WO2016031972A1 - 靴形成用部材及び靴 - Google Patents
靴形成用部材及び靴 Download PDFInfo
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- WO2016031972A1 WO2016031972A1 PCT/JP2015/074458 JP2015074458W WO2016031972A1 WO 2016031972 A1 WO2016031972 A1 WO 2016031972A1 JP 2015074458 W JP2015074458 W JP 2015074458W WO 2016031972 A1 WO2016031972 A1 WO 2016031972A1
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- WIPO (PCT)
- Prior art keywords
- shoe
- thermoplastic elastomer
- styrene
- methylstyrene
- resin
- Prior art date
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Classifications
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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
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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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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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
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Definitions
- the present invention relates to a shoe forming member and a shoe, and more particularly to a shoe forming member containing a thermoplastic elastomer and a shoe provided with such a shoe forming member.
- thermoplastic elastomers include urethane-based and olefin-based ones.
- An olefin-based thermoplastic elastomer in which a domain composed of a crosslinked elastomer is dispersed in a polypropylene resin matrix is superior in hydrolysis resistance compared to a urethane-based thermoplastic elastomer.
- the olefinic thermoplastic elastomer as described above is suitable as a material for a shoe forming member in that it has a relatively low density and hardly causes embrittlement at a low temperature.
- olefin-based thermoplastic elastomers are difficult to exert high adhesive strength with general adhesives. Therefore, even if the member made from an olefin type thermoplastic elastomer is utilized for formation of shoes, there exists a possibility that the use location may be restrict
- the present invention has an object to solve such problems, and an object is to improve the adhesiveness of a shoe forming member containing an olefin-based thermoplastic elastomer.
- the present invention according to a member for forming a shoe for solving the above-mentioned problem is a member for forming a shoe containing a thermoplastic elastomer, wherein the thermoplastic elastomer is a matrix containing a polypropylene resin and an aromatic polymer, and a cross-linking. And a domain containing an elastomer, and the aromatic polymer has a poly- ⁇ -methylstyrene structure in at least a part of the molecule.
- the present invention relating to a shoe for solving the above-described problems is characterized by comprising the above-described member for forming a shoe.
- thermoplastic elastomer contained in the shoe forming member of the present invention contains an aromatic polymer having a poly- ⁇ -methylstyrene structure in at least a part of the molecule in a matrix together with a polypropylene resin. And the adhesiveness which was excellent in the member for shoe formation can be exhibited because the thermoplastic elastomer matrix contains the specific aromatic polymer together with the polypropylene resin.
- FIG. 1 shows a shoe provided with a shoe forming member of the present embodiment.
- the shoe 1 includes an upper material 2 and shoe sole members 3 and 4.
- the shoe 1 includes a midsole 3 and an outer sole 4 as the sole member.
- the upper material 2 of the shoe 1 has a laminated structure including at least one reinforcing sheet material 21.
- the shoe forming member of the present embodiment is preferably the reinforcing sheet material 21 or the outer sole 4.
- thermoplastic elastomer suitable for forming the reinforcing sheet material 21 and the outer sole 4 will be described.
- the thermoplastic elastomer is a polyolefin-based thermoplastic elastomer, more specifically, a polypropylene-based thermoplastic elastomer.
- the thermoplastic elastomer has a microphase separation structure composed of a matrix containing a polypropylene resin and an aromatic polymer and a domain made of a crosslinked elastomer.
- the polypropylene resin may be a homopolypropylene resin that is a propylene homopolymer, a random polypropylene resin that is a random copolymer of propylene and ethylene, or a block polypropylene resin that is a block copolymer of propylene and ethylene.
- the aromatic polymer constituting the matrix together with the polypropylene resin is a homopolymer resin (homopolymer) of an ⁇ -methylstyrene monomer as long as it has a poly- ⁇ -methylstyrene structure in at least a part of the molecule.
- a copolymer resin (copolymer) composed of two or more types of monomers.
- ⁇ -methylstyrene monomer constituting the structural unit examples include ⁇ -methylstyrene, ⁇ -methyl-o-methylstyrene, ⁇ -methyl-m-methylstyrene. ⁇ -methyl-p-methylstyrene, ⁇ -methyl-2,6-dimethylstyrene, ⁇ -methyl-2,4-dimethylstyrene, ⁇ -methyl-2,4,6-trimethylstyrene, and the like.
- the homopolymer includes, as specific examples, poly- ⁇ -methylstyrene resin, poly- ⁇ -methyl-o-methylstyrene resin, poly- ⁇ -methyl-m-methylstyrene resin, poly- ⁇ -methyl-p. -Methylstyrene resin, poly- ⁇ -methyl-2,6-dimethylstyrene resin, poly- ⁇ -methyl-2,4-dimethylstyrene resin, poly- ⁇ -methyl-2,4,6-trimethylstyrene resin, etc. Can be mentioned.
