JP5506077B2 - Moisture permeable waterproof fabric and method for producing the same - Google Patents
Moisture permeable waterproof fabric and method for producing the same Download PDFInfo
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- JP5506077B2 JP5506077B2 JP2009104922A JP2009104922A JP5506077B2 JP 5506077 B2 JP5506077 B2 JP 5506077B2 JP 2009104922 A JP2009104922 A JP 2009104922A JP 2009104922 A JP2009104922 A JP 2009104922A JP 5506077 B2 JP5506077 B2 JP 5506077B2
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- permeable
- waterproof fabric
- fluorine
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- 239000004744 fabric Substances 0.000 title claims description 147
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 128
- 239000005871 repellent Substances 0.000 claims description 76
- 239000011342 resin composition Substances 0.000 claims description 72
- 230000002940 repellent Effects 0.000 claims description 70
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 65
- 229910052731 fluorine Inorganic materials 0.000 claims description 65
- 239000011737 fluorine Substances 0.000 claims description 65
- 239000012982 microporous membrane Substances 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 229920005749 polyurethane resin Polymers 0.000 claims description 38
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- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
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- 238000001035 drying Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
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- 229920005862 polyol Polymers 0.000 description 5
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- 229920002647 polyamide Polymers 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
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- 239000012943 hotmelt Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
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- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 238000009958 sewing Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 241000270666 Testudines Species 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- 230000001804 emulsifying effect Effects 0.000 description 1
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Professional, Industrial, Or Sporting Protective Garments (AREA)
- Laminated Bodies (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、主としてスポーツ衣料用や防寒衣料用として用いられる透湿性能及び防水性能に優れた透湿防水性布帛及びその製造方法に関するものである。 The present invention relates to a moisture-permeable and waterproof fabric excellent in moisture-permeable performance and waterproof performance mainly used for sports clothing and cold clothing and a method for producing the same.
スポーツ衣料や防寒衣料等には、身体からの発汗による水蒸気を衣料外へ放出する透湿機能と、雨水が衣料内に侵入するのを防止する防水機能とが要求されている。したがって、スポーツ衣料や防寒衣料等の素材として、従来より、透湿防水性布帛が用いられている。 Sports clothing, cold clothing, and the like are required to have a moisture permeable function for releasing water vapor generated by perspiration from the body to the outside of the clothing and a waterproof function for preventing rainwater from entering the clothing. Therefore, moisture-permeable and waterproof fabrics have been conventionally used as materials for sports clothing and cold clothing.
かかる透湿防水性布帛は、一般的に、ポリウレタン樹脂を主体とする微多孔膜形成用樹脂組成物を、布帛本体表面に塗布した後、水中に浸漬して前記組成物を湿式凝固させたり、或いは水中に浸漬することなく前記組成物を乾燥して、布帛本体表面に微多孔膜を形成することによって製造されている。たとえば、特許文献１には、ポリウレタン樹脂と撥水剤とシリカ微粉末を含有する微多孔膜形成用樹脂組成物を、布帛本体表面に塗布した後、水中に浸漬し、前記組成物を湿式凝固させて透湿防水性布帛を製造することが記載されている。このような方法で得られた透湿防水性布帛は、高い透湿度を持っているため透湿性能に優れており、また高い耐水圧を持っているため防水性能に優れたものであり、好ましいものである。 Such a moisture-permeable and waterproof fabric generally has a resin composition for forming a microporous film mainly composed of a polyurethane resin applied to the surface of the fabric body, and then immersed in water to wet-coagulate the composition. Alternatively, it is produced by drying the composition without being immersed in water to form a microporous film on the surface of the fabric body. For example, in Patent Document 1, a resin composition for forming a microporous film containing a polyurethane resin, a water repellent and silica fine powder is applied to the surface of a fabric body, and then immersed in water to wet-coagulate the composition. Manufacturing a moisture-permeable and waterproof fabric. The moisture-permeable and waterproof fabric obtained by such a method is excellent in moisture permeability because it has high moisture permeability, and is excellent in waterproof performance because it has high water pressure resistance, which is preferable. Is.
しかしながら、特許文献１に記載されているような従来の透湿防水性布帛は、当初は高い耐水圧を持っているが、洗濯を繰り返すと、耐水圧が低下し、所望の防水性能を失ってしまうという欠点があった。本発明は、洗濯を繰り返しても、耐水圧が低下しにくい透湿防水性布帛を提供することにある。 However, the conventional moisture-permeable waterproof fabric as described in Patent Document 1 initially has a high water pressure resistance, but when washing is repeated, the water pressure resistance decreases and the desired waterproof performance is lost. There was a drawback of end. An object of the present invention is to provide a moisture-permeable and waterproof fabric in which the water pressure resistance is unlikely to decrease even after repeated washing.
上記課題を解決するために、本発明は微多孔膜形成用樹脂組成物中に油溶性のフッ素系界面活性剤を混合させておき、得られる微多孔膜中に当該フッ素系界面活性剤を含有せしめて、これにより洗濯を繰り返しても耐水圧が低下しにくいようにしたものである。すなわち、本発明は、布帛本体の片面に、ポリウレタン樹脂を主体とする微多孔膜が積層されてなる透湿防水性布帛において、前記微多孔膜には、フッ素系撥水剤１〜９質量％及び油溶性のフッ素系界面活性剤０．１〜２質量％が含有されていることを特徴とする透湿防水性布帛及びその製造方法に関するものである。ただし、前記微多孔膜中にシリカ微粉末が３〜４５質量％含有されているものを除く。 In order to solve the above-mentioned problems, the present invention mixes an oil-soluble fluorosurfactant in a resin composition for forming a microporous membrane, and contains the fluorosurfactant in the resulting microporous membrane. In this way, the water pressure resistance is less likely to decrease even after repeated washing. That is, the present invention relates to a moisture permeable waterproof fabric in which a microporous membrane mainly composed of a polyurethane resin is laminated on one side of the fabric body, and the microporous membrane includes 1 to 9% by mass of a fluorine-based water repellent. And 0.1 to 2% by mass of an oil-soluble fluorosurfactant, and a method for producing the moisture-permeable and waterproof fabric. However, the fine porous film excluding those containing 3 to 45% by mass of silica fine powder.
本発明に用いる布帛本体としては、従来公知の織物、編物又は不織布等が用いられる。具体的には、ナイロン６、ナイロン６６で代表されるポリアミド系合成繊維、ポリエチレンテレフタレートで代表されるポリエステル系合成繊維、ポリアクリルニトリル系合成繊維、ポリビニルアルコール系合成繊維などの合成繊維、トリアセテートなどの半合成繊維、或いはナイロン６／綿、ポリエチレンテレフタレート／綿などの混合繊維からなる織物、編物又は不織布等が用いられる。 As the fabric body used in the present invention, a conventionally known woven fabric, knitted fabric, nonwoven fabric or the like is used. Specifically, polyamide synthetic fiber represented by nylon 6, nylon 66, polyester synthetic fiber represented by polyethylene terephthalate, synthetic fiber such as polyacrylonitrile synthetic fiber, polyvinyl alcohol synthetic fiber, triacetate, etc. A semi-synthetic fiber or a woven fabric, a knitted fabric or a non-woven fabric made of a mixed fiber such as nylon 6 / cotton or polyethylene terephthalate / cotton is used.
布帛本体は撥水加工されているのが好ましい。すなわち、従来公知の撥水剤エマルジョンに布帛本体を浸漬するか、布帛本体の表面に撥水剤エマルジョンを塗布して、撥水加工を施すのが好ましい。撥水剤エマルジョンとしては、従来公知のフッ素系撥水剤エマルジョン、シリコーン系撥水剤エマルジョン或いはパラフィン系撥水剤エマルジョン等を使用しうる。本発明においては、フッ素系撥水剤エマルジョンを使用するのが好ましく、この中でも、フッ素系撥水剤中にパーフルオロオクタン酸が残留していたり或いはフッ素系撥水剤から経時的にパーフルオロオクタン酸が生成しにくいものを用いるのが好ましい。この理由は、パーフルオロオクタン酸は難分解性で、環境に残留する性質があるため、地球環境に好ましくないからである。かかるフッ素系撥水剤としては、側鎖に炭素数１〜６のパーフルオロアルキル基を有するアクリレート化合物を重合して得られたものが代表的である。具体的には、旭硝子株式会社製「アサヒガード ＡＧ−Ｅ０６１」、ダイキン工業株式会社製「ユニダイン ＴＧ−５５２１」、日華化学株式会社製「ＮＫガード ＳＣＨ−０２」、クラリアントジャパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」等が挙げられる。 The fabric body is preferably water-repellent. That is, it is preferable to immerse the fabric body in a conventionally known water repellent emulsion or apply the water repellent emulsion to the surface of the fabric body to perform the water repellent treatment. As the water repellent emulsion, a conventionally known fluorine water repellent emulsion, silicone water repellent emulsion, paraffin water repellent emulsion or the like can be used. In the present invention, it is preferable to use a fluorinated water repellent emulsion, and among them, perfluorooctanoic acid remains in the fluorinated water repellent or perfluorooctane over time from the fluorinated water repellent. It is preferable to use one that does not easily generate an acid. This is because perfluorooctanoic acid is difficult to decompose and remains in the environment, which is undesirable for the global environment. A typical example of such a fluorine-based water repellent is one obtained by polymerizing an acrylate compound having a C 1-6 perfluoroalkyl group in the side chain. Specifically, “Asahi Guard AG-E061” manufactured by Asahi Glass Co., Ltd., “Unidyne TG-5521” manufactured by Daikin Industries, Ltd., “NK Guard SCH-02” manufactured by Nikka Chemical Co., Ltd., “NUVA manufactured by Clariant Japan Co., Ltd. N2114 LIQ "and the like.
