonated polyethylene-based elastomer a commercially available product may be used.
  • the commercially available product include "TOSO-CSM TS-530" (trade name) manufactured by Tosoh Corporation and "Hypalon” (trade name) manufactured by DuPont Inc.
  • the polyester-based elastomer is a polymer containing an ester component.
  • the polyester-based elastomer may be an ester homopolymer. It is preferable that the polyester-based elastomer be a copolymer composed of a polyester or a derivative thereof as its hard segment and a polyether or a polyester having a low glass transition temperature (Tg) as its soft segment.
  • Tg glass transition temperature
  • polyester-based elastomer examples include a polyester-polyether copolymer composed of an aromatic crystalline polyester, such as polyethylene terephthalate or polybutylene terephthalate, as its hard segment and a polyether as its soft segment; and a polyester-polyester copolymer composed of an aromatic crystalline polyester as its hard segment and an aliphatic polyester as its soft segment.
  • a polyester-polyether copolymer composed of an aromatic crystalline polyester, such as polyethylene terephthalate or polybutylene terephthalate, as its hard segment and a polyether as its soft segment
  • polyester-polyester copolymer composed of an aromatic crystalline polyester as its hard segment and an aliphatic polyester as its soft segment.
  • the polyamide-based elastomer is a polymer containing a polyamide component.
  • the polyamide-based elastomer may be an amide homopolymer or may be a copolymer of a polyamide component with another component.
  • Examples of the copolymer include a copolymer composed of an aliphatic or aromatic polyamide or a derivative thereof as its hard segment and a component like a polyester or a polyether as its soft segment.
  • Examples of the aliphatic or aromatic polyamide include nylon 6, nylon 64, nylon 66, nylon 610, nylon 612, nylon 46, nylon 9, nylon 11, nylon 12, N-alkoxymethyl-modified nylons, hexamethylenediamine-isophthalic acid condensation copolymer, and metaxyloyldiamine-adipic acid condensation copolymer.
  • the polystyrene-based elastomer is a polymer containing a styrene component.
  • the polystyrene-based elastomer may be a styrene homopolymer. It is preferable that the polystyrene-based elastomer be a copolymer composed of a polystyrene or a derivative thereof as its hard segment and a component like butadiene as its soft segment.
  • the content of the hard segment in the polystyrene-based elastomer is not particularly limited. However, if the content of the hard segment is too low, the hard segment does not readily agglomerate, while if the content of the hard segment is too high, plasticity and elasticity of the polystyrene-based elastomer may be low. From these viewpoints, it is preferable that the content of the hard segment in the polystyrene-based elastomer ranges from 10% by mass to 65% by mass, more preferably from 20% by mass to 40% by mass, in the whole elastomer.
  • the polystyrene-based elastomer is not particularly limited and examples thereof include a styrene-butadiene block copolymer (abbreviated as SBR), a hydrogenated styrene-butadiene block copolymer (SEB), a styrene-butadiene-styrene block copolymer (SBS), a styrene-butadiene-butylene-styrene block copolymer (SBBS), a styrene-ethylene-butadiene-styrene block copolymer (SEBS), a styrene-isoprene block copolymer (SIR), a styrene-ethylene-propylene block copolymer (SEP), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-propylene-s
  • the olefin-based elastomer is a polymer composed of a polyethylene and/or a polypropylene having rubber-like elasticity imparted thereto.
  • Typical examples of the olefin-based elastomer include a polypropylene-based elastomer and an ⁇ -olefin-based elastomer.
  • the polypropylene-based elastomer contains a polypropylene component, preferably contains a copolymer of a propylene with an ethylene.
  • the polypropylene-based elastomer may be a propylene homopolymer or may be a copolymer of a polypropylene component with another component.
  • Examples of the polypropylene-based elastomer include a polypropylene homopolymer and a propylene-ethylene random copolymer.
  • the ⁇ -olefin-based elastomer may be a copolymer of a polyethylene and/or a polypropylene with an ⁇ -olefin.
  • the ⁇ -olefin is not particularly limited but it is preferable that the ⁇ -olefin be an ⁇ -olefin having 4 to 20 carbon atoms.
  • the ⁇ -olefin may be a single type of ⁇ -olefin or may be a combination of two or more types of ⁇ -olefins.
  • Examples of the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.
  • 1-butene, 1-hexene, and 1-octene are preferable.