- the aromatic polymer is a copolymer resin
- specific examples thereof include copolymer resins of two or more of the ⁇ -methylstyrene monomers.
- specific examples thereof include a vinyl monomer copolymerizable with an ⁇ -methylstyrene monomer and one or more ⁇ -methylstyrene monomers.
- a copolymer resin may be mentioned.
- the aromatic polymer is a copolymer resin, it may be a block copolymer resin or a graft copolymer resin.
- vinyl monomer copolymerizable with the ⁇ -methylstyrene monomer examples include olefin monomers, acrylic monomers, styrene monomers, vinyl ether monomers, diene monomers, and the like.
- olefin monomer examples include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, and vinylcyclohexane. Octene, norbornene and the like.
- acrylic monomer examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth).
- styrene monomer examples include styrene, 4-methylstyrene, 4-ethylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4- Examples include benzylstyrene, 4- (phenylbutyl) styrene, 2,4,6-trimethylstyrene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and methoxystyrene.
- vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, methyl propenyl ether, ethyl propenyl ether, and the like. Is mentioned.
- diene monomer examples include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, and ethylidene norbornene.
- These vinyl monomers may have a functional group such as a hydroxyl group or an amino group.
- the aromatic polymer constituting the matrix together with the polypropylene resin is preferably the homopolymer, and more preferably poly- ⁇ -methylstyrene resin.
- the ratio of the polypropylene resin and the aromatic polymer in the thermoplastic elastomer is not particularly limited, but exhibits excellent adhesion and wear resistance to the reinforcing sheet material 21 and the outer sole 4.
- the aromatic polymer is contained in the thermoplastic elastomer in a mass ratio higher than that of the polypropylene resin.
- the aromatic polymer is preferably contained in the thermoplastic elastomer at a ratio of 1.5 times or more, more preferably 7.5 times or more of the polypropylene resin by mass.
- the aromatic polymer is preferably contained in the thermoplastic elastomer at a mass ratio of 20 times or less of the polypropylene resin.
- the cross-linked elastomer constituting the domain in the thermoplastic elastomer is not particularly limited, but is preferably a styrene elastomer from the viewpoint of affinity with the matrix. That is, the cross-linked elastomer constituting the domain is styrene-ethylene-butylene copolymer resin (SEB), styrene-butadiene-styrene copolymer resin (SBS), hydrogenated product of SBS (styrene-ethylene-butylene-styrene).
- SEB styrene-ethylene-butylene copolymer resin
- SBS styrene-butadiene-styrene copolymer resin
- hydrogenated product of SBS styrene-ethylene-butylene-styrene
- SEBS Styrene-isoprene-styrene copolymer resin
- SIBS hydrogenated product of SIS (styrene-ethylene-propylene-styrene copolymer resin (SEPS)), styrene-isobutylene-styrene copolymer Polymer resin (SIBS), styrene-butadiene-isoprene-styrene copolymer resin (SBIS), SBIS hydrogenated product (styrene-ethylene-ethylene / propylene-styrene copolymer resin (SEEPS)), styrene-butadiene-styrene -Butadiene copolymer resin (S SB), styrene - butadiene - styrene - butadiene - is preferably a styrenic polymer such as styrene copolymer resin
- the domain is preferably a crosslinked elastomer obtained by crosslinking SEBS or SEEPS, and particularly preferably a crosslinked elastomer obtained by crosslinking SEEPS, in that the thermoplastic elastomer can exhibit excellent wear resistance.
- the domains are supplied with a styrenic polymer as described above together with a polypropylene resin and an aromatic polymer to a kneading apparatus such as an extruder.
- the styrenic polymer is formed by dynamic crosslinking.
- thermoplastic elastomer When producing a thermoplastic elastomer by carrying out dynamic crosslinking with a kneading apparatus, it is not necessary to supply all of the styrenic polymer, polypropylene resin and aromatic polymer to the kneading apparatus at the same time.
- a part of the polymer, polypropylene resin, and aromatic polymer is primarily kneaded with a kneading device to obtain a primary kneaded product, and then the remainder is added to the primary kneaded product so as to perform secondary kneading. It may be.
- thermoplastic elastomer As a method for producing a thermoplastic elastomer, a polypropylene resin and a part or all of an aromatic polymer are added to a kneading apparatus later, and a primary kneaded product having a higher styrene polymer content than the thermoplastic elastomer to be produced. It is preferable to employ a method in which a part of or a whole of the constituent material of the matrix is added to the primary kneaded material and then secondarily kneaded after being prepared in the presence of a crosslinking agent. According to such a preferred embodiment, the styrene polymer and the crosslinking agent can be present in the primary kneaded material in a high concentration state, and the crosslinking efficiency of the styrene polymer can be improved.