布帛本体を撥水加工する方法としても、従来公知の方法を採用しうる。具体的には、パディング法、コーティング法、グラビアコーティング法、スプレー法等の手段を採用しうる。たとえば、パディング法では、撥水剤エマルジョンに布帛本体を浸漬後、マングルで絞り、所定の付与量に調整し、８０〜１５０℃の温度で乾燥後、１５０〜１８０℃の温度で３０秒〜２分間のキュアリングを行う。これによって、両面に撥水加工が施された布帛本体が得られる。また、グラビアコーティング法では、高メッシュのグラビアロールを用いて片面のみに撥水剤エマルジョンを付着させ、その後、同様にして乾燥及びキュアリングを行う。これによって、片面のみに撥水加工が施された布帛本体が得られる。また、乾燥及びキュアリングを行った後、鏡面ロールを具備するカレンダー加工機を用いて、布帛本体表面の目潰し加工を行うのが好ましい。これは、後で塗布する微多孔膜形成用樹脂組成物が、布帛本体内部に深く浸透するのを防止するためである。 A conventionally known method can also be adopted as a method for water-repellent treatment of the fabric body. Specifically, means such as a padding method, a coating method, a gravure coating method, and a spray method can be employed. For example, in the padding method, the fabric body is immersed in a water repellent emulsion, then squeezed with a mangle, adjusted to a predetermined application amount, dried at a temperature of 80 to 150 ° C, and then at a temperature of 150 to 180 ° C for 30 seconds to 2 seconds. Cure for a minute. As a result, a fabric body having a water repellent finish on both sides is obtained. In the gravure coating method, a water repellent emulsion is attached to only one surface using a high mesh gravure roll, and thereafter drying and curing are performed in the same manner. As a result, a fabric body having a water-repellent finish on only one surface is obtained. Moreover, after drying and curing, it is preferable to crush the surface of the fabric body using a calendar processing machine having a mirror surface roll. This is to prevent the resin composition for forming a microporous film to be applied later from penetrating deeply into the fabric body.
撥水剤の付与量は、布帛本体中に、固形分換算で０．１〜３質量％が好ましく、０．３〜２質量％がより好ましい。付与量が０．１質量％未満になると、布帛本体に十分な撥水性能を付与し難く、一方、３質量％を超えると、得られる透湿防水性布帛の風合いが硬化しやくなったり、微多孔膜との接着性が低下したり、或いは微多孔膜の透湿性能に悪影響を及ぼす恐れが生じる。 The applied amount of the water repellent is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass in terms of solid content in the fabric body. When the applied amount is less than 0.1% by mass, it is difficult to impart sufficient water repellency to the fabric body. On the other hand, when the applied amount exceeds 3% by mass, the texture of the resulting moisture-permeable waterproof fabric is hard to be cured. Adhesion with the microporous membrane may be reduced, or the moisture permeability of the microporous membrane may be adversely affected.
撥水剤エマルジョン中には、撥水耐久性を向上させる目的で、トリアジン化合物、イソシアネート化合物等を混合してもよい。これらの中では、環境面からイソシアネート化合物が好適である。また、撥水剤エマルジョンの加工安定性の面からは、イソシアネート基をアセトオキシム、フェノール、カプロラクタム等でブロックした熱解離タイプのブロックイソシアネート化合物がより好適である。 In the water repellent emulsion, a triazine compound, an isocyanate compound or the like may be mixed for the purpose of improving the water repellency durability. In these, an isocyanate compound is suitable from an environmental viewpoint. From the viewpoint of processing stability of the water repellent emulsion, a thermal dissociation type blocked isocyanate compound in which an isocyanate group is blocked with acetoxime, phenol, caprolactam or the like is more preferable.
布帛本体の片面に積層されるポリウレタン樹脂を主体とする微多孔膜は、以下のような微多孔膜形成用樹脂組成物を、従来公知の湿式凝固により又は従来公知の乾燥により成膜させて得られるものである。すなわち、かかる微多孔膜形成用樹脂組成物は、ポリウレタン樹脂を主体とし、フッ素系撥水剤１〜９質量％及び油溶性のフッ素系界面活性剤０．１〜２質量％を含有する液状のものである。なお、本発明において、さらにシリカ微粉末が３〜４５質量％含有されている微多孔膜形成用樹脂組成物を使用する場合は除かれている。この理由は、本件出願人が先に出願した特願２００９−９３８７に係る発明との同一性を回避するためである。 The microporous film mainly composed of polyurethane resin laminated on one side of the fabric body is obtained by forming a resin composition for forming a microporous film as described below by a conventionally known wet coagulation or by a conventionally known drying. It is what That is, the resin composition for forming a microporous film is a liquid containing mainly a polyurethane resin and containing 1 to 9% by mass of a fluorine-based water repellent and 0.1 to 2% by mass of an oil-soluble fluorine-based surfactant. Is. In addition, in this invention, when using the resin composition for microporous film formation in which 3-45 mass% of silica fine powder is contained is excluded. The reason for this is to avoid the identity with the invention according to Japanese Patent Application No. 2009-9387 filed earlier by the present applicant.
微多孔膜形成用樹脂組成物中の固形分の主体であるポリウレタン樹脂としては、ポリイソシアネート成分とポリオール成分とを反応させて得られる従来公知のものを採用しうる。ポリイソシアネート成分としては、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネート等が単独で又は混合して用いられる。具体的には、トリレン−２，４−ジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、１，６−ヘキサンジイソシアネート又は１，４−シクロヘキサンジイソシアネート等を主成分として用い、必要に応じ３官能以上のポリイソシアネートを使用してもよい。一方、ポリオール成分としては、ポリエーテルポリオールやポリエステルポリオール等が用いられる。ポリエーテルポリオールとしては、ポリエチレングリコール、ポリプロピレングリコール又はポリテトラエチレングリコール等が用いられる。ポリエステルポリオールとしては、エチレングリコールやプロピレングリコール等のジオールと、アジピン酸やセバチン酸等の二塩基酸との反応生成物、又はカプロラクトン等の開環重合物を用いることができ、勿論、オキシ酸モノマー或いはそのプレポリマーの重合物も用いることができる。なお、高度の透湿性能を得るには、ポリオール成分として、ポリエチレングリコールやポリオキシプロピレンポリオキシエチレン共重合体等のポリオキシエチレン基を相対的に多くしたものを用いるのがよい。 As the polyurethane resin which is the main component of the solid content in the resin composition for forming a microporous film, a conventionally known one obtained by reacting a polyisocyanate component and a polyol component can be employed. As the polyisocyanate component, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and the like are used alone or in combination. Specifically, a polyisocyanate having 3 or more functional groups is used as the main component, such as tolylene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate or 1,4-cyclohexane diisocyanate. May be used. On the other hand, polyether polyol, polyester polyol, or the like is used as the polyol component. As the polyether polyol, polyethylene glycol, polypropylene glycol, polytetraethylene glycol or the like is used. As the polyester polyol, a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone can be used. Alternatively, a polymer of the prepolymer can also be used. In order to obtain high moisture permeability, it is preferable to use a polyol component having a relatively large number of polyoxyethylene groups such as polyethylene glycol and polyoxypropylene polyoxyethylene copolymer.
