JP2015172157A - Elastic composite material - Google Patents
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- JP2015172157A JP2015172157A JP2014049158A JP2014049158A JP2015172157A JP 2015172157 A JP2015172157 A JP 2015172157A JP 2014049158 A JP2014049158 A JP 2014049158A JP 2014049158 A JP2014049158 A JP 2014049158A JP 2015172157 A JP2015172157 A JP 2015172157A
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- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 239000000835 fiber Substances 0.000 claims abstract description 124
- 239000003365 glass fiber Substances 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 52
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 50
- 239000000057 synthetic resin Substances 0.000 claims abstract description 50
- 229920001971 elastomer Polymers 0.000 claims abstract description 43
- 239000005060 rubber Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005871 repellent Substances 0.000 claims description 26
- 239000004743 Polypropylene Substances 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002972 Acrylic fiber Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 238000010586 diagram Methods 0.000 abstract 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- BSYQEPMUPCBSBK-UHFFFAOYSA-N [F].[SiH4] Chemical compound [F].[SiH4] BSYQEPMUPCBSBK-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WNYHOOQHJMHHQW-UHFFFAOYSA-N 1-chloropyrene Chemical compound C1=C2C(Cl)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WNYHOOQHJMHHQW-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】靴底等に使用される、防滑性と耐久性に優れた材料を提供することを目的とする。【解決手段】ゴム又は弾性合成樹脂を含む母材と、ガラス繊維と、合成樹脂繊維とを含む弾性複合材料であって、前記合成樹脂繊維は前記ガラス繊維よりも撥水性が高く、前記母材の表面から前記ガラス繊維及び前記合成樹脂繊維の少なくとも一部が突出している、弾性複合材料である。前記ガラス繊維及び前記合成樹脂繊維は、混繊糸として含まれることが好ましい。当該弾性複合材料は、履物底として好適に用いられる。【選択図】図１PROBLEM TO BE SOLVED: To provide a material having excellent anti-slip property and durability, which is used for a shoe sole or the like. An elastic composite material containing a base material containing rubber or an elastic synthetic resin, glass fibers, and synthetic resin fibers, the synthetic resin fibers having higher water repellency than the glass fibers, and the base material. It is an elastic composite material in which at least a part of the glass fiber and the synthetic resin fiber protrudes from the surface of the above. The glass fiber and the synthetic resin fiber are preferably contained as a mixed fiber. The elastic composite material is preferably used as a footwear sole. [Selection diagram] Fig. 1
Description
本発明は弾性を有する複合材料に関する。より詳細には、母材であるゴム等の弾性高分子材料と、ガラス繊維等とが組み合わされた複合材料であって、防滑用部材として用いられるものに関する。 The present invention relates to a composite material having elasticity. More specifically, the present invention relates to a composite material in which an elastic polymer material such as rubber as a base material and glass fiber or the like are combined and used as an anti-slip member.
雪上や凍結路の歩行に適した、滑りにくい靴底を有する靴が知られている。このような靴底に用いられる、雪氷面での防滑性を有する材料として、ゴム又は合成樹脂のマトリックスにガラス繊維を混合し、ガラス繊維の一部をマトリックスの表面から突出させたものが知られている（特許文献１）。この材料は、表面に突出したガラス繊維の一本一本が雪氷面をひっかくことによって、防滑性を発揮する。 Shoes having a non-slip sole that is suitable for walking on snow and frozen roads are known. As a material having anti-slip properties on the snow and ice surface used for such a shoe sole, a material in which glass fiber is mixed into a rubber or synthetic resin matrix and a part of the glass fiber protrudes from the surface of the matrix is known. (Patent Document 1). This material exhibits anti-slip properties because each glass fiber protruding from the surface scratches the surface of snow and ice.
また特許文献２には、ゴムや合成樹脂のマトリックス中に、非親水処理した天然植物繊維を含有し、当該天然植物繊維が履物底の表面に露出した防滑履物底が開示されている。特許文献２の発明は、防滑履物底に天然植物繊維をそのまま使用すると、天然植物繊維の有する親水性や吸水性ゆえに、弾性、ゴム成分との接着性、耐久性等が不十分であるという課題に対して、天然植物繊維をフェノールやイソシアネート等で処理することによって非親水化し、耐久性を向上させたものである。 Further, Patent Document 2 discloses a non-slip footwear bottom in which a natural vegetable fiber subjected to non-hydrophilic treatment is contained in a rubber or synthetic resin matrix, and the natural plant fiber is exposed on the surface of the footwear bottom. The invention of Patent Document 2 is that when natural plant fibers are used as they are in the non-slip footwear, the elasticity, water adhesion, durability, etc. are insufficient due to the hydrophilicity and water absorption of the natural plant fibers. In contrast, natural plant fibers are rendered non-hydrophilic by treatment with phenol, isocyanate, or the like, thereby improving durability.
しかしながら、特許文献１，２のようにガラス繊維や天然植物繊維を用いた靴底は、雪面を歩行する時に靴底に雪が付着してしまうことがあった。靴底に雪が付着すると、表面から突出した繊維が雪に覆われて雪氷面に接触しなくなるため、防滑性が発揮されない。 However, as in Patent Documents 1 and 2, a shoe sole using glass fiber or natural plant fiber sometimes has snow attached to the shoe sole when walking on the snow surface. When snow adheres to the shoe sole, the fibers protruding from the surface are covered with snow and do not come into contact with the snow ice surface, so that the slip resistance is not exhibited.
一方、濡れた路面や凍結面など、靴底と地面との接触面に水膜が介在する場合に滑りが生じ易くなることに着目し、水膜の形成を抑制するために、靴底等の表面に撥水性を付与することが提案されている（特許文献３）。特許文献３は、弾性を有する樹脂と無機充填剤とを含む弾性体組成物において、弾性樹脂から露出した無機充填剤の表面に、撥水性被膜形成分子を共有結合させて、撥水性単分子膜を形成することを開示している。 On the other hand, pay attention to the fact that slippage is likely to occur when a water film is present on the contact surface between the shoe sole and the ground, such as a wet road surface or a frozen surface. It has been proposed to impart water repellency to the surface (Patent Document 3). Patent Document 3 discloses a water repellent monomolecular film in which, in an elastic composition comprising an elastic resin and an inorganic filler, a water repellent film-forming molecule is covalently bonded to the surface of the inorganic filler exposed from the elastic resin. Is disclosed.