- the aromatic polymer in the present embodiment is incompatible with the polypropylene resin.
- the fact that the aromatic polymer and the polypropylene resin are incompatible indicates that, for example, a melt-kneaded product containing these at a mass ratio of 1: 1 is prepared, and the melt-kneaded product has a phase separation structure. It can be confirmed by being seen.
- thermoplastic elastomer of this embodiment exhibits a specific morphology.
- the domains in the thermoplastic elastomer of the present embodiment are dispersed in the matrix while being covered with the polypropylene resin.
- “the domain is covered with the polypropylene resin” does not mean that the domain is entirely covered with the polypropylene resin. That is, “the domain is covered with the polypropylene resin” includes a case where “a part of the domain is covered with the polypropylene resin”. Further, “the domain is covered with the polypropylene resin” does not mean that “the polypropylene resin covers the entire surface of the domain”. That is, “the domain is covered with the polypropylene resin” means that “the polypropylene resin covers a part of the surface of the domain” is included.
- the polypropylene resin of this embodiment has a lower melt viscosity than the aromatic polymer, it is effective for making the thermoplastic elastomer excellent in moldability. That is, when a thermoplastic elastomer is heated, the polypropylene resin that melts and has a low viscosity exists around the domain, so that the polypropylene resin exhibits a lubricant function when plastically deformed. .
- the melt viscosity of polypropylene resin and aromatic polymer is a twin-bore capillary rheometer (barrel diameter: 15 mm) with a die (die diameter: 1 mm, die length: 16 mm) on one side and an orifice with a diameter of 1 mm on the other side. For example, it can be measured under conditions of a temperature of 230 ° C. and a shear rate of 50 (1 / s).
- the domain includes a domain that is entirely covered with a polypropylene resin.
- the thermoplastic elastomer exhibits such a morphology can be confirmed by, for example, an atomic force microscope.
- FIG. 2 shows the result of observing the thermoplastic elastomer according to the present embodiment with an atomic force microscope.
- the white part is a polypropylene resin
- the black part surrounded by the polypropylene resin is a styrene-based crosslinked elastomer. is there.
- the other part in FIG. 2 is a part mainly occupied by the aromatic polymer.
- the styrene-based crosslinked elastomer used as the domain has a content of 15% by mass or more and 50% by mass in the thermoplastic elastomer in order to exhibit excellent flexibility and strength in the reinforcing sheet material 21 and the outer sole 4. % Or less is preferable.
- crosslinking agent for crosslinking the styrenic polymer into a crosslinked elastomer include organic peroxides.
- organic peroxide include 1,1-bis (1,1-dimethylethylperoxy) cyclohexane, 1,1-bis (1,1-dimethylbutylperoxy) cyclohexane, 4,4-bis.
- the amount of the cross-linking agent used can usually be 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the styrenic polymer.
- a crosslinking aid may be used in combination with the above crosslinking agent.
- the crosslinking aid preferably has at least one of an acryloyl group and a methacryloyl group, and preferably has a plurality.
- the compound represented by the following general formula (1) is suitable as a crosslinking aid used in combination with the crosslinking agent in order to crosslink the styrene polymer.
- R 1 represents alkylene having a chain length of 2 to 10 carbon atoms, or substituted alkylene in which a hydrogen atom of the alkylene is substituted with a substituent
- a 1 ” and “A 2 ” Each independently represents a direct bond or an ether bond
- X 1 ” and “X 2 ” each independently represents an acryloyl group or a methacryloyl group.
- R 1 in the general formula (1) has a structure represented by the following general formula (2).
- R 2 and R 3 are hydrogen atom, hydroxyl group, alkyl group having 2 to 3 carbon atoms, (meth) acryloyloxy group, (meth) acryloyloxymethyl group, or (meth) acryloyloxy Represents an ethyl group.
- both “A 1 ” and “A 2 ” are ether bonds, and one of “X 1 ” and “X 2 ” is acryloyl. It is preferred that the other is a methacryloyl group.
- the general formula (2) it is particularly preferable that one of “R 2 ” and “R 3 ” is a hydrogen atom and the other is a hydroxyl group.
- 2-hydroxy-3-acryloyloxypropyl methacrylate represented by the following formula (3) is particularly preferable.
- the thermoplastic elastomer can exhibit excellent wear resistance, and the thermoplastic elastomer can be made suitable as a material for a shoe forming member.
- the wear resistance improves as the amount of the crosslinking aid used increases.