微多孔膜形成用樹脂組成物中に含有されるフッ素系撥水剤としては、従来公知のものが用いられる。本発明において、フッ素系撥水剤を使用するのは、フッ素系界面活性剤と混合しやすく、調製しやすく且つ塗布しやすい微多孔膜形成用樹脂組成物を得ることができるからである。本発明においては、フッ素系撥水剤の中でも、そこにパーフルオロオクタン酸が残留していたり或いはそこから経時的にパーフルオロオクタン酸が生成しにくいものを用いるのが好ましい。この理由は、パーフルオロオクタン酸は難分解性で、環境に残留する性質があるため、地球環境に好ましくないからである。かかるフッ素系撥水剤は、側鎖に炭素数１〜６のパーフルオロアルキル基を有するアクリレート化合物を重合して得られたものである。具体的には、旭硝子株式会社製「アサヒガード ＡＧ−Ｅ０６１」、ダイキン工業株式会社製「ユニダイン ＴＧ−５５２１」、日華化学株式会社製「ＮＫガード ＳＣＨ−０２」、クラリアントジャパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」等が挙げられる。 A conventionally well-known thing is used as a fluorine-type water repellent contained in the resin composition for microporous film formation. In the present invention, the fluorine-based water repellent is used because it is possible to obtain a resin composition for forming a microporous film that is easy to mix with a fluorine-based surfactant, easy to prepare, and easy to apply. In the present invention, among the fluorine-based water repellents, it is preferable to use those in which perfluorooctanoic acid remains or from which perfluorooctanoic acid is difficult to be formed over time. This is because perfluorooctanoic acid is difficult to decompose and remains in the environment, which is undesirable for the global environment. Such a fluorine-based water repellent is obtained by polymerizing an acrylate compound having a C 1-6 perfluoroalkyl group in the side chain. Specifically, “Asahi Guard AG-E061” manufactured by Asahi Glass Co., Ltd., “Unidyne TG-5521” manufactured by Daikin Industries, Ltd., “NK Guard SCH-02” manufactured by Nikka Chemical Co., Ltd., “NUVA manufactured by Clariant Japan Co., Ltd. N2114 LIQ "and the like.
フッ素系撥水剤は、微多孔膜形成用樹脂組成物の固形分中において、１〜９質量％含有されている。フッ素系撥水剤の含有量が１質量％未満であると、洗濯を繰り返したとき、微多孔膜中の微孔に洗剤が吸着しやすくなるので、好ましくない。すなわち、微孔に洗剤が吸着していると、水を呼び込みやすくなり、洗濯耐久性（耐水圧の洗濯耐久性）が低下するので、好ましくない。また、フッ素系撥水剤の含有量が９質量％を超えると、微多孔膜形成用樹脂組成物の安定性が悪くなり、塗布しにくくなって、均一な微多孔膜が形成しにくくなる。この結果、微多孔膜に班が生じ、耐水圧及び洗濯耐久性共に低下するので、好ましくない。 The fluorine-based water repellent is contained in an amount of 1 to 9% by mass in the solid content of the resin composition for forming a microporous film. When the content of the fluorine-based water repellent is less than 1% by mass, the detergent is easily adsorbed into the micropores in the microporous membrane when washing is repeated, which is not preferable. That is, if the detergent is adsorbed in the micropores, it is not preferable because water is easily attracted and washing durability (washing durability of water pressure resistance) is lowered. Moreover, when content of a fluorine-type water repellent exceeds 9 mass%, stability of the resin composition for microporous film formation will worsen, it will become difficult to apply | coat, and it will become difficult to form a uniform microporous film. As a result, spots are formed in the microporous membrane, and both the water pressure resistance and the washing durability are deteriorated.
微多孔膜形成用樹脂組成物中に含有される油溶性のフッ素系界面活性剤としては、パーフルオロアルキル基よりなる疎水基と、ポリオキシアルキレン基、スルホン酸基又はカルボン酸基等の親水基とを有し、界面活性能のあるものが採用される。ここで、油溶性とは、トルエンに対して５０質量％以上溶解又は相溶するという意味である。すなわち、トルエン１００質量部に対してフッ素系界面活性剤５０質量部を混合攪拌したとき、１時間経過後においても、相分離を起こさないということである。本発明において、油溶性のフッ素系界面活性剤を用いる理由は、微多孔膜形成用樹脂組成物の溶媒として主に有機溶媒が使用されることから、ここにフッ素系界面活性剤を均一に溶解又は分散させるためである。そして、フッ素系界面活性剤の界面活性能により、フッ素系撥水剤を均一に微多孔膜中に存在させるためである。油溶性のフッ素系界面活性剤としては、ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−６５１」 、「ＳＵＲＦＬＯＮ Ｓ−６１１」 、「ＳＵＲＦＬＯＮ Ｓ−３８６」 及び「ＳＵＲＦＬＯＮ Ｓ−２４３」等が用いられる。 The oil-soluble fluorosurfactant contained in the resin composition for forming a microporous film includes a hydrophobic group comprising a perfluoroalkyl group and a hydrophilic group such as a polyoxyalkylene group, a sulfonic acid group, or a carboxylic acid group. And having surface activity is employed. Here, oil-soluble means that 50% by mass or more dissolves or is compatible with toluene. That is, when 50 parts by mass of a fluorosurfactant is mixed and stirred with respect to 100 parts by mass of toluene, phase separation does not occur even after 1 hour. In the present invention, the reason why an oil-soluble fluorosurfactant is used is that an organic solvent is mainly used as a solvent for the resin composition for forming a microporous film, so that the fluorosurfactant is uniformly dissolved therein. Or to disperse. This is because the fluorine-based water repellent is uniformly present in the microporous film by the surface activity of the fluorine-based surfactant. As the oil-soluble fluorosurfactant, “SURFLON S-651”, “SURFLON S-611”, “SURFLON S-386”, “SURFLON S-243” and the like manufactured by AGC Seimi Chemical Co., Ltd. are used.
また、本発明においては、油溶性で且つ水溶性のフッ素界面活性剤を用いるのが、特に好ましい。微多孔膜形成用樹脂組成物中には水も存在しているため、フッ素系界面活性剤が油溶性で且つ水溶性である方が、微多孔膜形成用樹脂組成物中により均一に溶解又は分散するからである。ここで、水溶性とは、油溶性の場合と同様に、水に対して５０質量％以上溶解又は相溶するという意味である。すなわち、水１００質量部に対してフッ素系界面活性剤５０質量部を混合攪拌したとき、１時間経過後においても、相分離を起こさないということである。油溶性且つ水溶性のフッ素系界面活性剤としては、ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」 や「ＳＵＲＦＬＯＮ Ｓ−２４３」 等が用いられる。 In the present invention, it is particularly preferable to use an oil-soluble and water-soluble fluorine surfactant. Since water is also present in the microporous film-forming resin composition, the fluorosurfactant is more soluble or even more soluble in the microporous film-forming resin composition if it is oil-soluble and water-soluble. This is because they are dispersed. Here, the term “water-soluble” means that 50% by mass or more dissolves or is compatible with water, as in the case of oil solubility. That is, when 50 parts by mass of a fluorosurfactant is mixed and stirred with respect to 100 parts by mass of water, phase separation does not occur even after 1 hour. Examples of the oil-soluble and water-soluble fluorosurfactant include “SURFLON S-386” and “SURFLON S-243” manufactured by AGC Seimi Chemical Co., Ltd.
なお、本発明においては、水溶性であるが油溶性ではないフッ素系界面活性剤や、水溶性でも油溶性でもないフッ素系界面活性剤は使用することができない。たとえば、前者のフッ素系界面活性剤としては、ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−２４１」 、「ＳＵＲＦＬＯＮ Ｓ−２２１」 、「ＳＵＲＦＬＯＮ Ｓ−２１１」 等が存在するが、このようなフッ素系界面活性剤は使用できない。また、後者のフッ素系界面活性剤としては、ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−４２０」 等が存在するが、このようなフッ素系界面活性剤も使用できない。 In the present invention, a fluorine-based surfactant that is water-soluble but not oil-soluble, or a fluorine-based surfactant that is neither water-soluble nor oil-soluble can be used. For example, as the former fluorosurfactant, “SURFLON S-241”, “SURFLON S-221”, “SURFLON S-211”, etc., manufactured by AGC Seimi Chemical Co., Ltd. exist. Activators cannot be used. In addition, as the latter fluorosurfactant, there is “SURFLON S-420” manufactured by AGC Seimi Chemical Co., Ltd., but such a fluorosurfactant cannot be used.