特許文献３の実施例には、無機充填剤を含むゴムタイヤの表面に撥水剤を処理することによって、タイヤ表面の水に対する接触角が向上したことが示されている。しかしながら、タイヤの防滑性については開示されていないため、撥水性と防滑性の関連は明らかでない。また、実用上、タイヤや靴底は、雪氷面等と繰り返し接触することによる摩耗が避けられないため、タイヤ等の最表面のみに撥水性単分子膜を設ける方策は耐久性に問題がある。 The example of Patent Document 3 shows that the contact angle with respect to water on the tire surface is improved by treating the surface of the rubber tire containing an inorganic filler with a water repellent. However, since the slip resistance of the tire is not disclosed, the relationship between water repellency and slip resistance is not clear. In practice, since tires and shoe soles are inevitably worn by repeated contact with snow and ice surfaces, the measure of providing a water-repellent monomolecular film only on the outermost surface of the tire or the like has a problem in durability.
上述のとおり、雪氷面において十分な防滑性と耐久性とを有する防滑性材料は未だ得られていない。そこで本発明は、靴底等に使用される、防滑性と耐久性に優れた材料を提供することを目的とする。 As described above, an anti-slip material having sufficient anti-slip property and durability on the surface of snow and ice has not been obtained yet. Then, an object of this invention is to provide the material excellent in slip resistance and durability used for shoe soles.
発明者らは上記課題を解決するために検討を進め、ガラス繊維がゴム材料の表面から突出した靴底において、ガラス繊維の撥水性を向上させることによって、ガラス繊維への着雪を抑制することに着想した。そして、ガラス繊維の表面をシラン処理することによって着雪が抑制されることを見出し、さらに、ガラス繊維と合成樹脂繊維とを併用することで、ガラス繊維への着雪が抑制されるだけでなく、氷上での防滑性も向上することを見出し、本発明を完成した。 The inventors proceeded with studies to solve the above-mentioned problems, and in the shoe sole in which the glass fiber protruded from the surface of the rubber material, by suppressing the water repellency of the glass fiber, the snow accumulation on the glass fiber is suppressed. Inspired by. And, it is found that by applying silane treatment to the surface of the glass fiber, the use of glass fiber and synthetic resin fiber in combination not only suppresses snow accumulation on the glass fiber but also on ice. As a result, the present invention has been completed.
すなわち本発明は、ゴム又は弾性合成樹脂を含む母材と、ガラス繊維と、合成樹脂繊維とを含む弾性複合材料であって、前記合成樹脂繊維は前記ガラス繊維よりも撥水性が高く、前記母材の表面から前記ガラス繊維及び前記合成樹脂繊維の少なくとも一部が突出している、弾性複合材料に関する。 That is, the present invention is an elastic composite material including a base material containing rubber or elastic synthetic resin, glass fiber, and synthetic resin fiber, wherein the synthetic resin fiber has higher water repellency than the glass fiber, and The present invention relates to an elastic composite material in which at least a part of the glass fiber and the synthetic resin fiber protrudes from the surface of the material.
本発明の弾性複合材料は、前記ガラス繊維及び前記合成樹脂繊維の少なくとも一部が、前記母材の表面に対して略垂直の方向に突出していることが好ましく、１μｍ〜５００μｍ突出していることがより好ましい。 In the elastic composite material of the present invention, it is preferable that at least a part of the glass fiber and the synthetic resin fiber protrude in a direction substantially perpendicular to the surface of the base material, and protrude from 1 μm to 500 μm. More preferred.
また、前記ガラス繊維と前記合成樹脂繊維とは、混繊糸として含まれていることが好ましく、特に、前記合成樹脂繊維は、撥水性を有するポリプロピレン繊維、ポリテトラフルオロエチレン繊維、フッ素繊維、又は、撥水性は前記２種の繊維に比して低いが強靭なポリエチレンテレフタレート繊維、ポリアミド繊維、アクリル繊維、生分解性を有するポリブチレンサクシネート繊維、ポリ乳酸繊維から選ばれる１種類又は２種類以上の合成樹脂繊維であることが好ましい。また、前記合成繊維の断面形状は、着雪を減じる点から円形以外に、楕円や星形など異形であることが好ましい。また、前記ガラス繊維は、その表面に撥水性被膜を有することがより好ましい。加えて、マトリックスゴムとの接着性を高める点から、ガラス繊維の断面形状も楕円や眉型など表面積の多い形状が好ましい。 Further, the glass fiber and the synthetic resin fiber are preferably contained as a mixed yarn, and in particular, the synthetic resin fiber is a polypropylene fiber, polytetrafluoroethylene fiber, fluorine fiber, or The water repellency is lower than that of the above two types of fibers, but one or two or more types selected from tough polyethylene terephthalate fibers, polyamide fibers, acrylic fibers, biodegradable polybutylene succinate fibers, and polylactic acid fibers. The synthetic resin fiber is preferable. In addition, the cross-sectional shape of the synthetic fiber is preferably an irregular shape such as an ellipse or a star in addition to a circle in terms of reducing snow accretion. Moreover, it is more preferable that the glass fiber has a water-repellent coating on its surface. In addition, the cross-sectional shape of the glass fiber is preferably a shape with a large surface area, such as an ellipse or an eyebrow shape, from the viewpoint of improving the adhesion to the matrix rubber.
本発明の弾性複合材料は、特に履物底として好適に用いられる。本発明は、底面の少なくとも一部に前記のいずれかの弾性複合材料を有する、防滑性履物に関する。 The elastic composite material of the present invention is preferably used particularly as a footwear bottom. The present invention relates to a non-slip footwear having any of the elastic composite materials described above on at least a part of a bottom surface.
本発明の弾性複合材料は、ゴム又は弾性合成樹脂を含む母材の表面から、ガラス繊維と、ガラス繊維よりも撥水性の高い合成樹脂繊維とが突出しており、表面に雪が付着しにくい。このため、ガラス繊維が雪氷面をひっかくことによる防滑性が雪上でも失われることなく発揮される。また、本発明の弾性複合材料は氷上での防滑性にも優れ、すなわち、ひっかき効果のみならず摩擦による防滑性にも優れている。本発明は、ガラス繊維と合成樹脂繊維という２種類の繊維の構造と、撥水性等の物性との相乗効果によって、着雪の抑制と氷上での防滑効果とが得られると考えられる。これらの効果は、繊維表面に撥水性被膜を有する場合、さらに優れたものとなる。
本発明の弾性複合材料は履物底として好適に用いられ、雪氷面上で滑りにくく、より安全に歩行することができる防滑性履物が得られる。
In the elastic composite material of the present invention, glass fibers and synthetic resin fibers having higher water repellency than glass fibers protrude from the surface of the base material containing rubber or elastic synthetic resin, and snow hardly adheres to the surface. For this reason, the slip resistance due to the glass fiber scratching the snow and ice surface is exhibited without being lost even on the snow. In addition, the elastic composite material of the present invention is excellent in anti-slip properties on ice, that is, excellent in anti-slip properties due to friction as well as a scratch effect. According to the present invention, it is considered that the suppression of snow accretion and the anti-slip effect on ice are obtained by the synergistic effect of the structure of two types of fibers, glass fiber and synthetic resin fiber, and physical properties such as water repellency. These effects are further improved when the fiber surface has a water-repellent coating.