- the crosslinking aid is usually preferably contained in an amount of 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more with respect to 100 parts by mass of the styrenic polymer. .
- the cross-linking aid is preferably contained in a proportion of 0.03 mol or more with respect to 100 parts by mass of the styrenic polymer, and in a proportion of 0.05 mol or more. It is more preferable to make it contain. In addition, it is not necessary to contain a crosslinking aid excessively.
- the upper limit is about 100 parts by mass with respect to 100 parts by mass of the styrenic polymer, and the upper limit is about 1 mol with respect to 100 parts by mass of the styrenic polymer. Is done.
- the thermoplastic elastomer may further contain additives other than those described above.
- additives include hardness adjusting agents such as paraffin oil, tackifiers such as terpene resins, anti-aging agents, Examples include processing aids, inorganic fillers, silane coupling agents, antibacterial agents, fragrances, and pigments.
- paraffin oil is an effective component for adjusting the thermoplastic elastomer to a texture according to the purpose.
- the ratio of the paraffin oil to the total 100 parts by mass of the polypropylene resin, the aromatic polymer, and the crosslinked elastomer is 10 parts by mass or more and 50 parts by mass or less. It is preferable.
- thermoplastic elastomer exhibits fluidity in the polypropylene resin and the aromatic polymer constituting the matrix by heating, so that various molding methods such as injection molding, transfer molding, press molding, etc. Therefore, it is easy to shape into a desired shape. That is, the thermoplastic elastomer is suitable as a forming material when the reinforcing sheet material 21 and the outer sole 4 are formed by the molding method described above. Moreover, the thermoplastic elastomer is excellent in adhesiveness. Therefore, when the reinforcing sheet material 21 is formed from this thermoplastic elastomer, for example, a special bonding method is employed to form the upper material 2 by bonding the reinforcing sheet material 21 to another sheet. You don't have to. Further, when the outer sole 4 is formed of the thermoplastic elastomer, for example, it is not necessary to employ a special bonding method for bonding the outer sole 4 to the midsole 3.
- the member for forming a shoe using the thermoplastic elastomer of the present embodiment is not only excellent in recyclability but also has an effect of facilitating the manufacture of the shoe.
- the member for shoe formation of the present invention may be formed only by the thermoplastic elastomer as described above, or may be formed by using other materials such as a fabric and a nonwoven fabric in combination.
- the shoe forming member of the present invention may be formed by foaming the above thermoplastic elastomer with a foaming agent or the like.
- thermoplastic elastomer of this embodiment is also excellent in wear resistance. Accordingly, when the thermoplastic elastomer is contained only in a part of the shoe forming member, the thermoplastic elastomer is contained in a portion exposed on the outer surface or the inner surface of the shoe in causing the shoe forming member to exhibit the effect related to wear resistance. It is preferred that Further, conventionally known technical matters relating to the shoe forming member can be applied to the shoe forming member of the present invention as long as the effects of the present invention are not significantly impaired.
- thermoplastic elastomer Abrasion resistance and peel strength> (Production of thermoplastic elastomer)
- the following materials (a) to (e) are supplied to a twin-screw extruder, the kneaded product is dynamically cross-linked while kneading with the twin-screw extruder, and the kneaded product and (f) are dry blended.
- Styrene polymer 100 parts by mass
- Paraffin oil P-200: 100 parts by mass
- Crosslinking agent organic peroxide (2,5-dimethyl-2,5-bis ( (t-butylperoxy) hexane): 2 parts by mass
- Cross-linking aid (2-hydroxy-3-acryloyloxypropyl methacrylate): 10 parts by mass
- Polypropylene resin homo PP: 20 parts by mass
- f) Poly- ⁇ -methylstyrene resin 30 to 380 parts by mass
- ⁇ Evaluation 2 About abrasion resistance and peel strength>
- A Relative comparison of wear resistance using the following three types (a1) to (a3) as the styrenic polymer and (d) the following five types (d1) to (d5) as the crosslinking aid Went.
- the blending amount of (d) the crosslinking aid in the raw materials for forming the thermoplastic elastomer is 0.1 mol / kg or 0.06, and (a) 100 parts by mass of the styrene polymer (f) poly- ⁇
- a test piece was prepared in the same manner as in “Evaluation 1” except that the content of methylstyrene resin was 280 parts by mass, and evaluation was performed in the same manner as in “Evaluation 1”. The evaluation results are shown below.
- the domain of the thermoplastic elastomer is particularly preferably a cross-linked elastomer obtained by cross-linking (a1) SEEPS among styrene-based polymers.
- a1 SEEPS cross-linking
- SEEPS cross-linking
- the domain of the thermoplastic elastomer is particularly preferably a cross-linked elastomer obtained by cross-linking (a1) SEEPS among styrene-based polymers.