本発明で用いるフッ素系界面活性剤の化学構造の代表例は、疎水基として炭素数１〜６のパーフルオロアルキル基を持ち、親水基としてポリオキシエチレン基又はポリオキシプロピレン基等のポリオキシアルキレン基を持つものである。たとえば、側鎖に炭素数１〜６のパーフルオロアルキル基と共にポリオキシエチレン基又はポリオキシプロピレン基を持つアクリレート化合物を重合させたオリゴマーが用いられる。また、ポリオキシエチレン基又はポリオキシプロピレン基を持つ化合物に、炭素数１〜６のパーフルオロアルキル基を側鎖に持つアクリレート化合物を重合させたオリゴマーを付加させたものが用いられる。ここで、疎水基として、炭素数１〜６のパーフルオロアルキル基が用いられる理由は、フッ素系撥水剤の説明中でも述べたのと同様である。すなわち、地球環境に悪影響を与えるパーフルオロオクタン酸がフッ素系界面活性剤中に残留していたり或いはフッ素系界面活性剤から経時的に生成しにくいからである。 Typical examples of the chemical structure of the fluorosurfactant used in the present invention include a perfluoroalkyl group having 1 to 6 carbon atoms as a hydrophobic group and a polyoxyalkylene such as a polyoxyethylene group or a polyoxypropylene group as a hydrophilic group. It has a group. For example, an oligomer obtained by polymerizing an acrylate compound having a polyoxyethylene group or a polyoxypropylene group together with a perfluoroalkyl group having 1 to 6 carbon atoms in the side chain is used. Moreover, what added the oligomer which superposed | polymerized the acrylate compound which has a C1-C6 perfluoroalkyl group in a side chain to the compound which has a polyoxyethylene group or a polyoxypropylene group is used. Here, the reason why the perfluoroalkyl group having 1 to 6 carbon atoms is used as the hydrophobic group is the same as described in the explanation of the fluorine-based water repellent. That is, it is because perfluorooctanoic acid that has an adverse effect on the global environment remains in the fluorosurfactant or is hardly generated from the fluorosurfactant over time.
油溶性のフッ素系界面活性剤は、微多孔膜形成用樹脂組成物の固形分中において、０．１〜２質量％含有されている。フッ素系界面活性剤の含有量が０．１質量％未満であると、微多孔膜形成用樹脂組成物の安定性や塗布性が悪くなり、形成される微多孔膜の耐水圧が低下すると共に洗濯耐久性も低下するので、好ましくない。また、フッ素系界面活性剤の含有量が２質量％を超えると、形成される微多孔膜の撥水性が低下し、耐水圧が低下すると共に洗濯耐久性も低下するので、好ましくない。 The oil-soluble fluorosurfactant is contained in an amount of 0.1 to 2% by mass in the solid content of the resin composition for forming a microporous film. When the content of the fluorosurfactant is less than 0.1% by mass, the stability and coating properties of the resin composition for forming a microporous film are deteriorated, and the water pressure resistance of the formed microporous film is reduced. Since washing durability also falls, it is not preferable. On the other hand, when the content of the fluorosurfactant exceeds 2% by mass, the water repellency of the formed microporous film is lowered, the water pressure resistance is lowered, and the washing durability is also lowered.
微多孔膜形成用樹脂組成物中には、前記したポリウレタン樹脂、フッ素系撥水剤及び油溶性のフッ素系界面活性剤の他に、第三成分として架橋性イソシアネート化合物が含有されているのが好ましい。これは、微多孔膜を形成するポリウレタン樹脂を架橋させ、微多孔膜の強度の向上や、微多孔膜と布帛本体の接着力の向上を図るためである。架橋性イソシアネート化合物は、微多孔膜形成用樹脂組成物の固形分中に１〜１０質量％程度含有させるのが好ましい。架橋性イソシアネート化合物の含有量が１質量％未満であると、微多孔膜の強度向上や、微多孔膜と布帛本体の接着力向上が図りにくくなる。また、架橋性イソシアネート化合物の含有量が１０質量％を超えると、微多孔膜の風合いが硬くなる傾向が生じる。 The resin composition for forming a microporous film contains a crosslinkable isocyanate compound as a third component in addition to the polyurethane resin, the fluorine-based water repellent and the oil-soluble fluorine-based surfactant. preferable. This is because the polyurethane resin forming the microporous membrane is crosslinked to improve the strength of the microporous membrane and to improve the adhesion between the microporous membrane and the fabric body. The crosslinkable isocyanate compound is preferably contained in an amount of about 1 to 10% by mass in the solid content of the resin composition for forming a microporous film. When the content of the crosslinkable isocyanate compound is less than 1% by mass, it is difficult to improve the strength of the microporous membrane and to improve the adhesion between the microporous membrane and the fabric body. Moreover, when content of a crosslinkable isocyanate compound exceeds 10 mass%, the tendency for the texture of a microporous film to become hard will arise.
架橋性イソシアネート化合物としては、トリレン２，４−ジイソシアネート、ジフェニルメタンジイソシアネート、イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート等が用いられる。また、これらのジイソシアネート類３モルと、活性水素を含有する化合物１モルとの付加反応によって得られるトリイソシアネート類も用いられる。なお、活性水素を含有する化合物としては、たとえば、トリメチロールプロパン、グリセリン等を用いることができる。架橋性イソシアネート化合物のうち、特にブロックイソシアネートを用いると、微多孔膜形成用樹脂組成物の安定性及びポットライフの点で有利である。ブロックイソシアネートとしては、熱処理によって解離するタイプが好ましく、具体的には、フェノール、ラクタム、メチルケトオキシム等で付加ブロック体を形成させたものが好適である。 As the crosslinkable isocyanate compound, tolylene 2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or the like is used. Triisocyanates obtained by addition reaction of 3 mol of these diisocyanates with 1 mol of a compound containing active hydrogen are also used. In addition, as a compound containing active hydrogen, a trimethylol propane, glycerol, etc. can be used, for example. Of the crosslinkable isocyanate compounds, the use of blocked isocyanate is particularly advantageous in terms of stability and pot life of the resin composition for forming a microporous film. As the blocked isocyanate, a type that dissociates by heat treatment is preferable, and specifically, those obtained by forming an additional block with phenol, lactam, methyl ketoxime, or the like are preferable.
さらに、第三成分としては、ポリウレタン樹脂以外の樹脂が少量、たとえば固形分中に２０質量％以下程度含有されていてもよい。かかる樹脂としては、たとえば、ポリアクリル酸、ポリ塩化ビニル、ポリスチレン、ポリブタジエン、ポリアミノ酸、ポリカーボネート等の重合体又は共重合体が用いられる。また、これらの重合体又は共重合体をフッ素やシリコン等で変成したものも用いられる。その他にも、第三成分として、顔料、フィラーなどの各種添加剤、抗菌剤、消臭剤、難燃剤等の各種機能材を含有させてもよい。 Furthermore, as the third component, a resin other than the polyurethane resin may be contained in a small amount, for example, about 20% by mass or less in the solid content. Examples of such a resin include polymers or copolymers such as polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid, and polycarbonate. Also, those obtained by modifying these polymers or copolymers with fluorine, silicon or the like can be used. In addition, various functional materials such as various additives such as pigments and fillers, antibacterial agents, deodorants, and flame retardants may be contained as the third component.
微多孔膜形成用樹脂組成物中には、ポリウレタン樹脂、フッ素系撥水剤及び油溶性のフッ素系界面活性剤を均一に溶解又は分散させるために、公知の有機溶媒や水が用いられる。特に、ポリウレタン樹脂に対する親溶媒であるＮ，Ｎ−ジメチルホルムアミドを用いるのが好ましい。有機溶媒や水の含有量も、従来公知の割合であって、概ね３０〜８５質量％程度である。 In the resin composition for forming a microporous film, a known organic solvent or water is used in order to uniformly dissolve or disperse the polyurethane resin, the fluorine-based water repellent and the oil-soluble fluorine-based surfactant. In particular, it is preferable to use N, N-dimethylformamide, which is a parent solvent for polyurethane resins. The content of the organic solvent and water is also a conventionally known ratio, and is about 30 to 85% by mass.