The elastic composite material of the present invention is suitably used as a footwear bottom, and it is possible to obtain an anti-slip footwear that is less slippery on the snow and ice surface and can be walked more safely.
＜弾性複合材料＞
弾性複合材料の母材は、ゴム又は弾性合成樹脂を含み、ゴム又は弾性合成樹脂を主成分とするものである。ゴムとしては例えば、天然ゴムや、スチレンブタジエンゴム、ブタジエンゴム、イソプレンゴム、ニトリルブタジエンゴム、クロロプレンゴム等のジエン系ゴムや、ブチルゴム、エチレンプロピレンゴム、ウレタンゴム、シリコーンゴム、クロロスルフォン化ゴム、アクリルゴム、エピクロルヒドリンゴム等の非ジエン系ゴムが挙げられ、これらのいずれかを単独で、又は２種以上を組み合わせて使用することができる。弾性合成樹脂としては、熱可塑性エラストマーと称されるものが挙げられ、スチレン系エラストマー、オレフィン系エラストマー、塩ビ系エラストマー、ウレタンエラストマー、エステル系エラストマー、アミド系エラストマー等が挙げられ、これらのいずれかを単独で、又は２種以上を組み合わせて使用することができる。母材は、複合材料の使用用途や求める物性によって適宜選択すればよいが、例えば、履物底として用いる場合、天然ゴム、アクリルニトリルブタジエンゴム、クロロピレンゴム、スチレンブタジエンゴムやそれらを互いに配合させたゴム等が好適に用いられる。
<Elastic composite material>
The base material of the elastic composite material contains rubber or elastic synthetic resin, and is mainly composed of rubber or elastic synthetic resin. Examples of rubber include natural rubber, diene rubbers such as styrene butadiene rubber, butadiene rubber, isoprene rubber, nitrile butadiene rubber, and chloroprene rubber, butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, chlorosulfonated rubber, acrylic Non-diene rubbers such as rubber and epichlorohydrin rubber can be used, and any of these can be used alone or in combination of two or more. Examples of the elastic synthetic resin include what is called a thermoplastic elastomer, and examples thereof include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like. It can be used alone or in combination of two or more. The base material may be selected as appropriate depending on the intended use of the composite material and the required physical properties. For example, when used as a footwear bottom, natural rubber, acrylonitrile butadiene rubber, chloropyrene rubber, styrene butadiene rubber and the like are blended with each other. Rubber or the like is preferably used.
母材であるゴムや弾性合成樹脂には任意の添加剤等を含んでよく、添加剤としては例えば、炭酸カルシウムや炭酸マグネシウム、シリカ、カーボンブラック等の充填剤や、硫黄、可塑剤、着色剤、軟化剤、硬化剤、劣化防止剤等が挙げられる。 Rubber or elastic synthetic resin, which is a base material, may contain any additive, and examples of additives include fillers such as calcium carbonate, magnesium carbonate, silica, and carbon black, sulfur, plasticizer, and colorant. , Softeners, curing agents, deterioration inhibitors and the like.
前記の母材に含まれるガラス繊維及び合成樹脂繊維としては、公知のものを用いることができる。合成樹脂繊維は、ガラス繊維よりも撥水性の高い繊維が用いられる。ここで、ガラス繊維よりも撥水性が高いとは、接触角がガラス繊維のそれより大であることを意味しており、例えば、ポリプロピレン繊維、ポリテトラフルオロエチレン繊維，フッ素繊維，ポリエチレンテレフタレート繊維、ポリアミド繊維、アクリル繊維、ポリブチレンサクシネート繊維、ポリ乳酸繊維等が挙げられる。合成樹脂繊維は、撥水性、安定性、母材との接着性等を考慮して適宜選択されるが、中でも撥水性と湿潤安定性に優れるポリプロピレン繊維、ポリテトラフルオロエチレン繊維、フッ素繊維が好ましく用いられる。 As the glass fiber and the synthetic resin fiber contained in the base material, known ones can be used. As the synthetic resin fiber, a fiber having higher water repellency than the glass fiber is used. Here, the higher water repellency than the glass fiber means that the contact angle is larger than that of the glass fiber. For example, polypropylene fiber, polytetrafluoroethylene fiber, fluorine fiber, polyethylene terephthalate fiber, Examples thereof include polyamide fiber, acrylic fiber, polybutylene succinate fiber, and polylactic acid fiber. The synthetic resin fiber is appropriately selected in consideration of water repellency, stability, adhesion to the base material, etc., among which polypropylene fiber, polytetrafluoroethylene fiber, and fluorine fiber, which are excellent in water repellency and wet stability, are preferable. Used.
本発明の複合材料において、ガラス繊維及び合成樹脂繊維は、複合材料の面に対して略垂直に配向されて、複合材料の表面からその一部が突出している。略垂直に配向されているとは、例えば複合材料が靴底である場合、靴底の接地面に対して突出した繊維が略垂直になることを意味する。略垂直であることで、繊維が雪氷面をひっかくことによる防滑性をより効果的に得られる。突出した繊維の全てが略垂直に配向していることが好ましいが、繊維がランダムに配向され、そのうちの一部が略垂直方向に突出しているのでもよい。繊維がランダムに配向されている場合は、繊維の表面がより多く複合体の表面に露出するため、複合材料の表面の凹凸や、繊維の摩擦特性によっても防滑性が得られる。 In the composite material of the present invention, the glass fiber and the synthetic resin fiber are oriented substantially perpendicular to the surface of the composite material, and a part thereof protrudes from the surface of the composite material. For example, when the composite material is a shoe sole, the fiber that protrudes with respect to the ground contact surface of the shoe sole becomes substantially vertical. By being substantially vertical, it is possible to more effectively obtain slip resistance due to the fibers scratching the surface of snow and ice. Although it is preferable that all the protruding fibers are oriented substantially vertically, the fibers may be randomly oriented, and some of them may protrude in a substantially vertical direction. When the fibers are randomly oriented, more fiber surfaces are exposed on the surface of the composite, so that anti-slip properties can also be obtained depending on the unevenness of the surface of the composite material and the frictional properties of the fibers.