  • Examples of the ⁇ -olefin-based elastomer include an ethylene-1-butene copolymer, a propylene-1-butene copolymer, an ethylene-1-hexene copolymer, a propylene-1-hexene copolymer, an ethylene-1-octene copolymer, and a propylene-1-octene copolymer.
  • One of these may be used alone, or a combination of two or more of these may be used.
  • ⁇ -olefin-based elastomer a commercially available product may be used.
  • examples of the commercially available product include "Tafmer” (trade name) manufactured by Mitsui Chemicals, Inc.
  • the urethane-based elastomer is a polymer containing a urethane component.
  • the urethane-based elastomer may be a urethane homopolymer or may be a copolymer of a polyurethane component with another component. It is preferable that the urethane-based elastomer be a copolymer composed of a polyurethane or a derivative thereof as its hard segment and a component like a polyether or a polyester as its soft segment.
  • urethane-based elastomer examples include a polyether-containing polyurethane and a polyester-containing polyurethane.
  • vinyl chloride-based elastomer examples include a highly polymerized polyvinyl chloride elastomer, and a partially crosslinked polyvinyl chloride elastomer in which the crosslinked part functions as their hard segment and the linear part functions as their soft segment.
  • the acrylic-based elastomer is an acrylic-based polymer containing one, two, or more acrylic monomers.
  • thermoplastic elastomer of the present invention may consist of (a) a first elastomer, (b) a second elastomer, or (c) a combination of a first elastomer and a second elastomer.
  • the second elastomer is appropriately selected from thermoplastic elastomers other than the following six types of thermoplastic elastomers: a chlorinated polyethylene-based elastomer, a chlorosulfonated polyethylene-based elastomer, a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, and a urethane-based elastomer.
  • thermoplastic elastomers other than the following six types of thermoplastic elastomers: a chlorinated polyethylene-based elastomer, a chlorosulfonated polyethylene-based elastomer, a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, and a urethane-based elastomer.
  • the ratio between the first elastomer and the second elastomer is not particularly limited. It is preferable for the mass ratio (first elastomer) : (second elastomer) to range from 100 : 0 to 60 : 40, more preferably from 85 : 15 to 65 : 35 because with this mass ratio, it is easy to regulate the surface free energy to 12 mJ/m 2 or higher.
  • the mass ratio (first elastomer) : (second elastomer) of 100 : 0 mentioned above corresponds to a case in which the thermoplastic elastomer consists solely of a first elastomer, which does not fit the description "the thermoplastic elastomer consists of a combination of a first elastomer and a second elastomer". Despite that, the expression "the mass ratio (first elastomer) : (second elastomer) ranging from 100 : 0 to 60 : 40" is employed above for describing the ratio between both elastomers.
  • thermoplastic elastomer examples include rubbers.
  • the rubbers are not particularly limited and examples thereof include synthetic rubbers such as butadiene rubber (BR), isoprene rubber (IR), and chloroprene (CR); natural rubber (NR); and copolymer rubbers such as styrene-butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and butyl rubber (IIR).
  • synthetic rubbers such as butadiene rubber (BR), isoprene rubber (IR), and chloroprene (CR); natural rubber (NR); and copolymer rubbers such as styrene-butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and butyl rubber (IIR).
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile butadiene rubber
  • IIR butyl rubber
  • the content thereof is not particularly limited provided that the resulting outer sole has a surface free energy of 12 mJ/m 2 or higher.
  • the content of the additional polymers other than the thermoplastic elastomer may be higher than 0 part by mass and 500 parts by mass or lower, preferably higher than 0 part by mass and 400 parts by mass or lower, relative to 100 parts by mass of the thermoplastic elastomer.
  • the foaming agent is used in the case in which the outer sole of the present invention is made into a foamed article.
  • Use of the foaming agent is required in chemical foaming for foaming the composition.
  • use of the foaming agent may not be required.
  • foaming agent examples include sodium hydrogen carbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DNPT), azobisisobutyronitrile, barium azodicarboxylate, and p,p'-oxybisbenzenesulfonyl hydrazine (OBSH).
  • ADCA azodicarbonamide
  • DNPT dinitrosopentamethylenetetramine
  • OBSH azobisisobutyronitrile
  • barium azodicarboxylate examples include p,p'-oxybisbenzenesulfonyl hydrazine (OBSH).