本発明に係る透湿防水性布帛を得る方法としては、以下のような従来公知の方法が挙げられる。たとえば、布帛本体の片面に、コンマコーターやナイフコーター等の公知の手段で微多孔膜形成用樹脂組成物を塗布した後、湿式凝固液に浸漬させることにより、微多孔膜を形成する方法が挙げられる。湿式凝固に用い得る微多孔膜形成用樹脂組成物は、基本的には、ポリウレタン樹脂、フッ素系撥水剤及び油溶性のフッ素系界面活性剤をＮ，Ｎ−ジメチルホルムアミドやＮ−メチルピロリドン等の水と置換しやすい極性溶媒に溶解又は分散させたものである。湿式凝固液としては、水又はＮ，Ｎ−ジメチルホルムアミドを好ましくは３０質量％以下、より好ましくは５〜３０質量％含有する水溶液が用いられる。凝固液の温度は５〜３５℃程度が好ましく、凝固時間は３０秒〜５分間程度である。湿式凝固液にて微多孔膜形成用樹脂組成物を凝固させ、微多孔膜を得た後、Ｎ，Ｎ−ジメチルホルムアミドを除去するため、３５〜８０℃の温度下で１〜１０分間湯洗する。そして、湯洗後、５０〜１５０℃の温度下で１〜１０分間乾燥することにより、微多孔膜が形成された透湿防水性布帛が得られるのである。 Examples of the method for obtaining the moisture-permeable and waterproof fabric according to the present invention include the following known methods. For example, a method of forming a microporous film by applying a resin composition for forming a microporous film on one side of a fabric main body by a known means such as a comma coater or a knife coater and then immersing it in a wet coagulation liquid. It is done. The resin composition for forming a microporous film that can be used for wet coagulation is basically a polyurethane resin, a fluorine-based water repellent, an oil-soluble fluorine-based surfactant, N, N-dimethylformamide, N-methylpyrrolidone, etc. It is dissolved or dispersed in a polar solvent that can easily be replaced with water. As the wet coagulating liquid, an aqueous solution containing water or N, N-dimethylformamide is preferably 30% by mass or less, more preferably 5 to 30% by mass. The temperature of the coagulation liquid is preferably about 5 to 35 ° C., and the coagulation time is about 30 seconds to 5 minutes. The resin composition for forming a microporous film is coagulated with a wet coagulation liquid to obtain a microporous film, and then washed with hot water at a temperature of 35 to 80 ° C. for 1 to 10 minutes in order to remove N, N-dimethylformamide. To do. And after water washing, the moisture-permeable waterproof fabric in which the microporous film was formed is obtained by drying for 1 to 10 minutes at the temperature of 50-150 degreeC.
また、布帛本体の片面に、コンマコーターやナイフコーター等の公知の手段で微多孔膜形成用樹脂組成物を塗布した後、当該組成物を乾燥して、有機溶剤や水を蒸発させることにより成膜して、微多孔膜を形成する方法も挙げられる。かかる方法で用い得る微多孔膜形成用樹脂組成物は、メチルエチルケトンやトルエン等の有機溶剤中に、０．１〜５μｍ程度の大きさのポリウレタン微粒子を、少量の乳化剤や親水性ポリウレタン樹脂等で乳化分散させたＷ／Ｏ型（油中水型）エマルジョンからなるものが用いられる。 Further, after applying a resin composition for forming a microporous film on one side of the fabric body by a known means such as a comma coater or a knife coater, the composition is dried to evaporate an organic solvent or water. There is also a method of forming a microporous film by forming a film. The resin composition for forming a microporous film that can be used in such a method is obtained by emulsifying polyurethane fine particles having a size of about 0.1 to 5 μm in a small amount of an emulsifier or a hydrophilic polyurethane resin in an organic solvent such as methyl ethyl ketone or toluene. What consists of the dispersed W / O type (water-in-oil type) emulsion is used.
また、布帛本体の片面に、コンマコーターやナイフコーター等の公知の手段で微多孔膜形成用樹脂組成物を塗布した後、当該組成物を乾燥して、水等を蒸発させて成膜し、その後、膜中から特定成分を溶出させて、微多孔膜を形成する方法も挙げられる。かかる方法で用い得る微多孔膜形成用樹脂組成物は、ポリウレタン微粒子が乳化剤等で水に分散したり、或いは乳化剤なしに自己乳化して自己分散しているＯ／Ｗ型（水中油型）エマルジョン中に、３０〜１００℃の温水によって溶出し得る糊剤，澱粉又は水溶性ポリウレタン樹脂等の特定成分を混合したものが用いられる。特定成分を溶出するには、家庭用洗濯機、工業用洗濯機或いは染色機等を使用して、３０〜１００℃の温水を用いて、５〜１５分間程度ソーピングすればよい。 Moreover, after applying the resin composition for forming a microporous film on one side of the fabric body by a known means such as a comma coater or a knife coater, the composition is dried, and water is evaporated to form a film. Then, the method of eluting a specific component from a film | membrane and forming a microporous film | membrane is also mentioned. The resin composition for forming a microporous film that can be used in such a method is an O / W type (oil-in-water type) emulsion in which polyurethane fine particles are dispersed in water with an emulsifier or the like, or are self-emulsified without an emulsifier A mixture of specific components such as paste, starch or water-soluble polyurethane resin that can be eluted with hot water at 30 to 100 ° C. is used. In order to elute a specific component, it is sufficient to use a household washing machine, an industrial washing machine, or a dyeing machine, etc., and use soapy water at 30 to 100 ° C. for about 5 to 15 minutes.
さらに、ポリウレタン樹脂を水及び／又は有機溶剤に溶解させた溶液に、ガス発泡剤等を混入して、乾燥成膜時に発泡させることにより、微多孔膜を形成する方法も挙げられる。その他にも、ポリウレタン樹脂液を、界面活性剤や気泡剤等を用いて、安定的に気泡を生じさせて、乾燥成膜し微多孔膜を形成する方法も挙げられる。以上の各種従来公知の方法で微多孔膜を得られるのであるが、微多孔膜の厚さは所望に応じて適宜設定すればよい。一般的には、微多孔膜の厚さは１０〜５０μｍ程度である。微多孔膜の厚さが薄くなると、耐水圧が低下する傾向があり、厚くなると風合いが低下する傾向が生じる。 Furthermore, a method of forming a microporous film by mixing a gas foaming agent or the like in a solution in which a polyurethane resin is dissolved in water and / or an organic solvent and foaming at the time of dry film formation is also included. In addition, there may be mentioned a method of forming a microporous film by forming a dry film with a polyurethane resin liquid by using a surfactant, a foaming agent or the like to stably generate bubbles. Although the microporous membrane can be obtained by the various conventional methods described above, the thickness of the microporous membrane may be appropriately set as desired. In general, the thickness of the microporous membrane is about 10 to 50 μm. When the thickness of the microporous membrane is reduced, the water pressure resistance tends to decrease, and when the thickness is increased, the texture tends to decrease.
本発明においては、微多孔膜の表面に更に無孔膜を積層しても差し支えない。また、布帛本体と微多孔膜の間に無孔膜を挿入しても差し支えない。もちろん、無孔膜としては透湿性の無孔膜を採用するのであるが、無孔膜を積層すると、耐水圧が更に向上する。無孔膜としては、微多孔膜がポリウレタン樹脂を主体とするものであるから、微多孔膜との接着性が良好なポリウレタン樹脂膜を用いるのが好ましい。無孔膜を形成するには、無孔膜形成用樹脂組成物を微多孔膜表面に塗布して乾燥すればよい。また、離型紙等の離型基材表面に無孔膜形成用樹脂組成物を塗布して乾燥し、無孔膜を得た後、これを微多孔膜表面に積層貼合してもよい。さらに、布帛本体表面に無孔膜形成用樹脂組成物を塗布して乾燥して無孔膜を得た後、当該無孔膜表面に微多孔膜を設けてもよい。無孔膜形成用樹脂組成物としては、一般的に、ポリウレタン樹脂を有機溶媒に溶解させたものを用いる。有機溶媒としては、微多孔質膜表面に直接に無孔膜形成用樹脂組成物を塗布する場合は、Ｎ，Ｎ−ジメチルホルムアミドの含有率が少ない、或いはこれを全く含まないものを用いる方が好ましい。なぜなら、Ｎ，Ｎ−ジメチルホルムアミドは、ポリウレタン樹脂の親溶媒に当たるので、有機溶媒中にこれが多く含まれていると、微多孔膜の表層が侵蝕される恐れがあるからである。なお、離型基材表面に無孔膜形成用樹脂組成物を塗布して、一旦無孔膜を形成した後、微多孔質膜と熱圧着或いは接着剤にて貼合する方法等の他の方法を採用する場合には、有機溶媒中のＮ，Ｎ−ジメチルホルムアミドの含有率にこだわる必要はなく、乾燥性や圧着性等を考慮して行えばよい。 In the present invention, a nonporous film may be further laminated on the surface of the microporous film. Further, a nonporous film may be inserted between the fabric body and the microporous film. Of course, a moisture-permeable non-porous film is adopted as the non-porous film. However, when the non-porous film is laminated, the water pressure resistance is further improved. As the non-porous film, since the microporous film is mainly composed of a polyurethane resin, it is preferable to use a polyurethane resin film having good adhesion to the microporous film. In order to form the nonporous film, the resin composition for forming a nonporous film may be applied to the surface of the microporous film and dried. Moreover, after apply | coating the resin composition for nonporous film formation to surface of mold release base materials, such as a release paper, and drying and obtaining a nonporous film, this may be laminated | stacked on the microporous film surface. Furthermore, after applying the resin composition for nonporous film formation to the fabric main body surface and drying and obtaining a nonporous film, you may provide a microporous film on the nonporous film surface. As the resin composition for forming a nonporous film, generally, a polyurethane resin dissolved in an organic solvent is used. As the organic solvent, when the nonporous film-forming resin composition is directly applied to the surface of the microporous film, it is preferable to use a solvent having a low content of N, N-dimethylformamide or not containing it at all. preferable. This is because N, N-dimethylformamide hits the parent solvent of the polyurethane resin, and if the organic solvent is contained in a large amount, the surface layer of the microporous film may be eroded. In addition, after apply | coating the resin composition for non-porous film formation to the mold release base-material surface, once forming a non-porous film, other methods, such as bonding with a microporous film with thermocompression bonding or an adhesive, etc. When adopting the method, it is not necessary to pay attention to the content of N, N-dimethylformamide in the organic solvent, and it may be carried out in consideration of the drying property and the pressure bonding property.