突出した繊維の長さは、目的や用途によって任意に選択できるが、例えば１μｍ〜５００μｍとすることができ、５μｍ〜１００μｍがより好ましく、１０μｍ〜３０μｍが特に好ましい。突出部をこの範囲の長さとすることで、雪氷面を歩行する際には突出した繊維が雪氷面をひっかいて防滑効果を得られるとともに、十分な耐久性が得られる。 Although the length of the protruding fiber can be arbitrarily selected depending on the purpose and application, it can be, for example, 1 μm to 500 μm, more preferably 5 μm to 100 μm, and particularly preferably 10 μm to 30 μm. By setting the length of the protruding portion within this range, when walking on the surface of the snow and ice, the protruding fibers can scratch the surface of the snow and ice to obtain an anti-slip effect, and sufficient durability can be obtained.
上記のガラス繊維と合成樹脂繊維とは、別々の糸として含有されていてもよいが、一本の糸にガラス繊維と合成樹脂繊維とが含有されている混繊糸（コミングルヤーン）であることが好ましい。混繊糸である場合、例えば、直径１０〜２５μｍのガラス繊維単糸と、直径１０〜２５μｍの合成樹脂繊維単糸とを含む糸を用いることができる。このようなコミングルヤーンとしては市販のものを用いることもでき、例えば、Fiber Glass Industries社のTWINTEX（登録商標）やComfil ApS社のCOMFIL（登録商標）を用いることができる。コミングルヤーンを用いると、複合材料の表面において、ガラス繊維の近傍に撥水性の高い合成樹脂繊維を確実に存在させられるため、ガラス繊維への水膜の形成が抑制され、それによってガラス繊維への着雪が抑制されると考えられている。 The glass fiber and the synthetic resin fiber may be contained as separate yarns, but are mixed fiber (comingle yarn) in which the glass fiber and the synthetic resin fiber are contained in one yarn. It is preferable. In the case of a blended yarn, for example, a yarn including a glass fiber single yarn having a diameter of 10 to 25 μm and a synthetic resin fiber single yarn having a diameter of 10 to 25 μm can be used. As such a comingle yarn, a commercially available product can be used. For example, TWINTEX (registered trademark) manufactured by Fiber Glass Industries or COMFIL (registered trademark) manufactured by Comfil ApS can be used. By using the Comingle yarn, synthetic resin fibers with high water repellency can be surely present in the vicinity of the glass fibers on the surface of the composite material, so that formation of a water film on the glass fibers is suppressed, thereby It is thought that the snowfall of snow is suppressed.
本発明の複合材料における繊維成分（ガラス繊維及び合成樹脂繊維）の割合は、母材に対して繊維成分を１ｗｔ％〜３０ｗｔ％とすることができ、５ｗｔ％〜１５ｗｔ％であればより好ましい。この範囲とすることで、防滑性能と、複合材料の強度及び耐久性を両立することができる。また、複合材料の表面における突出した繊維の本数は、複合材料１ｍｍ２あたり１０本〜５００本程度であり、２０本〜１００本程度であればより好ましい。 The ratio of the fiber component (glass fiber and synthetic resin fiber) in the composite material of the present invention is preferably 1 wt% to 30 wt% with respect to the base material, and more preferably 5 wt% to 15 wt%. By setting it as this range, it is possible to achieve both the anti-slip performance and the strength and durability of the composite material. The number of protruding fibers on the surface of the composite material is about 10 to 500 per 1 mm 2 of the composite material, and more preferably about 20 to 100.
ガラス繊維及び合成樹脂繊維は、特に表面処理をせずに用いることもできるが、ガラス繊維の表面に撥水性被膜を有するものを用いることが好ましい。撥水性被膜としては、ガラス繊維の表面に、シランカップリング反応を用いて各種の有機基や疎水性基が共有結合されてなる被膜がある。撥水性被膜の形成のために用いられるシランカップリング剤としては、各種のアルコキシシラン化合物が挙げられ、例えば、γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−Ｎ’−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、γ−アニリノプロピルトリメトキシシランなどのアミノ基含有シランカップリング剤、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシランなどのメルカプト基含有シランカップリング剤、メチルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリメトキシシラン等のアルキルアルコキシシラン、トリフルオロプロピルトリメトキシシラン、パーフルオロポリエーテルアルコキシシラン等のフッ素系シラン化合物などが挙げられる。これらシランカップリング剤は単独または２種以上を併用することができる。これらのうちでも、アミノシラン、メルカプトシラン、フッ素シラン，デシルトリメトキシシラン等が好ましく用いられる。シランカップリング剤は、撥水性や母材との接着性を考慮して適宜選択することができる。 Glass fibers and synthetic resin fibers can be used without any surface treatment, but those having a water-repellent coating on the surface of the glass fibers are preferably used. Examples of the water-repellent coating include a coating in which various organic groups and hydrophobic groups are covalently bonded to the surface of glass fiber using a silane coupling reaction. Examples of the silane coupling agent used for forming the water-repellent coating include various alkoxysilane compounds such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltri Amino group-containing silane coupling agents such as methoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ- Mercapto group-containing silane coupling agents such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxy Examples include silane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, alkylalkoxysilane such as decyltrimethoxysilane, fluorine-based silane compounds such as trifluoropropyltrimethoxysilane, and perfluoropolyetheralkoxysilane. . These silane coupling agents can be used alone or in combination of two or more. Of these, aminosilane, mercaptosilane, fluorine silane, decyltrimethoxysilane and the like are preferably used. The silane coupling agent can be appropriately selected in consideration of water repellency and adhesiveness with the base material.
なお、本明細書において、「繊維表面に撥水性被膜を有する」とは、繊維表面の全体又は一部が撥水性被膜に覆われた状態を意味し、また、繊維表面の全体又は一部に不連続的に疎水性基又は撥水性基を有する状態も含む。さらに、繊維表面に何らかの撥水処理がなされて、処理後の繊維表面が処理前の繊維表面よりも撥水性の高い状態であることも含む。 In this specification, “having a water-repellent coating on the fiber surface” means a state in which the entire or part of the fiber surface is covered with the water-repellent coating, The state which has a hydrophobic group or a water-repellent group discontinuously is also included. Furthermore, it also includes that the fiber surface is subjected to some water repellent treatment, and the treated fiber surface is in a state of higher water repellency than the untreated fiber surface.