- a1 SEEPS cross-linking
- thermoplastic elastomer according to the present embodiment is suitable as a material for a shoe forming member.
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Abstract
Description
このアッパー材やソール材といった靴形成用部材は、リサイクル性や成形性の観点から熱可塑性エラストマーによって形成させることが検討されている(下記特許文献1参照)。
ポリプロピレン樹脂マトリックス中に架橋エラストマーからなるドメインを分散させたオレフィン系の熱可塑性エラストマーは、ウレタン系の熱可塑性エラストマーに比べて耐加水分解性に優れている。
また、上記のようなオレフィン系の熱可塑性エラストマーは、比較的低密度であるとともに低温での脆化を生じにくい点において靴形成用部材の材料として適している。
その反面、オレフィン系の熱可塑性エラストマーは、一般的な接着剤では高い接着力が発揮されにくい。
そのためオレフィン系熱可塑性エラストマー製の部材は、靴の形成に利用するにしてもその使用箇所が制限されるおそれを有する。
そして、靴形成用部材は、熱可塑性エラストマーのマトリックス中にポリプロピレン樹脂とともに特定の芳香族系ポリマーが含有されていることで優れた接着性が発揮されうる。
図1は、本実施形態の靴形成用部材を備えた靴を示したものである。
該靴1は、アッパー材2と靴底用部材3,4とを有している。
該靴1は、前記靴底用部材として、ミッドソール3、及び、アウターソール4を有している。
該靴1の前記アッパー材2は、少なくとも1枚の補強用シート材21を含む積層構造を有している。
本実施形態の靴形成用部材は、具体的には、前記補強用シート材21や前記アウターソール4などであることが好ましい。
前記熱可塑性エラストマーは、ポリオレフィン系の熱可塑性エラストマーであり、より具体的にはポリプロピレン系の熱可塑性エラストマーである。
該熱可塑性エラストマーは、ポリプロピレン樹脂と芳香族系ポリマーとを含むマトリックスと、架橋エラストマーからなるドメインとによるミクロ相分離構造を有している。
即ち、前記ホモポリマーは、具体例として、ポリ-α-メチルスチレン樹脂、ポリ-α-メチル-o-メチルスチレン樹脂、ポリ-α-メチル-m-メチルスチレン樹脂、ポリ-α-メチル-p-メチルスチレン樹脂、ポリ-α-メチル-2,6-ジメチルスチレン樹脂、ポリ-α-メチル-2,4-ジメチルスチレン樹脂、ポリ-α-メチル-2,4,6-トリメチルスチレン樹脂などが挙げられる。
また、前記芳香族系ポリマーが共重合体樹脂である場合、その具体例としては、α-メチルスチレン系モノマーと共重合可能なビニル系モノマーと、α-メチルスチレン系モノマーの1種以上との共重合体樹脂が挙げられる。
なお、前記芳香族系ポリマーは、共重合体樹脂である場合、ブロック共重合体樹脂であってもグラフト共重合体樹脂であってもよい。
具体的には、前記芳香族系ポリマーは、質量で前記ポリプロピレン樹脂の1.5倍以上、より好ましくは7.5倍以上の割合で前記熱可塑性エラストマーに含有されることが好ましい。
また、前記芳香族系ポリマーは、質量で前記ポリプロピレン樹脂の20倍以下の割合で前記熱可塑性エラストマーに含有されることが好ましい。
即ち、前記ドメインを構成する架橋エラストマーは、スチレン-エチレン-ブチレン共重合体樹脂(SEB)、スチレン-ブタジエン-スチレン共重合体樹脂(SBS)、SBSの水素添加物(スチレン-エチレン-ブチレン-スチレン共重合体樹脂(SEBS))、スチレン-イソプレン-スチレン共重合体樹脂(SIS)、SISの水素添加物(スチレン-エチレン-プロピレン-スチレン共重合体樹脂(SEPS))、スチレン-イソブチレン-スチレン共重合体樹脂(SIBS)、スチレン-ブタジエン-イソプレン-スチレン共重合体樹脂(SBIS)、SBIS水素添加物(スチレン-エチレン-エチレン/プロピレン-スチレン共重合体樹脂(SEEPS))、スチレン-ブタジエン-スチレン-ブタジエン共重合体樹脂(SBSB)、スチレン-ブタジエン-スチレン-ブタジエン-スチレン共重合体樹脂(SBSBS)などのスチレン系ポリマーを架橋剤によって架橋させた架橋エラストマーであることが好ましい。
なかでも前記ドメインは、熱可塑性エラストマーに優れた耐摩耗性を発揮させ得る点においてSEBSやSEEPSを架橋させた架橋エラストマーとすることが好ましく、SEEPSを架橋させた架橋エラストマーとすることが特に好ましい。
熱可塑性エラストマーの製造方法としては、ポリプロピレン樹脂、及び、芳香族系ポリマーの一部又は全部を後から混練装置に加え、製造する熱可塑性エラストマーよりもスチレン系ポリマーの含有率が高い1次混練物を架橋剤の存在のもとで作製した後で、該1次混練物にマトリックスの構成材料の一部又は全部を加えて2次混練させる方法を採用することが好ましい。