無孔膜形成用樹脂組成物の粘度は、塗布しやすいように、１００〜１００００ｍＰａ・ｓ（２５℃）程度が好ましい。また、無孔膜形成用樹脂組成物の固形分含有量は、１０〜３０質量％程度であるのが好ましい。無孔膜形成用樹脂組成物を塗布して無孔膜を形成する手段としては、従来公知の方法を採用すればよい。たとえば、ナイフコーター、コンマコーター、リバースコーター又は高メッシュ・低深度のグラビアロールを用いて、無孔膜形成用樹脂組成物を微多孔膜表面、離型基材表面或いは布帛本体表面に塗布した後、乾燥して無孔膜を形成すればよい。 The viscosity of the nonporous film-forming resin composition is preferably about 100 to 10,000 mPa · s (25 ° C.) so that it can be easily applied. Moreover, it is preferable that solid content of the resin composition for non-porous film formation is about 10-30 mass%. A conventionally known method may be employed as a means for forming the nonporous film by applying the nonporous film forming resin composition. For example, after applying the nonporous film forming resin composition to the surface of the microporous film, the surface of the release substrate or the surface of the fabric body using a knife coater, comma coater, reverse coater or gravure roll of high mesh / low depth It may be dried to form a nonporous film.
無孔膜の厚さは、０．５〜１２μｍ程度が好ましい。無孔膜の厚さが０．５μｍ未満であると、目的とする耐水圧の向上が不十分となる傾向が生じる。無孔膜の厚さが１２μｍを超えると、無孔膜自体の透湿度にもよるが、一般的に透湿度が低下する。 The thickness of the nonporous film is preferably about 0.5 to 12 μm. When the thickness of the non-porous film is less than 0.5 μm, there is a tendency that the intended improvement in water pressure resistance is insufficient. When the thickness of the nonporous film exceeds 12 μm, the moisture permeability generally decreases although it depends on the moisture permeability of the nonporous film itself.
本発明に係る透湿防水性布帛の微多孔膜表面又は無孔膜表面に、所定の柄が印刷されていてもよい。柄を印刷するには、柄印刷用組成物を微多孔膜表面又は無孔膜表面に、グラビアロール、ロータリースクリーン又はフラットスクリーン等を用いて所定の柄で塗布し乾燥すればよい。柄印刷用組成物は、基本的には、樹脂とこれを溶解させるための有機溶媒とが含有されてなるものである。また、樹脂を硬化させるための樹脂硬化剤が含有されていてもよい。樹脂としては、ポリウレタン系樹脂、アクリル系樹脂、ポリエステル系樹脂、塩化ビニル系樹脂、ポリオレフィン系樹脂、エチレン・酢酸ビニル樹脂等が単独で又は混合して用いられる。特に、微多孔膜はポリウレタン樹脂を主体とするものであり、無孔膜も多くの場合ポリウレタン樹脂を主体とするものであるから、微多孔膜又は無孔膜との接着性の観点から、ポリウレタン系樹脂を採用するのが好ましい。 A predetermined pattern may be printed on the surface of the microporous membrane or the nonporous membrane of the moisture-permeable and waterproof fabric according to the present invention. In order to print the pattern, the pattern printing composition may be applied to the surface of the microporous film or the nonporous film with a predetermined pattern using a gravure roll, a rotary screen, a flat screen or the like, and dried. The pattern printing composition basically includes a resin and an organic solvent for dissolving the resin. Further, a resin curing agent for curing the resin may be contained. As the resin, a polyurethane resin, an acrylic resin, a polyester resin, a vinyl chloride resin, a polyolefin resin, an ethylene / vinyl acetate resin, or the like may be used alone or in combination. In particular, the microporous membrane is mainly composed of a polyurethane resin, and the non-porous membrane is also mainly composed of a polyurethane resin. Therefore, from the viewpoint of adhesion to the microporous membrane or the non-porous membrane, polyurethane is used. It is preferable to employ a base resin.
柄印刷用組成物中には、樹脂と有機溶媒の他に、以下のような第三成分が含有されていてもよい。たとえば、柄の耐摩耗性の向上を図るため磨耗向上剤或いは柄の滑り性を向上させるため滑剤を含有させておいてもよい。摩耗向上剤或いは滑剤としては、ポリジメチルシロキサン等のシリコン系化合物、摺動剤等で用いられているＬ−リジンと有機酸の反応生成物であるＮe −ラウロイル−Ｌ−リジン等の平板状粉体、湿式法（沈降法、ゲル法）による微多孔性の非晶質シリカ（二酸化珪素）微粉末が用いられる。また、その他の耐熱性有機フィラー微粉末や無機フィラー微粉末等が用いられる。さらに、透湿防水性布帛の増量を図るための充填剤、柄に所望の色彩や模様を与えるためのパール顔料等の顔料或いは染料、透湿防水性布帛に抗菌機能を与えるための抗菌剤、透湿防水性布帛の消臭効果を与えるための消臭剤等が、第三成分として含有されていてもよい。柄印刷用組成物の粘度は、印刷条件や柄によって適宜決定しうる事項であり、一般的には１００〜１００００ｍＰａ・ｓ（２５℃）の範囲で選択される。 The pattern printing composition may contain the following third component in addition to the resin and the organic solvent. For example, a wear improver for improving the wear resistance of the handle or a lubricant for improving the slipperiness of the handle may be contained. As a wear improver or lubricant, a flat powder such as Ne-lauroyl-L-lysine, which is a reaction product of L-lysine and organic acid used in silicon compounds such as polydimethylsiloxane and sliding agents, etc. And microporous amorphous silica (silicon dioxide) fine powder by a wet method (precipitation method, gel method) is used. Further, other heat-resistant organic filler fine powder, inorganic filler fine powder, and the like are used. Furthermore, a filler for increasing the moisture permeable waterproof fabric, a pigment or dye such as a pearl pigment for giving a desired color or pattern to the handle, an antibacterial agent for giving an antibacterial function to the moisture permeable waterproof fabric, A deodorizing agent or the like for giving a deodorizing effect of the moisture permeable waterproof fabric may be contained as a third component. The viscosity of the pattern printing composition is a matter that can be appropriately determined depending on the printing conditions and pattern, and is generally selected in the range of 100 to 10,000 mPa · s (25 ° C.).
所定の柄としては、どのようなもので採用しうる。たとえば、ドット状、格子状、線状、斜線型、市松模様、ピラミッド型、亀甲柄、ある特定のネームや商標柄或いはランダム状柄等が採用され、これらは意匠性を発揮しやすい柄であり、好ましいものである。所定柄の占有面積は、透湿防水性布帛の透湿度に悪影響を及ぼさない範囲であれば任意である。一般的には、２〜５０％程度の範囲である。２％未満では、たとえ細線柄を主体としても意匠性の発揮が困難となりやすく、また、占有面積が５０％超えると布帛の透湿性能に影響を生じやすいので好ましくない。所定柄の厚さは、０. ５〜１０μｍ程度でよい。柄の厚さが０. ５μｍ未満では見栄え感やコントラスト感が劣り、意匠性が乏しくなる傾向となる。また、柄の厚さが１０μｍを超えると、柄自体が摩耗脱落しやすくなり、耐久性に難点を生じやすい傾向となる。 Any predetermined pattern can be used. For example, dot, lattice, linear, diagonal, checkered, pyramid, turtle shell, specific name, trademark pattern, or random pattern, etc. are used, and these patterns are easy to exhibit design. Is preferable. The area occupied by the predetermined pattern is arbitrary as long as it does not adversely affect the moisture permeability of the moisture-permeable and waterproof fabric. Generally, it is about 2 to 50% of range. If it is less than 2%, it is difficult to exhibit the design properties even if it is mainly composed of a fine line pattern, and if the occupied area exceeds 50%, the moisture permeability of the fabric is likely to be affected. The thickness of the predetermined pattern may be about 0.5 to 10 μm. If the thickness of the handle is less than 0.5 μm, the appearance and the contrast are inferior and the design property tends to be poor. On the other hand, when the thickness of the handle exceeds 10 μm, the handle itself tends to be worn off and tends to cause difficulty in durability.