本発明の弾性複合材料は防滑性が求められる用途に好適に用いられる。例えば、靴、サンダル、スリッパ等の履物底、床材、敷物、ローラー、パレット、グリップ等の部材として使用される。また汎用的な防滑シール、防滑マット等として使用することも可能である。中でも、履物底に使用されることが好ましい。履物底として使用される場合、履物の底面全体が本発明の弾性複合材料からなっていてもよいし、底面の一部が本発明の弾性複合材料からなっていてもよい。底面の一部が本発明の弾性複合材料からなる場合、足先部や踵部等、特に地面と接する部分を本発明の弾性複合材料で構成することが好ましい。靴底において、本発明の弾性複合材料と他の材料とを組み合わせる場合、組み合わせる材料は特に制限されず、所望の特性を有する任意の材料を用いることができる。例えば、汎用的なゴム底材や合成樹脂材を用いてもよく、また、撥水処理したゴムや合成樹脂材料や、撥水性繊維を含むゴムや合成樹脂材料等を用いることもできる。ガラス繊維等を含有した複合材料が用いられていない箇所に付着した雪がアンカーとなって、靴底全体に着雪することもあるため、ガラス繊維等を含有した複合材料以外の部分も、撥水性の材料で構成することが好ましい。 The elastic composite material of the present invention is suitably used for applications requiring anti-slip properties. For example, it is used as a member such as footwear bottoms such as shoes, sandals, slippers, flooring materials, rugs, rollers, pallets, grips and the like. It can also be used as a general-purpose anti-slip seal, anti-slip mat or the like. Among these, it is preferable to be used for footwear bottoms. When used as a footwear bottom, the entire bottom surface of the footwear may be made of the elastic composite material of the present invention, or a part of the bottom surface may be made of the elastic composite material of the present invention. When a part of the bottom surface is made of the elastic composite material of the present invention, it is preferable that a portion in contact with the ground, such as a toe portion or a heel portion, is made of the elastic composite material of the present invention. When combining the elastic composite material of the present invention with another material in a shoe sole, the material to be combined is not particularly limited, and any material having desired characteristics can be used. For example, a general-purpose rubber bottom material or synthetic resin material may be used, and a water-repellent treated rubber or synthetic resin material, a rubber containing water-repellent fibers, a synthetic resin material, or the like may be used. Since snow attached to places where composite materials containing glass fibers etc. are not used can become anchors and snowfall on the entire shoe sole, parts other than composite materials containing glass fibers etc. are also water-repellent It is preferable to comprise with the material of.
弾性複合材料を靴底に適用する場合、弾性複合材料の厚みは特に制限されないが、例えば厚み１〜２０ｍｍの靴底部材とすることができる。また、弾性複合材料に任意の溝を形成して、排水性やグリップ性を高めることも好ましい。 When the elastic composite material is applied to the shoe sole, the thickness of the elastic composite material is not particularly limited, but can be a shoe sole member having a thickness of 1 to 20 mm, for example. It is also preferable to form an arbitrary groove in the elastic composite material to improve drainage and grip properties.
＜弾性複合材料の製造方法＞
本発明の弾性複合材料の製造方法は特に制限されず、公知の方法に従って、又は公知の方法を一部修正して製造することができる。例えば、次の方法が挙げられる。
ゴム等の母材シート上に、予め撥水性被膜を形成したガラス繊維及び合成樹脂繊維（混繊糸であることが好ましい）を一方向に引き揃えて載置し、母材シートとガラス繊維及び合成樹脂繊維とを圧着する。続いて、圧着した材料を、繊維と直交方向に所定の幅で裁断する。この裁断の幅が、完成した弾性複合材料の厚み方向となるため、所望の厚みから裁断の幅を決めることができる。続いて、裁断した材料を、繊維の断面が上下方向になるように複数並べて載置し、ヒートプレス機を用いて加硫及び架橋を行うことで、複数の裁断材料を一体化し、厚み方向に繊維が配向した複合体を得る。続いてグラインダーを用いて当該複合体の片面を擦過することによって、母材の表層を削り取り、複合体の表面からガラス繊維及び合成樹脂繊維を露出させる。削り取る母材表層の厚みによって、複合体の表面から突出する繊維の長さを調整できる。
<Method for producing elastic composite material>
The method for producing the elastic composite material of the present invention is not particularly limited, and can be produced according to a known method or by partially modifying the known method. For example, the following method is mentioned.
A glass fiber and a synthetic resin fiber (preferably a mixed fiber) on which a water-repellent film is formed in advance are placed on a base material sheet such as rubber in one direction, and the base material sheet, the glass fiber, Crimp the synthetic resin fiber. Subsequently, the pressure-bonded material is cut with a predetermined width in a direction orthogonal to the fibers. Since the cutting width is in the thickness direction of the completed elastic composite material, the cutting width can be determined from a desired thickness. Subsequently, a plurality of the cut materials are placed side by side so that the cross section of the fiber is in the vertical direction, and by vulcanization and crosslinking using a heat press machine, the plurality of cut materials are integrated in the thickness direction. A composite with oriented fibers is obtained. Subsequently, the surface of the base material is scraped off by rubbing one side of the composite using a grinder, and glass fibers and synthetic resin fibers are exposed from the surface of the composite. The length of the fiber protruding from the surface of the composite can be adjusted by the thickness of the surface layer of the base material to be scraped.
別の製造方法として、次の方法がある。すなわち、原料ゴム、予め撥水被膜を形成したガラス繊維及び合成樹脂繊維（混繊糸であることが好ましい）、硫黄や添加剤等の成分をロール混練し、繊維入りゴム生地を得る。続いて当該ゴム生地を圧延することによって、繊維が圧延方向に配向した圧延ゴム生地を得る。当該圧延ゴム生地を裁断し、積層する。続いて、積層した圧延ゴム生地を積層面と直交方向に裁断することによって、裁断面に繊維が配向した材料を得る。当該裁断積層材料をプレスによって一体化することで、弾性材料複合体を得る。続いてグラインダーを用いて当該複合体の片面を擦過することによって、母材の表層を削り取り、複合体の表面からガラス繊維及び合成樹脂繊維を露出させる。削り取る母材表層の厚みによって、複合体の表面から突出する繊維の長さを調整できる。 As another manufacturing method, there is the following method. That is, raw rubber, glass fiber and water-repellent coating previously formed, synthetic resin fiber (preferably mixed fiber), sulfur and additives are roll-kneaded to obtain a rubber fabric containing fibers. Subsequently, by rolling the rubber dough, a rolled rubber dough having fibers oriented in the rolling direction is obtained. The rolled rubber dough is cut and laminated. Subsequently, the laminated rolled rubber dough is cut in a direction orthogonal to the lamination surface to obtain a material in which fibers are oriented in the cut surface. An elastic material composite is obtained by integrating the cut laminated material by pressing. Subsequently, the surface of the base material is scraped off by rubbing one side of the composite using a grinder, and glass fibers and synthetic resin fibers are exposed from the surface of the composite. The length of the fiber protruding from the surface of the composite can be adjusted by the thickness of the surface layer of the base material to be scraped.