このような好ましい態様によれば、スチレン系ポリマーや架橋剤を1次混練物中に高濃度な状態で存在させることができ、スチレン系ポリマーの架橋効率の向上を図ることができる。
なお、芳香族系ポリマーとポリプロピレン樹脂とが非相溶性を示すものであることは、例えば、これらを1:1の質量割合で含む溶融混練物を作製し、該溶融混練物に相分離構造が見られることで確認することができる。
具体的には、本実施形態の熱可塑性エラストマーにおける前記ドメインは、前記ポリプロピレン樹脂に覆われた状態でマトリックス中に分散している。
なお、ここで“ドメインがポリプロピレン樹脂に覆われている”とは、“ドメインが全てポリプロピレン樹脂によって覆われている”というような限定的な意味ではない。
即ち、“ドメインがポリプロピレン樹脂に覆われている”とは、“ドメインの一部がポリプロピレン樹脂で覆われた状態になっている”という場合をも含む意味である。
また、“ドメインがポリプロピレン樹脂に覆われている”とは、“ポリプロピレン樹脂がドメインの全表面を覆っている”というような限定的な意味ではない。
即ち、“ドメインがポリプロピレン樹脂に覆われている”とは、“ポリプロピレン樹脂がドメインの表面の一部を覆っている”という場合をも含む意味である。
即ち、熱可塑性エラストマーは、加熱状態にした際、溶融して粘度の低い状態になったポリプロピレン樹脂がドメインの周りに存在するために塑性変形させる際にポリプロピレン樹脂が潤滑剤的な機能を発揮する。
なお、ポリプロピレン樹脂や芳香族系ポリマーの溶融粘度は、一方にダイ(ダイ径:1mm、ダイ長さ:16mm)を装着し、他方を直径1mmのオリフィスとしたツインボアキャピラリーレオメータ(バレル径:15mm)によって求めることができ、例えば、温度230℃、せん断速度50(1/s)の条件で測定することができる。
熱可塑性エラストマーが、このようなモルフォロジーを示すものかどうかは、例えば、原子間力顕微鏡などで確認することができる。
この点に関して図2を参照しつつ説明する。
図2は、本実施形態に係る熱可塑性エラストマーを原子間力顕微鏡で観察した結果を示すもので、白色部分がポリプロピレン樹脂であり、該ポリプロピレン樹脂で包囲された黒色部分がスチレン系の架橋エラストマーである。
また、図2におけるその他の部分は、主として芳香族系ポリマーによって占められている部分である。
このように熱可塑性エラストマーのドメインがポリプロピレン樹脂に覆われた状態でマトリックス中に分散していることは、原子間力顕微鏡によって確認することができる。
該有機過酸化物は、具体例として、1,1-ビス(1,1-ジメチルエチルパーオキシ)シクロヘキサン、1,1-ビス(1,1-ジメチルブチルパーオキシ)シクロヘキサン、4,4-ビス[(t-ブチル)パーオキシ]ペンタン酸ブチル、ジクミルパーオキサイド、t-ブチルα-クミルパーオキサイド、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン、2,5-ビス(t-ブチルパーオキシ)-2,5-ジメチル-3-ヘキシン、ジベンゾイルパーオキサイド、ビス(4-メチルベンゾイル)パーオキサイド、2,5-ジメチル-2,5-ビス(ベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシベンゾエート、t-ヘキシルパーオキシベンゾエートなどが挙げられる。
該架橋助剤は、アクリロイル基及びメタクリロイル基の内の少なくとも1つを有していることが好ましく、複数有していることが好ましい。
なかでも、下記一般式(1)で表される化合物は、前記スチレン系ポリマーを架橋するために前記架橋剤と併用する架橋助剤として好適である。
また、前記一般式(2)における、「R2」及び「R3」は、何れか一方が水素原子で、他方が水酸基であることが特に好ましい。
即ち、下記式(4)で表されるトリメチロールプロパントリメタクリレートなども好ましい架橋助剤として挙げることができる。
前記架橋剤とともに前記架橋助剤を用いて前記スチレン系ポリマーを架橋させる場合、前記架橋助剤の使用量が多いほど耐摩耗性は向上する。
従って、架橋助剤は、通常、前記スチレン系ポリマー100質量部に対して1質量部以上含有させることが好ましく、5質量部以上含有させることがより好ましく、10質量部以上含有させることが特に好ましい。
より具体的には、前記スチレン系ポリマーを架橋させる場合、前記架橋助剤は、スチレン系ポリマー100質量部に対して0.03mol以上の割合で含有させることが好ましく、0.05mol以上の割合で含有させることがより好ましい。
なお、架橋助剤は過度に含有させる必要はなく、通常、前記スチレン系ポリマー100質量部に対して100質量部程度が上限とされ、前記スチレン系ポリマー100質量部に対して1mol程度が上限とされる。