また、本発明では、縫製の簡略化や着用多汗時のべたつき防止等の観点から、布帛本体を表地として、微多孔膜表面或いは無孔膜表面に接着剤を用いて、裏地を貼合してもよい。すなわち、微多孔膜或いは無孔膜と裏地とを接着剤を介して貼合してもよい。このようにして得られた透湿防水性布帛は、布帛本体／微多孔膜／接着剤／裏地、布帛本体／微多孔膜／無孔膜／接着剤／裏地或いは布帛本体／無孔膜／微多孔膜／接着剤／裏地の順で積層された形態となっている。 Further, in the present invention, from the viewpoint of simplification of sewing and prevention of stickiness when wearing a lot of sweat, the fabric body is used as a surface material, and an adhesive is used on the surface of the microporous membrane or the nonporous membrane to bond the backing. May be. That is, a microporous film or a nonporous film and a backing may be bonded via an adhesive. The moisture-permeable and waterproof fabric thus obtained is a fabric body / microporous membrane / adhesive / lining, fabric body / microporous membrane / nonporous membrane / adhesive / lining, or fabric body / nonporous membrane / fine. It is a laminated form in the order of porous film / adhesive / lining.
裏地としては、布帛本体と同様のものが用いられる。特に、コスト、風合い、軽量性及びシームテープ接着性等から鑑みて、繊度が１５〜７８デシテックスのポリアミド系合成繊維やポリエステル系合成繊維、或いは前記と同繊度クラスのポリアミド系合成繊維／木綿やポリエステル系合成繊維／木綿の混合繊維よりなる織編物、不織布などが好ましい。その中でも、繊度が１５〜４４デシテックスのポリアミド系長繊維或いはポリエステル系長繊維よりなる編織物又は不織布が、縫製部へのシームテープ接着の容易さやシーリング部分の防水性能、並びにそれらの耐久性が有利となるので、より好ましい。なお、シームテープとは、縫製品の縫い目に防水の目的で貼合する接着テープのことである。 As the lining, the same material as that of the fabric body is used. In particular, in view of cost, texture, lightness, seam tape adhesion, etc., a polyamide synthetic fiber or polyester synthetic fiber having a fineness of 15 to 78 dtex, or a polyamide synthetic fiber / cotton or polyester of the same fineness class as described above A woven or knitted fabric or nonwoven fabric made of a mixed fiber of a synthetic fiber / cotton is preferred. Among them, a knitted fabric or non-woven fabric made of polyamide long fibers or polyester long fibers having a fineness of 15 to 44 dtex is advantageous in terms of ease of seam tape adhesion to the sewing portion, waterproof performance of the sealing portion, and durability thereof. Therefore, it is more preferable. The seam tape is an adhesive tape that is bonded to the seam of the sewing product for the purpose of waterproofing.
裏地を貼合するための接着剤としては、従来公知のものを採用すればよい。たとえば、天然ゴム、ニトリルゴム系やクロロプレンゴム系等の合成ゴム、酢酸ビニル系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、エチレン−酢酸ビニル共重合樹脂、ポリウレタン系樹脂等が単独で又は混合して用いられる。接着剤の種類としては、接着耐久性の観点から、硬化型接着剤を用いるのが好ましい。硬化型接着剤は、水酸基、イソシアネート基、アミノ基又はカルボキシル基等の反応基を持ついわゆる架橋性を有したポリウレタン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリエチレン−酢酸ビニル共重合体樹脂等が自己架橋するか、或いはイソシアネート系化合物又はエポキシ系化合物等の架橋剤と架橋して、硬化するものである。これらの中でも、ポリウレタン系樹脂が柔軟性に富み、かつ透湿性にも優れているので好ましい。 What is necessary is just to employ | adopt a conventionally well-known thing as an adhesive agent for bonding a lining. For example, natural rubber, synthetic rubber such as nitrile rubber or chloroprene rubber, vinyl acetate resin, acrylic resin, polyamide resin, polyester resin, ethylene-vinyl acetate copolymer resin, polyurethane resin, etc. alone or Used as a mixture. As the type of adhesive, it is preferable to use a curable adhesive from the viewpoint of adhesion durability. Curing adhesives include so-called crosslinkable polyurethane resins, polyester resins, polyamide resins, polyethylene-vinyl acetate copolymer resins having reactive groups such as hydroxyl groups, isocyanate groups, amino groups or carboxyl groups. It is self-crosslinked or is cured by crosslinking with a crosslinking agent such as an isocyanate compound or an epoxy compound. Among these, polyurethane-based resins are preferable because they are rich in flexibility and excellent in moisture permeability.
また、接着剤の性状は、エマルジョン型、溶剤型或いはホットメルト型等のいずれであってもよい。エマルジョン型又は溶剤型の接着剤の場合は、粘度を５００〜５０００ｍＰａ・ｓ程度として、グラビアロールやコンマコーター等の塗布手段で、微多孔膜表面、無孔膜表面又は裏地表面に、全面に又は部分的に塗布する。塗布後、微多孔膜又は無孔膜と裏地とをラミネート機で圧着又は熱圧着して貼合すればよい。また、ホットメルト型の接着剤の場合は、８０〜１８０℃程度の温度をホットメルト型接着剤に与えて、溶融させた後、微多孔膜表面、無孔膜表面又は裏地表面に、全面に又は部分的に塗布する。そして、必要により冷却しながら、ラミネート機で微多孔膜又は無孔膜と裏地とを圧着して貼合すればよい。 Further, the properties of the adhesive may be any of an emulsion type, a solvent type and a hot melt type. In the case of an emulsion-type or solvent-type adhesive, the viscosity is about 500 to 5000 mPa · s, and it is applied to the entire surface of the microporous film surface, non-porous film surface or lining surface by a coating means such as a gravure roll or a comma coater, or Apply partially. After coating, the microporous film or nonporous film and the backing may be bonded by pressure bonding or thermocompression bonding with a laminating machine. In the case of a hot-melt type adhesive, a temperature of about 80 to 180 ° C. is applied to the hot-melt type adhesive and melted, and then the entire surface is applied to the surface of the microporous film, the nonporous film or the backing surface. Or apply partially. And what is necessary is just to carry out the pressure bonding of a microporous film or a non-porous film | membrane, and a backing with a laminating machine, cooling as needed.
接着剤は、前記したように、微多孔膜等の表面に全面に又は部分的に適用される。透湿性能や風合いの観点からは、部分的に適用するのが好ましい。たとえば、点状、線状、市松模様、亀甲模様等の形態で、微多孔膜等の表面全体に亙って均一に適用するのが好ましい。接着剤の占有面積は、１０〜８０％程度が好ましい。接着剤の占有面積が１０％未満では、接着剤の膜厚を厚くしても接着力が不十分となって、裏地が剥離しやすくなる傾向が生じる。また、接着剤の占有面積が８０％を超えると、接着力は十分となりやすいが、特に透湿性能が低下する恐れが生じる。しかしながら、接着剤として透湿性のあるポリウレタン系接着剤を使用すれば、接着剤の占有面積が８０％を超えても、差し支えない。適用した接着剤の厚さは、接着剤の占有面積や裏地の凹凸性やスパン感などにも依るが、５〜１００μｍ程度でよい。接着剤の厚さが５μｍ未満では、裏地との接着力が不十分となる傾向が生じる。接着剤の厚さが１００μｍを超えると、透湿防水性布帛の透湿性能が低下したり、風合いが硬化したりする傾向となる。 As described above, the adhesive is applied to the entire surface or a part of the surface of the microporous film or the like. It is preferable to apply partially from the viewpoint of moisture permeability and texture. For example, it is preferably applied uniformly over the entire surface of the microporous membrane or the like in the form of a dot, line, checkered pattern, turtle shell pattern or the like. The area occupied by the adhesive is preferably about 10 to 80%. When the area occupied by the adhesive is less than 10%, the adhesive force becomes insufficient even if the thickness of the adhesive is increased, and the lining tends to be easily peeled off. In addition, when the area occupied by the adhesive exceeds 80%, the adhesive force tends to be sufficient, but the moisture permeation performance may be lowered. However, if a moisture-permeable polyurethane adhesive is used as the adhesive, the occupied area of the adhesive may exceed 80%. The thickness of the applied adhesive may be about 5 to 100 μm, although it depends on the area occupied by the adhesive, the unevenness of the lining and the span feeling. If the thickness of the adhesive is less than 5 μm, the adhesive strength with the backing tends to be insufficient. If the thickness of the adhesive exceeds 100 μm, the moisture-permeable performance of the moisture-permeable and waterproof fabric tends to decrease, or the texture tends to harden.