ガラス繊維やガラス繊維を含む混繊糸の撥水処理は、公知の方法に従って、又は公知の方法を一部修正して行うことができる。例えば、シランカップリング剤を所定の濃度になるよう有機溶媒や水（例えばアルコール水溶液）で希釈した溶液に、繊維を浸漬し、（例えば３０秒間〜１分間）、続いて電気炉等で乾燥させる（例えば、１００℃で１時間）ことによって、繊維表面に撥水性被膜を形成させる。この方法によれば、繊維の表面全体に撥水性被膜が形成されるため、複合材料の使用に従って繊維の一部が摩耗しても、撥水表面が失われることがない。つまり、複合材料を作成した後に複合体の表面に撥水性被膜を形成するよりも、予め撥水処理をした繊維を用いて複合材料を作製する方が、撥水性表面の耐久性に優れる。 The water-repellent treatment of glass fiber or a mixed fiber containing glass fiber can be performed according to a known method or by partially modifying a known method. For example, the fiber is immersed in a solution diluted with an organic solvent or water (for example, an alcohol aqueous solution) so that the silane coupling agent has a predetermined concentration (for example, for 30 seconds to 1 minute), and then dried in an electric furnace or the like. (For example, at 100 degreeC for 1 hour), a water-repellent film is formed in the fiber surface. According to this method, since the water-repellent coating is formed on the entire surface of the fiber, the water-repellent surface is not lost even if part of the fiber is worn according to the use of the composite material. That is, rather than forming a water-repellent film on the surface of the composite after preparing the composite material, it is more excellent in durability of the water-repellent surface to prepare the composite material using fibers that have been subjected to water-repellent treatment in advance.
＜実施例及び比較例の作製＞
［材料］
生ゴム（厚み0.5mm、社内品）
ガラス繊維（RS220RL-510：日東紡社製）（以下、GFと記すことがある。）
ガラス繊維／ポリプロピレン繊維コミングルヤーン（TWINTEX（登録商標）：Fiber Glass Industries社製）（以下、GF/PPと記すことがある。）
アミノシラン（KBE903：信越化学工業社製）
メルカプトシラン（KBM803：信越化学工業社製）
フッ素シラン（KBM7103：信越化学工業社製）
デシルトリメトキシシラン（KBM8103：信越化学工業社製）
<Production of Examples and Comparative Examples>
[material]
Raw rubber (thickness 0.5mm, in-house product)
Glass fiber (RS220RL-510: Nittobo Co., Ltd.) (hereinafter sometimes referred to as GF)
Glass fiber / polypropylene fiber Comingle yarn (TWINTEX (registered trademark): manufactured by Fiber Glass Industries) (hereinafter sometimes referred to as GF / PP)
Aminosilane (KBE903: manufactured by Shin-Etsu Chemical Co., Ltd.)
Mercaptosilane (KBM803: Shin-Etsu Chemical Co., Ltd.)
Fluorosilane (KBM7103: Shin-Etsu Chemical Co., Ltd.)
Decyltrimethoxysilane (KBM8103: Shin-Etsu Chemical Co., Ltd.)
［実施例１］
次の方法に従って弾性複合材料を作製した。
（１）GF/PPとゴムシートとを交互に積層した。繊維は一方向に並べた。
（２）繊維とゴムシートの接着性を向上させるためプレス機を用いて5MPaで材料を圧縮した。
（３）プレス後、並べた繊維に対して90°になるように積層した材料を短冊状に5mm幅で切断した。
（４）金型に繊維が90°となるように材料を敷き詰め、ヒートプレス機（ＡＹＳＲ−５：神藤金属工業）を用いて155℃、9.8MPa、9分の条件で加硫を行った。
（５）金型が冷めた後材料を取り出し、砥石車を用いて材料の表面を研削し繊維をゴム表面から突出させて、弾性複合材料を得た。
[Example 1]
An elastic composite material was produced according to the following method.
(1) GF / PP and rubber sheets were laminated alternately. The fibers were arranged in one direction.
(2) The material was compressed at 5 MPa using a press to improve the adhesion between the fiber and the rubber sheet.
(3) After pressing, the material laminated so as to be 90 ° with respect to the arranged fibers was cut into strips with a width of 5 mm.
(4) The material was spread on the mold so that the fibers were 90 °, and vulcanization was performed using a heat press machine (AYSR-5: Shinto Metal Industry) at 155 ° C., 9.8 MPa, and 9 minutes.
(5) After the mold was cooled, the material was taken out, the surface of the material was ground using a grinding wheel, and the fiber was protruded from the rubber surface to obtain an elastic composite material.
上記の方法で得られた複合材料の表面の拡大像を図１に示す。上図はレーザ顕微鏡像である。図では、画像の中央帯部（農色部分）に繊維が多数突出していることが観察され、上下の薄色部分が母材であるゴムである。下図は，上図で得られた表面の凹凸を３次元立体画像化しており、突出部（繊維部分）が約５μｍ〜５０μｍであることがわかる。 An enlarged image of the surface of the composite material obtained by the above method is shown in FIG. The upper figure is a laser microscope image. In the figure, it is observed that many fibers protrude from the central band portion (agricultural color portion) of the image, and the upper and lower light-colored portions are rubbers that are base materials. The lower figure shows a three-dimensional stereoscopic image of the surface irregularities obtained in the upper figure, and it can be seen that the protruding part (fiber part) is about 5 μm to 50 μm.
［実施例２］
GF/PPを積層する前に、次の手順でGF/PPに対してシラン処理を行った。
（Ｉ）アルコール水溶液（エタノール／水＝９／１）にアミノシランを１ｗｔ％となるよう添加し、１５００ｒｐｍ、１５分間ホモジナイザーを用いて撹拌して、アミノシラン溶液を得た。
（II）GF/PPをアミノシラン溶液に３０秒間浸漬した。
（III）電気炉を用いて、１００℃、１時間で浸漬後の繊維を乾燥した。
上記方法で得たアミノシラン処理GF/PPを用いて、実施例１と同様の方法で弾性複合材料を得た。
[Example 2]
Before laminating GF / PP, silane treatment was performed on GF / PP by the following procedure.
(I) Aminosilane was added to an aqueous alcohol solution (ethanol / water = 9/1) so as to be 1 wt%, and the mixture was stirred using a homogenizer at 1500 rpm for 15 minutes to obtain an aminosilane solution.
(II) GF / PP was immersed in an aminosilane solution for 30 seconds.
(III) The fibers after immersion were dried at 100 ° C. for 1 hour using an electric furnace.
Using the aminosilane-treated GF / PP obtained by the above method, an elastic composite material was obtained in the same manner as in Example 1.