  • a foaming aid may be concurrently used with the foaming agent.
  • the foaming aid include zinc oxide, urea, and urea derivatives.
  • the content of the foaming agent is not particularly limited and is appropriately determined.
  • the content of the foaming agent ranges from 0.5 parts by mass to 5 parts by mass relative to 100 parts by mass of the thermoplastic elastomer.
  • the reinforcing agent is not particularly limited and may be a conventionally known reinforcing agent.
  • Examples of the reinforcing agent include silica, carbon black, activated calcium carbonate, and magnesium silicate ultrafine particles.
  • the reinforcing agent is hydrous silica (white carbon), which can give a low-foamed outer sole having a relatively low density, an excellent mechanical strength, and an excellent abrasion resistance.
  • the content of the reinforcing agent is not particularly limited and is appropriately determined.
  • the content of the reinforcing agent ranges from 10 parts by mass to 40 parts by mass relative to 100 parts by mass of the thermoplastic elastomer.
  • the crosslinking agent is not particularly limited and may be a conventionally known crosslinking agent.
  • the crosslinking agent examples include a sulfur-containing compound and an organic peroxide.
  • the sulfur-containing compound include sulfur, sulfur halides, di-2-benzothiazolyl disulfide, and N-oxydiethylene-2-benzothiazolylsulfenamide.
  • the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2.5-di(t-butylperoxy)hexane, and1,1-di(t-butylperoxy)cyclohexane.
  • a crosslinking promoter may be concurrently used with the crosslinking agent.
  • the content of the crosslinking agent is not particularly limited and is appropriately determined.
  • the content of the crosslinking agent ranges from 0.1 parts by mass to 5 parts by mass, preferably from 0.3 parts by mass to 3 parts by mass, relative to 100 parts by mass of the thermoplastic elastomer.
  • composition used for producing the outer sole of the present invention may contain other additives, such as a heat stabilizer, a light stabilizer, an antioxidant, an ultraviolet absorber, a colorant, a plasticizer, an antistatic agent, a thickener, a processed oil, and stearic acid.
  • additives such as a heat stabilizer, a light stabilizer, an antioxidant, an ultraviolet absorber, a colorant, a plasticizer, an antistatic agent, a thickener, a processed oil, and stearic acid.
  • composition is shaped into the sole of a shoe.
  • the composition is prepared by mixing the thermoplastic elastomer, and optionally one or more of the additional polymers other than the thermoplastic elastomer, and various additives such as the crosslinking agent, each in a certain amount.
  • the resulting composition is kneaded in a mixing roll, a pressure kneader, or an extruder, for example, while being heated to a temperature ranging from 70°C to 150°C.
  • the resulting composition After thorough kneading, the resulting composition is poured into a press mold, followed by, for example, pressing for a certain period of time while being heated to a temperature ranging from 150°C to 200°C. Thus, an outer sole can be obtained. Alternatively, after thorough kneading, the resulting composition is transferred into an injection molding machine for injection molding, and thereby an outer sole can be obtained.
  • the resulting primary molded article may be used as it is as the outer sole.
  • the primary molded article obtained by hot-pressing the composition may be subjected to secondary processing and the resulting product may be used as the outer sole of the present invention.
  • the outer sole may be a foamed article produced by foaming the composition, or may be a non-foamed article produced from the composition without foaming.
  • foaming the composition the outer sole having the above-described arithmetic mean roughness, Ra, can be easily obtained. From the view points of a high arithmetic mean roughness and excellent cushioning effect, it is preferable that the outer sole of the present invention be a foamed article.
  • the foaming ratio is not particularly limited but ranges from 1.05 to 1.4, for example, preferably from 1.05 to 1.2.
  • the density of the outer sole is not particularly limited. From the viewpoint of weight reduction, it is preferable that the density of the outer sole be 0.6 g/cm 3 or lower, more preferably 0.55 g/cm 3 or lower, further preferably 0.5 g/cm 3 or lower. It is preferable that the lower limit to the density of the outer sole be as low as possible, typically 0.2 g/cm 3 or higher, preferably 0.3 g/cm 3 or higher. The density is measured in accordance with JIS Z 8807.
  • the outer sole of the present invention is used as the outer sole of a shoe, attached to the bottom side of the body of the shoe, for example.
  • the outer sole of the present invention is attached to the entire area of the bottom side of the shoe body.