該パラフィンオイルを熱可塑性エラストマーに含有させる場合は、前記ポリプロピレン樹脂、前記芳香族系ポリマー、及び、前記架橋エラストマーの合計100質量部に対するパラフィンオイルの割合は、10質量部以上50質量部以下とすることが好ましい。
即ち、前記熱可塑性エラストマーは、補強用シート材21やアウターソール4を上記のような成形方法によって形成させる際の形成材料として好適である。
しかも、熱可塑性エラストマーは、接着性に優れている。
従って、この熱可塑性エラストマーで補強用シート材21を形成させた場合には、例えば、該補強用シート材21を他のシートに貼り合わせてアッパー材2を形成させるために特殊な接着方法を採用しなくても済むことになる。
また、前記熱可塑性エラストマーでアウターソール4を形成させた場合には、例えば、該アウターソール4をミッドソール3に貼り合わせるために特殊な接着方法を採用しなくても済むことになる。
なお、本発明の靴形成用部材は、上記のような熱可塑性エラストマーのみによって形成させてもよく、或いは、布帛や不織布等の他の素材を併用して形成させてもよい。
また、本発明の靴形成用部材は、上記のような熱可塑性エラストマーを発泡剤などによって発泡させて形成させてもよい。
従って、熱可塑性エラストマーは、靴形成用部材の一部にのみ含有されるような場合、耐摩耗性に係る効果を靴形成用部材に発揮させる上において靴の外面や内面において露出する部位に含有されることが好ましい。
さらに、靴形成用部材に関して従来公知の技術事項は、本発明の効果が著しく損なわれない範囲においては、これを本発明の靴形成用部材にも採用することができる。
(熱可塑性エラストマーの作製)
以下の(a)~(e)の材料を2軸押出機に供給し、該2軸押出機で混練を行いつつ混練物を動的架橋し、該混練物と(f)とをドライブレンドして射出成形機に供給し、該射出成形機でテストピースを作製した。
(a)スチレン系ポリマー(SEEPS):100質量部
(b)パラフィンオイル(P-200):100質量部
(c)架橋剤(有機過酸化物(2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン)):2質量部
(d)架橋助剤(2-ヒドロキシ-3-アクリロイロキシプロピルメタクリレート):10質量部
(e)ポリプロピレン樹脂(ホモPP):20質量部
(f)ポリ-α-メチルスチレン樹脂:30~380質量部
上記のようにして得られた熱可塑性エラストマー製のテストピースについて下記項目による評価を実施した。
1)硬度:JIS K6301:1975 スプリング式硬さ試験機A形、瞬間時
2)密度:JIS K7112:1999 プラスチック-非発泡プラスチックの密度及び比重の測定方法、水中置換法(23℃)
3)引張強度:JIS K6301:1975 ダンベル2号形、「切断時引張強さ」
4)伸び:JIS K6301:1975 ダンベル2号形、「切断時伸び」
5)引裂強度:JIS K6301:1975 B形
6)DIN摩耗:JIS K6264-2:2005(B法、温度:23℃、試験片の付加力:10N、摩耗距離:40m)
7)剥離強度(接着性):JIS K 6854-2(T型剥離法、剛性被着材:熱可塑性エラストマー製テストピース(プライマー塗布)、被着材:ウレタン製の平板、剛性被着材と被着材とをウレタン系接着剤により接着、試験温度20±3℃、チャック間距離:20mm、引張速度0.00083±0.00004m/s)。
なお、プライマーとしては、一般的なオレフィン材料に用いられるもの(塩素化ポリプロピレンを含むプライマー等)を使用した。
(a)スチレン系ポリマーとして下記(a1)~(a3)の3種のもの及び(d)架橋助剤として下記(d1)~(d5)の5種のものを用いて耐摩耗性の相対比較を行った。
a)スチレン系ポリマー
(a1)SEEPS
(a2)SEBS
(a3)SBS
d)架橋助剤
(d1)2-ヒドロキシ-3-アクリロイロキシプロピルメタクリレート
(d2)トリメチロールプロパントリメタクリレート
(d3)エチレングリコールジメタクリレート
(d4)トリアリルイソシアヌレート(TAIC)
(d5)ポリエチレングリコール(#600)ジアクリレート
熱可塑性エラストマーを形成させるための原材料に占める(d)架橋助剤の配合量を0.1mol/kg又は0.06とし、且つ、(a)スチレン系ポリマー100質量部に対する(f)ポリ-α-メチルスチレン樹脂の含有量を280質量部とした以外は先の「評価1」と同様にテストピースを作製し、「評価1」と同様に評価を実施した。
評価の結果を下記に示す。
また、これまでの評価結果から、ポリオレフィン系の熱可塑性エラストマーであっても、ポリ-α-メチルスチレン構造を有している芳香族系ポリマーをマトリックスに含有させることで優れた接着性を発揮するとともに優れた耐摩耗性が発揮されることがわかる。