［実施例３］
アミノシランに替えて、メルカプトシランを用いたこと以外は実施例２と同様の方法で弾性複合材料を得た。
[Example 3]
An elastic composite material was obtained in the same manner as in Example 2 except that mercaptosilane was used instead of aminosilane.
［実施例４］
アミノシランに替えて、フッ素シランを用いたこと以外は実施例２と同様の方法で弾性複合材料を得た。
[Example 4]
An elastic composite material was obtained in the same manner as in Example 2 except that fluorine silane was used instead of aminosilane.
［実施例５］
アミノシランに替えて、デシルトリメトキシシランを用いたこと以外は実施例２と同様の方法で弾性複合材料を得た。
[Example 5]
An elastic composite material was obtained in the same manner as in Example 2 except that decyltrimethoxysilane was used instead of aminosilane.
［比較例１］
GF/PPに替えて、GFを用いたこと以外は実施例１と同様の方法で弾性複合材料を得た。
[Comparative Example 1]
An elastic composite material was obtained in the same manner as in Example 1 except that GF was used instead of GF / PP.
［実施例６］
次の方法に従って弾性複合材料を作製した。
（１）原料ゴム１１５部に、添加剤等６７部、ガラス繊維／ポリプロピレン繊維コミングルヤーン（GF/PP）３３部、硫黄５部を添加し、ロール混練によって繊維入りゴム生地を得た。
（２）繊維入りゴム生地を圧延、裁断、積層した。
（３）積層した繊維入りゴム生地を、積層面と直交する方向に裁断し、裁断した積層体をプレス処理によって一体化し、繊維入り加硫ゴムを得た。
（４）繊維入り加硫ゴムの一面をグラインダーで鋤き、加硫ゴムの表層を除去することによって、ガラス繊維が表面に突出した弾性複合材料を得た。
[Example 6]
An elastic composite material was produced according to the following method.
(1) To 115 parts of raw rubber, 67 parts of additives, 33 parts of glass fiber / polypropylene fiber combing yarn (GF / PP) and 5 parts of sulfur were added, and a fiber-containing rubber fabric was obtained by roll kneading.
(2) Rolled, cut and laminated the rubber fabric containing fibers.
(3) The laminated fiber-containing rubber fabric was cut in a direction orthogonal to the lamination surface, and the cut laminate was integrated by a press treatment to obtain a fiber-containing vulcanized rubber.
(4) One surface of the vulcanized rubber containing fibers was ground with a grinder, and the surface layer of the vulcanized rubber was removed to obtain an elastic composite material with glass fibers protruding on the surface.
［実施例７］
GF/PPを原料ゴムに添加する前に、次の手順でGF/PPに対してシラン処理を行った。
（Ｉ）アルコール水溶液（エタノール／水＝９／１）にアミノシランを１ｗｔ％となるよう添加し、１５００ｒｐｍ、１５分間ホモジナイザーを用いて撹拌して、アミノシラン溶液を得た。
（II）GF/PPをアミノシラン溶液に１分間浸漬した。
（III）１００℃、１時間で浸漬後の繊維を乾燥した。
上記方法で得たアミノシラン処理GF/PPを用いて、実施例６と同様の方法で弾性複合材料を得た。
[Example 7]
Before adding GF / PP to the raw rubber, silane treatment was performed on GF / PP by the following procedure.
(I) Aminosilane was added to an aqueous alcohol solution (ethanol / water = 9/1) so as to be 1 wt%, and the mixture was stirred using a homogenizer at 1500 rpm for 15 minutes to obtain an aminosilane solution.
(II) GF / PP was immersed in an aminosilane solution for 1 minute.
(III) The fibers after immersion were dried at 100 ° C. for 1 hour.
Using the aminosilane-treated GF / PP obtained by the above method, an elastic composite material was obtained in the same manner as in Example 6.
［実施例８］
アミノシランに替えて、メルカプトシランを用いたこと以外は実施例７と同様の方法で弾性複合材料を得た。
[Example 8]
An elastic composite material was obtained in the same manner as in Example 7 except that mercaptosilane was used instead of aminosilane.
［実施例９］
アミノシランに替えて、フッ素シランを用いたこと以外は実施例７と同様の方法で弾性複合材料を得た。
[Example 9]
An elastic composite material was obtained in the same manner as in Example 7 except that fluorine silane was used instead of aminosilane.
［実施例１０］
アミノシランに替えて、デシルトリメトキシシランを用いたこと以外は実施例７と同様の方法で弾性複合材料を得た。
[Example 10]
An elastic composite material was obtained in the same manner as in Example 7 except that decyltrimethoxysilane was used instead of aminosilane.
［比較例２］
GF/PPに替えて、GFを用いたこと以外は実施例６と同様の方法で弾性複合材料を得た。
[Comparative Example 2]
An elastic composite material was obtained in the same manner as in Example 6 except that GF was used instead of GF / PP.
＜着雪試験＞
実施例１〜５及び比較例１の弾性複合材料について着雪試験を行った。
氷削機（EC-80E：中部コーポレーション）と冷凍庫で作製した氷を用いて人工雪を作製し、PP製ステージ（120mm×120mm）に積雪させた。試験片の重量を測定した後、試験片の繊維が突出した面と積雪面とを接地させ試験片に対して約10Nの押付け力を与えた。３０秒間放置し、その後押付け力を除去し材料を積雪面から引き離して、着雪を含んだ試験片の重量を測定した。試験前後の重量変化から着雪量を算出した。試験条件は、試験片の重量測定の直前に試験片表面に霧吹きを行う（湿雪条件）、霧吹きを行わない（乾雪条件）の２条件とし、各試験は５回ずつ行った。試験は屋外環境下（２℃、１７％ＲＨ）で行った。
<Snow accretion test>
A snow accretion test was performed on the elastic composite materials of Examples 1 to 5 and Comparative Example 1.
Artificial snow was made using ice produced with an ice-shaving machine (EC-80E: Chubu Corporation) and a freezer, and was placed on a PP stage (120 mm x 120 mm). After measuring the weight of the test piece, the surface of the test piece from which the fibers protruded and the snow-covered surface were grounded, and a pressing force of about 10 N was applied to the test piece. The sample was left for 30 seconds, and then the pressing force was removed, the material was pulled away from the snow-covered surface, and the weight of the test piece including snow was measured. The amount of snowfall was calculated from the weight change before and after the test. The test conditions were two conditions: spraying the surface of the test piece just before the weight measurement of the test piece (wet snow condition) and not spraying (dry snow condition), and each test was performed five times. The test was performed in an outdoor environment (2 ° C., 17% RH).