  • the outer sole of the present invention may be attached to a partial area of the bottom side of the shoe body.
  • the outer sole of the present invention may also be used as a reinforcing component, such as a shank component, of a shoe.
  • the shank component is a bottom-forming component, disposed in the area of a shoe that comes under the arch of a foot of the shoe's wearer.
  • the shape of the outer sole may be any shape.
  • the outer sole may be substantially platy, or may be substantially convex (like the outer soles of a pair of spikes with many circular truncated points).
  • the bottom side of the outer sole may be smooth, but it typically has irregularities in any appropriate form.
  • the bottom side of the outer sole herein refers to the side of the outer sole opposite to the upper side of the outer sole, that is, opposite to the side of the outer sole that is to be attached to the bottom side of the shoe body.
  • the outer sole is fixed to the shoe body with an adhesive, for example.
  • the adhesive is not particularly limited and examples thereof include conventionally known adhesives, such as solvent adhesives, emulsion adhesives, laser adhesives, and thermal adhesives.
  • the solvent adhesives are a type of adhesives containing a binder resin dissolved or dispersed in an organic solvent.
  • the emulsion adhesives are a type of adhesives containing a binder resin dispersed in water.
  • the laser adhesives are a type of adhesives that exhibits its adhesive ability upon laser irradiation.
  • the thermal adhesives are a type of adhesives that exhibits its adhesive ability upon heating.
  • Figs. 1 and 2 both illustrate a first embodiment of the shoe of the present invention.
  • a shoe 1a includes a shoe body 2a, a midsole 3a attached to the bottom side of the shoe body 2a, and an outer sole 5a attached to the bottom side of the midsole 3a.
  • the shape of the midsole 3a is substantially the same as that of the bottom side of the shoe body 2a.
  • the shape of the outer sole 5a is substantially the same as that of the bottom side of the midsole 3a.
  • the outer sole 5a is substantially platy.
  • the bottom side of the platy outer sole 5a has irregularities as intended, as shown in Fig. 2 .
  • the bottom side of the outer sole 5a may be smooth (not illustrated).
  • the upper side of the midsole 3a is bonded to the bottom side of the shoe body 2a with an adhesive, and the upper side of the outer sole 5a is bonded to the bottom side of the midsole 3a with an adhesive (the adhesive is not illustrated). In the case of using this shoe 1a, the bottom side of the outer sole 5a comes into contact with the ground.
  • the outer sole of the present invention may be used as the outer sole 5a of the shoe 1a, or as the midsole 3a of the shoe 1a, or as each of the midsole 3a and the outer sole 5a of the shoe 1a.
  • Fig. 3 illustrates a second embodiment of the shoe of the present invention.
  • a shoe 1b includes a shoe body 2b, a midsole 3b attached to the bottom side of the shoe body 2b, a first outer sole 51b attached to the front part of the bottom side of the midsole 3b, and a second outer sole 52b attached to the rear part of the bottom side of the midsole 3b.
  • the shape of the midsole 3b is substantially the same as that of the bottom side of the shoe body 2b.
  • Each of the first outer sole 51b and the second outer sole 52b is smaller than the bottom side of the midsole 3b.
  • the upper side of the midsole 3b is bonded to the bottom side of the shoe body 2b with an adhesive, and the upper sides of both the first outer sole 51b and the second outer sole 52b are bonded to the bottom side of the midsole 3b with an adhesive (the adhesive is not illustrated).
  • the bottom sides of both the first outer sole 51b and the second outer sole 52b come into contact with the ground and a partial area of the bottom side of the midsole 3b may also come into contact with the ground.
  • the outer sole of the present invention may be used as the first outer sole 51b and/or the second outer sole 52b of the shoe 1b.
  • each of the midsole 3a and the midsole 3b is not particularly limited.
  • the thickness of each of the midsole 3a and the midsole 3b is 2 mm or more, for example, preferably from 2 mm to 10 mm.
  • each of the outer sole 5a, the first outer sole 51b, and the second outer sole 52b is not particularly limited.
  • the thickness of each of the outer sole 5a, the first outer sole 51b, and the second outer sole 52b is 2 mm or more, for example, preferably from 2 mm to 20 mm.
  • the shoe body may protect substantially the entire instep, as illustrated in the figure, or may protect only a part of the instep (like a sandal).
  • the shoe of the present invention is not particularly limited in its applications.