(評価方法)
熱可塑性エラストマーを形成させるための原材料における(e)ポリプロピレン樹脂の配合量を20質量部に代えて60質量部とし、且つ、(f)ポリ-α-メチルスチレン樹脂を含有させずにテストピースを作製し、「評価1」と同様に評価を実施した。
評価の結果を下記に示す。
Claims (7)
- 熱可塑性エラストマーを含む靴形成用部材であって、
前記熱可塑性エラストマーは、
ポリプロピレン樹脂と芳香族系ポリマーとを含むマトリックスと、
架橋エラストマーを含むドメインとを含有し、
前記芳香族系ポリマーが分子中の少なくとも一部にポリ-α-メチルスチレン構造を有している靴形成用部材。 - 前記架橋エラストマーを含むドメインが前記ポリプロピレン樹脂で覆われている請求項1記載の靴形成用部材。
- 前記芳香族系ポリマーが、α-メチルスチレン系モノマーの単独重合体である請求項1又は2記載の靴形成用部材。
- 前記α-メチルスチレン系モノマーがα-メチルスチレンで、前記芳香族系ポリマーがポリ-α-メチルスチレン樹脂である請求項3記載の靴形成用部材。
- 前記架橋エラストマーは、架橋剤及び架橋助剤によってスチレン系ポリマーが架橋されたものであり、前記架橋助剤が下記一般式(1)で表される化合物である請求項1乃至4のいずれか1項に記載の靴形成用部材。
X1-A1-R1-A2-X2 ・・・(1)
(ただし、「R1」は、炭素数2~10の鎖長を有するアルキレン、又は、該アルキレンの水素原子を置換基によって置換した置換アルキレンを表しており、「A1」及び「A2」は、それぞれ独立して直接結合又はエーテル結合を表している。また、「X1」及び「X2」は、それぞれ独立してアクリロイル基又はメタクリロイル基を表している。)
- 前記架橋エラストマーは、スチレン-エチレン-ブチレン-スチレン共重合体樹脂(SEBS)又はスチレン-エチレン-エチレン/プロピレン-スチレン共重合体樹脂(SEEPS)が架橋されたものである請求項1乃至5のいずれか1項に記載の靴形成用部材。
- 請求項1乃至6の何れか1項に記載の靴形成用部材を備えた靴。
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2015
- 2015-08-28 US US15/506,360 patent/US20170273399A1/en not_active Abandoned
- 2015-08-28 AU AU2015309728A patent/AU2015309728B2/en active Active
- 2015-08-28 JP JP2016545643A patent/JP6464174B2/ja active Active
- 2015-08-28 EP EP15836864.7A patent/EP3187062B1/en active Active
- 2015-08-28 WO PCT/JP2015/074458 patent/WO2016031972A1/ja active Application Filing
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2019
- 2019-09-25 US US16/582,168 patent/US10939725B2/en active Active
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2021
- 2021-01-29 US US17/162,399 patent/US11771172B2/en active Active
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US10939725B2 (en) | 2021-03-09 |
EP3187062A1 (en) | 2017-07-05 |
AU2015309728B2 (en) | 2022-11-03 |
US20210153598A1 (en) | 2021-05-27 |
EP3187062B1 (en) | 2020-11-04 |
JPWO2016031972A1 (ja) | 2017-06-22 |
US20170273399A1 (en) | 2017-09-28 |
JP6464174B2 (ja) | 2019-02-06 |
AU2015309728A1 (en) | 2017-03-30 |
WO2016031046A1 (ja) | 2016-03-03 |
US11771172B2 (en) | 2023-10-03 |
US20200015546A1 (en) | 2020-01-16 |
EP3187062A4 (en) | 2018-04-25 |
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