結果は図２に示すとおり、湿雪条件、乾雪条件のいずれの場合も、GF/PPを用いた実施例１〜５の複合体は、GFを用いた比較例１よりも着雪量が少なかった。中でも、実施例２の着雪量は比較例の約１／２であった。すなわち、GF/PPを用いた弾性複合材料は、GFを用いたものと比較して着雪が抑制されることが確認された。 As shown in FIG. 2, the composites of Examples 1 to 5 using GF / PP have a larger amount of snowfall than Comparative Example 1 using GF as shown in FIG. There were few. Especially, the amount of snowfall of Example 2 was about 1/2 of the comparative example. That is, it was confirmed that the elastic composite material using GF / PP suppresses snow accretion compared to that using GF.
＜撥水性の評価＞
実施例１及び比較例１の弾性複合材料の動的撥水性を評価した。動的撥水性は、液体の固体に対する滑りやすさを示す指標である。
水滴0.1mLを水平に載置した試験片に滴下し、試験片を徐々に傾斜させていき、水滴が滑り出す角度βを測定し、転落角とした。
<Evaluation of water repellency>
The dynamic water repellency of the elastic composite materials of Example 1 and Comparative Example 1 was evaluated. The dynamic water repellency is an index indicating the slipperiness of a liquid with respect to a solid.
0.1 mL of water droplets were dropped on a horizontally placed test piece, the test piece was gradually inclined, and the angle β at which the water droplets slid was measured to obtain the falling angle.
結果は図３に示すとおり、実施例１の弾性複合材料は比較例１よりも転落角が３０％以上小さかった。すなわち、実施例１の弾性複合体は動的撥水性が高く、水滴が除去されやすい。この結果は、本発明の実施例である弾性複合材料の表面には、水膜が形成されにくいことを示すものである。 As a result, as shown in FIG. 3, the elastic composite material of Example 1 had a sliding angle of 30% or more smaller than that of Comparative Example 1. That is, the elastic composite of Example 1 has high dynamic water repellency, and water droplets are easily removed. This result shows that it is difficult to form a water film on the surface of the elastic composite material which is an example of the present invention.
＜防滑性試験＞
実施例６〜１０及び比較例２の弾性複合材料の防滑性能を評価した。
試験方法は、ＪＩＳ Ａ１４５４高分子系張り床材試験方法６．１２滑り性試験に準拠して行なった。滑りにくさの評価には、ＪＩＳ Ａ１４５４高分子系張り床材試験方法６．１２滑り性試験に指定されている、ＯＹ−ＰＳＭ小野式滑り試験機を使用した。滑りにくさの評価は最大静止摩擦係数：C.S.R．(coefficient of slip resistance）で示される。C.S.R．の許容範囲は０．４〜１．０で、０．４以下では滑りやすく危険、１．０以上では滑りにくいため、つんのめる危険があるとされている。
<Anti-slip test>
The anti-slip performance of the elastic composite materials of Examples 6 to 10 and Comparative Example 2 was evaluated.
The test method was performed in accordance with JIS A1454 polymer-based upholstery floor test method 6.12 slip test. For the evaluation of the difficulty of slipping, an OY-PSM Ono type slip tester specified in the JIS A1454 polymer-based tension flooring test method 6.12 slipperiness test was used. The evaluation of the difficulty of sliding is the maximum static friction coefficient: CSR. It is indicated by (coefficient of slip resistance). CSR. The allowable range is 0.4 to 1.0, and it is said that there is a risk of slipping when it is 0.4 or less, and it is difficult to slip when it is 1.0 or more.
結果を表１に示す。
表１に示されるとおり、実施例６〜１０の複合材料は、乾いた氷面、湿った氷面、乾いた大理石面において、比較例２よりも高いＣＳＲ値を示した。中でも、実施例７及び９は、湿った氷面において高いＣＳＲ値を示した。すなわち、本発明の実施例の複合材料はいずれも高い防滑性（特に、氷上防滑性）を有することが確認された。ガラス繊維と合成樹脂繊維とを併用することによって氷上防滑性が向上することは、予測されない有利な効果であった。 As shown in Table 1, the composite materials of Examples 6 to 10 exhibited higher CSR values than Comparative Example 2 on the dry ice surface, wet ice surface, and dry marble surface. Among them, Examples 7 and 9 showed high CSR values on wet ice surfaces. That is, it was confirmed that all the composite materials of the examples of the present invention have high slip resistance (particularly, slip resistance on ice). Improvement of anti-slip property on ice by using glass fiber and synthetic resin fiber in combination was an unexpected and advantageous effect.
Claims (8)
前記合成樹脂繊維は前記ガラス繊維よりも撥水性が高く、
前記母材の表面から、前記ガラス繊維及び前記合成樹脂繊維の少なくとも一部が突出している、弾性複合材料。 An elastic composite material including a base material containing rubber or elastic synthetic resin, glass fiber, and synthetic resin fiber,
The synthetic resin fiber has higher water repellency than the glass fiber,
An elastic composite material in which at least a part of the glass fiber and the synthetic resin fiber protrudes from the surface of the base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014049158A JP2015172157A (en) | 2014-03-12 | 2014-03-12 | Elastic composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014049158A JP2015172157A (en) | 2014-03-12 | 2014-03-12 | Elastic composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2015172157A true JP2015172157A (en) | 2015-10-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014049158A Pending JP2015172157A (en) | 2014-03-12 | 2014-03-12 | Elastic composite material |
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| JP (1) | JP2015172157A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190000184A1 (en) * | 2016-01-27 | 2019-01-03 | Honeywell International Inc. | Ice slip resistance formula and process |
| JP2020001854A (en) * | 2018-06-26 | 2020-01-09 | 株式会社日立ビルシステム | Passenger conveyor |
| JP2020124323A (en) * | 2019-02-04 | 2020-08-20 | 株式会社ムーンスター | Anti-slip footwear soles using fine diameter fibers |
-
2014
- 2014-03-12 JP JP2014049158A patent/JP2015172157A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190000184A1 (en) * | 2016-01-27 | 2019-01-03 | Honeywell International Inc. | Ice slip resistance formula and process |
| US10952499B2 (en) * | 2016-01-27 | 2021-03-23 | Honeywell International Inc. | Ice slip resistance formula and process |
| JP2020001854A (en) * | 2018-06-26 | 2020-01-09 | 株式会社日立ビルシステム | Passenger conveyor |
| JP7033020B2 (en) | 2018-06-26 | 2022-03-09 | 株式会社日立ビルシステム | Passenger conveyor |
| JP2020124323A (en) * | 2019-02-04 | 2020-08-20 | 株式会社ムーンスター | Anti-slip footwear soles using fine diameter fibers |
| JP7300273B2 (en) | 2019-02-04 | 2023-06-29 | 株式会社ムーンスター | Anti-slip footwear sole using fine fiber |
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