  • the shoe of the present invention may be used as a shoe for various ball sports, such as a soccer shoe or a rugby shoe; a running shoe, such as a jogging shoe or a marathon shoe; a shoe for track and field; a shoe for sports in general; a walking shoe; a flip flop; and the like.
  • the outer sole of the present invention has an excellent grip performance on a road surface.
  • the outer sole of the present invention also has an excellent grip performance on a wet road surface, particularly on a wet, smooth road surface.
  • the shoe of the present invention having this outer sole is suitable for use as a shoe for ball sports, a running shoe, a shoe for track and field, and a walking shoe.
  • ⁇ -Olefin-based elastomer "Tafmer DF810" (trade name) manufactured by Mitsui Chemicals, Inc., copolymer of ethylene and 1-butene.
  • Styrene-based elastomer (1) "Septon V9461” (trade name) manufactured by KURARAY CO., LTD., styrene-ethylene-ethylene-propylene-styrene block copolymer (abbreviated as SEEPS).
  • Styrene-based elastomer (2) "M1913" (trade name) manufactured by Asahi Kasei Chemicals Corporation, styrene-ethylene-butadiene-styrene block copolymer modified with maleic acid (abbreviated as MA-modified SEBS).
  • Polyamide-based elastomer (1) "1010C1" (trade name) manufactured by DSM, nylon 6 homopolymer.
  • Polyamide-based elastomer (2) "3010SR” (trade name) manufactured by DSM, nylon 66 homopolymer.
  • Urethane-based elastomer "ET195" (trade name) manufactured by BASF, copolymer composed of a polyurethane as its hard segment and a polyester as its soft segment.
  • Polypropylene-based elastomer "E-105-GM” (trade name) manufactured by Prime Polymer Co., Ltd.
  • Isoprene rubber "IR2200" (trade name) manufactured by Zeon Corporation.
  • Oil (1) processed oil, "PW90" (trade name) manufactured by Idemitsu Kosan Co., Ltd.
  • Oil (2) processed oil, "DOZ” (trade name) manufactured by New Japan Chemical Co., Ltd.
  • Oil (3) processed oil, "P200” (trade name) manufactured by JX Nippon Oil & Energy Corporation.
  • Crosslinking agent (1) dicumyl peroxide, "Percumyl D” (trade name) manufactured by Nippon Oil & Fats Co., Ltd.
  • Crosslinking agent (2) 2,5-dimethyl-2.5-di(t-butylperoxy)hexane, "Perhexa 25B-40" (trade name) manufactured by Nippon Oil & Fats Co., Ltd.
  • Crosslinking agent (3) sulfur, "sulfur #200" (trade name) manufactured by Hosoi Chemical Industry Co., Ltd.
  • Crosslinking aid (1) triallyl isocyanurate, "TAIC M-60” (trade name) manufactured by Nippon Kasei Chemical Company Limited.
  • Crosslinking aid (2) trimethylolpropane trimethacrylate, "SR350” (trade name) manufactured by Sartomer.
  • Crosslinking aid (3) "Nocceler” (trade name) manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.
  • Foaming agent azodicarbonamide, "Vinyfor AC#3C-K2" (trade name) manufactured by Eiwa Chemical Ind. Co., Ltd.
  • Foaming aid zinc oxide, "Activated Zinc White No.2" (trade name) manufactured by The Honjo Chemical Corporation.
  • Silane coupling agent "Si-69" (trade name) manufactured by Degussa Japan.
  • Stearic acid "Stearic Acid 50S” (trade name) manufactured by New Japan Chemical Co., Ltd.
  • Zinc oxide "Activated Zinc White No.2" (trade name) manufactured by The Honjo Chemical Corporation.
  • Example 2 In the same manner as in Example 1 and by using materials according to the proportion specified in Table 1, a composition was prepared and a foamed article was produced from the resulting composition.
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 Example 11
  • Example 12 Composition Styrene-based elastomer (1) 46.67 46.67 50.00 46.67 50.00 46.67 50.00 Styrene-based elastomer (2) 20.00 20.00 21.43 20.00 21.43 20.00 21.43 Polyamide-based elastomer (1) 20.00 28.57 Polyamide-based elastomer (2) 20.00 28.57 Urethane-based elastomer 20.00 28.57 Polypropylene -based elastomer 33.33 13.33 13.33 13.33 Oil (1) 66.67 66.67 71.43 66.67 71.43 66.67 71.43 Crosslinking agent (2) 1.33 1.33 1.43 1.33 1.33 1.43 Crosslinking aid (2) 6.67 6.67 7.14 6.67 7.14 6.67 7.14 Total 174.67 174.67 180.00 174.67 180.00 174.67 180.00 Surface free energy (mJ/m 2 ) 27.5 30.5 47.1
  • Example 13 Example 14 Example 15 Comparative Example 2 Composition Chlorinated polyethylene-based elastomer 100 20 Chlorosulfonated polyethylene-based elastomer 100 Isoprene rubber 80 100 Oil (2) 10 10 Oil (3) 20 Crosslinking agent (3) 2.0 2.0 Crosslinking aid (3) 2.3 2.3 4.0 Silica 20 20 45 Silane coupling agent 4.5 Stearic acid 2 Zinc oxide 5 Other additives 12 12 3 Total 100.0 144.3 146.3 185.5 Surface free energy (mJ/m 2 ) 29.4 29.9 24.3 19.0 Surface roughness Ra ( ⁇ m) 0.51 0.21 0.62 0.3 Coefficient of static friction 0.601 1.043 1.073 0.406 Coefficient of dynamic friction 0.397 0.493 0.448 0.351
  • a Wako 1st Grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as the device for contact angle measurement.
  • a contact angle meter (DM-510Hi manufactured by Kyowa Interface Science Co., Ltd.) was used as the device for contact angle measurement.
  • ⁇ H2O and ⁇ CH3I in Formulae (x1) and (x2) were obtained from a document ( D. H. Kaelble, The Journal of Adhesion, 2, 2 (1970) 66 .).
  • the arithmetic mean roughness, Ra, of each of the foamed articles and the non-foamed articles (for use as an outer sole) prepared in the examples and the comparative examples was measured in accordance with JIS B0601-2001. More specifically, the surface roughness (the arithmetic mean roughness) of each of these was measured with a One-shot 3D Measuring Macroscope VR-3000 manufactured by Keyence Corporation. The results are shown in Tables 1 to 3.
  • each of the foamed articles and the non-foamed articles prepared in the examples and the comparative examples was fixed to the bottom of a safety shoe that had no outer sole.
  • the resulting safety shoe was placed on a stainless steel surface that was wet with water. Then, the safety shoe was made to slide at a sliding rate of 0.22 m/second with a vertical load of 500 N being applied, while the coefficients of static friction and dynamic friction were being measured.
  • Tables 1 to 3 The results are shown in Tables 1 to 3.
  • Fig. 4 provides a graph showing the results of the coefficient of static friction and the coefficient of dynamic friction obtained in Examples 1 to 5 and Comparative Example 1.
  • each of the outer soles in Examples 1 to 5 has high coefficients of static friction and dynamic friction on a road surface compared to Comparative Example 1. Especially, an increase in the content of the chlorinated polyethylene-based elastomer has contributed to a remarkable increase in the coefficient of static friction. Evaluation was conducted as follows: the higher the coefficient of friction was, the more slip resistant the outer sole was.
  • the coefficient of static friction of the outer sole refers to the friction on a road surface at the time when the shoe's movement is started
  • the coefficient of dynamic friction of the outer sole refers to the friction on a road surface at the time when the shoe's movement is stopped.
  • the time when the shoe's movement is started refers to, for example, the time when the wearer starts to run or walk
  • the time when the shoe's movement is stopped refers to, for example, the time when the wearer changes the direction to proceed while running.
  • each of the outer soles in Examples 6 to 12 has high coefficients of static friction and dynamic friction on a road surface.
  • the coefficients of dynamic friction in Examples 8, 10, and 12 where no polypropylene-based elastomer is used are remarkably higher than those in Examples 6, 7, 9, and 11 where a polyolefin-based elastomer is used.
  • the coefficients of static friction in Examples 7 to 12 where a polyamide-based elastomer or a urethane-based elastomer is used are higher than that of Example 6 where no polyamide-based elastomer nor urethane-based elastomer is used. From a comparison between Example 7 and Example 8 and a comparison between Example 9 and Example 10, it has been proven that an outer sole having a higher content of polyamide-based elastomer has a higher surface free energy.
  • An outer sole of the present invention can be used as a component of a shoe.

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  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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