以上の説明したように、本発明に係る透湿防水性布帛は、布帛本体／微多孔膜、布帛本体／微多孔膜／無孔膜、布帛本体／無孔膜／微多孔膜、布帛本体／微多孔膜／柄印刷、布帛本体／微多孔膜／無孔膜／柄印刷、布帛本体／無孔膜／微多孔膜／柄印刷、布帛本体／微多孔膜／接着剤／裏地、布帛本体／微多孔膜／無孔膜／接着剤／裏地及び布帛本体／無孔膜／微多孔膜／接着剤／裏地の順で積層された各種のものがある。かかる透湿防水性布帛に、さらに耐水圧を向上させるため、撥水加工を施してもよい。撥水加工の方法は、目潰し加工を行うことは少ないが、基本的には、布帛本体を撥水加工する方法と同様にして行うことができる。 As described above, the moisture-permeable and waterproof fabric according to the present invention includes the fabric body / microporous membrane, the fabric body / microporous membrane / nonporous membrane, the fabric body / nonporous membrane / microporous membrane, and the fabric body / Microporous membrane / pattern printing, fabric body / microporous membrane / non-porous membrane / pattern printing, fabric body / nonporous membrane / microporous membrane / pattern printing, fabric body / microporous membrane / adhesive / lining, fabric body / There are various layers in the order of microporous membrane / nonporous membrane / adhesive / lining and fabric body / nonporous membrane / microporous membrane / adhesive / lining. In order to further improve the water pressure resistance, the moisture permeable waterproof fabric may be subjected to water repellent finishing. The method of water repellent finishing is rarely performed by crushing, but can basically be performed in the same manner as the method of water repellent finishing of the fabric body.
本発明にかかる透湿防水性布帛は、耐水圧、透湿性及び洗濯耐久性に優れており、スポーツ衣料や防寒衣料等の各種衣料の素材としてはもちろん、テント等の登山用具等の素材としても使用しうるものである。さらに、透湿防水性の必要な各種製品の素材としても、使用しうるものである。 The moisture-permeable and waterproof fabric according to the present invention is excellent in water pressure resistance, moisture permeability and washing durability, and can be used not only as a material for various clothing such as sports clothing and cold clothing, but also as a material for mountaineering equipment such as tents. It can be used. Furthermore, it can be used as a material for various products that require moisture permeability and waterproofness.
本発明に係る透湿防水性布帛は、布帛本体の片面に、ポリウレタン樹脂を主体とする微多孔膜が積層されてなるものであって、微多孔膜が、フッ素系撥水剤１〜９質量％及び油溶性のフッ素系界面活性剤０．１〜２質量％が含有されてなる微多孔膜形成用樹脂組成物を用いて形成されたものである。したがって、微多孔膜には、フッ素系撥水剤と油溶性のフッ素系界面活性剤が併存しており、微孔の細部までもフッ素系撥水剤が均一に付与される。また、透湿防水性布帛に洗濯を繰り返すと、洗剤が微孔に残留してゆくが、油溶性のフッ素系界面活性剤は、その作用は定かではないが、この洗剤を水洗によって脱離しやすくする。したがって、本発明に係る透湿防水性布帛は、当初の耐水圧及び透湿度にも優れているが、洗濯を繰り返しても当初の耐水圧が低下しにくく、洗濯耐久性に優れるという効果を奏する。 The moisture-permeable and waterproof fabric according to the present invention is formed by laminating a microporous film mainly composed of a polyurethane resin on one side of a fabric body, and the microporous film has 1 to 9 mass of a fluorine-based water repellent. % And an oil-soluble fluorosurfactant in an amount of 0.1 to 2% by mass. Therefore, the microporous film is coexisting with the fluorine-based water repellent and the oil-soluble fluorine-based surfactant, and the fluorine-based water repellent is evenly applied to the fine pores. In addition, when washing is repeated on a moisture-permeable and waterproof fabric, the detergent remains in the micropores, but the action of the oil-soluble fluorosurfactant is not clear, but it is easy to remove this detergent by washing with water. To do. Therefore, the moisture-permeable and waterproof fabric according to the present invention is excellent in the initial water pressure resistance and moisture permeability, but has an effect that the initial water pressure pressure is hardly lowered even after repeated washing, and is excellent in washing durability. .
以下、本発明を実施例に基づいて説明するが、本発明は実施例に限定されるものではない。本発明は、微多孔膜形成用樹脂組成物中に、フッ素系撥水剤及び油溶性のフッ素系界面活性剤を所定量含有させて微多孔膜を形成すると、洗濯耐久性に優れた透湿防水性布帛が得られるとの知見に基づくものとして、解釈されるべきである。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example. The present invention provides a moisture permeation excellent in washing durability when a microporous film is formed by containing a predetermined amount of a fluorine-based water repellent and an oil-soluble fluorosurfactant in a resin composition for forming a microporous film. It should be interpreted as being based on the knowledge that a waterproof fabric can be obtained.
実施例１
［布帛本体の準備］
経糸、緯糸の双方に、ナイロン６マルチフィラメント７８ｄｔｅｘ／６８ｆを用いて、経糸密度１１５本／２．５４ｃｍ、緯糸密度９５本／２．５４ｃｍの平組織織物を製織した。得られた平組織織物を精練した後、酸性染料（日本化薬株式会社製「Ｋａｙａｎｏｌ Ｂｌｕｅ Ｎ２Ｇ」）１．０％ｏｍｆを用いて染色して、染色織物を得た。その後、染色織物へ下記処方１の水分散液をパディング法（ピックアップ率４０％）にて付与した後、乾燥し、その後１７０℃×４０秒の熱処理を行った。続いて、一本が鏡面ロールである一対のカレンダーロールを用いて、温度１７０℃、圧力３００ｋＰａ、速度３０ｍ／分の条件でカレンダー加工して、布帛本体を得た。
〈処方１〉
フッ素系撥水剤エマルジョン ５０質量部
（日華化学株式会社製「ＮＫガード ＳＣＨ−０２」、固形分２０質量％）
ブロックタイプイソシアネート １０質量部
（明成化学工業株式会社製「メイカネート ＷＥＢ」）
イソプロピルアルコール ３０質量部
水 ９１０質量部
Example 1
[Preparation of fabric body]
A plain structure woven fabric having a warp density of 115 / 2.54 cm and a weft density of 95 / 2.54 cm was woven using nylon 6 multifilament 78 dtex / 68f for both the warp and the weft. The obtained plain tissue fabric was scoured and then dyed with 1.0% omf of an acid dye (“Kayanol Blue N2G” manufactured by Nippon Kayaku Co., Ltd.) to obtain a dyed fabric. Thereafter, an aqueous dispersion of the following formulation 1 was applied to the dyed fabric by the padding method (pickup rate 40%), and then dried, followed by heat treatment at 170 ° C. for 40 seconds. Subsequently, a pair of calender rolls, one of which is a mirror roll, was calendered under conditions of a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 30 m / min to obtain a fabric body.
<Prescription 1>
Fluorine-based water repellent emulsion 50 parts by mass (“NK Guard SCH-02” manufactured by Nikka Chemical Co., Ltd., solid content 20% by mass)
Block type isocyanate 10 parts by mass (“Meikanate WEB” manufactured by Meisei Chemical Co., Ltd.)
Isopropyl alcohol 30 parts by weight Water 910 parts by weight
［微多孔膜形成用樹脂組成物の調製］
下記処方２の微多孔膜形成用樹脂組成物を調液した。この微多孔膜形成用樹脂組成物は、固形分濃度が２０質量％で粘度が９０００ｍＰａ・ｓ／２５℃であり、固形分中のフッ素系撥水剤含有量が３質量％であり、油溶性のフッ素系界面活性剤含有量が０．５質量％であった。
〈処方２〉
エステル型ポリウレタン樹脂溶液 １００質量部
（大日精化工業株式会社製「レザミン ＣＵ４５５５」、固形分２７質量％）
イソシアネート化合物（架橋剤） ２質量部
（大日精化工業株式会社製「レザミンＸ」）
フッ素系撥水剤エマルジョン ３質量部
（クラリアントジャッパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」、
固形分３１質量％）
油溶性のフッ素系界面活性剤 ０．１５質量部
（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）
Ｎ，Ｎ−ジメチルホルムアミド ４５質量部
なお、調液は以下の手法で行った。まず、Ｎ，Ｎ−ジメチルホルムアミドに油溶性のフッ素系界面活性剤を溶解させた後、フッ素系撥水剤エマルジョンを添加混合して分散させ、その後他の成分を混合してから、ディスパー型攪拌機を用いて、真空脱泡しながら攪拌し調液した。
[Preparation of resin composition for forming microporous film]
A resin composition for forming a microporous film having the following formulation 2 was prepared. This resin composition for forming a microporous film has a solid content concentration of 20% by mass, a viscosity of 9000 mPa · s / 25 ° C., a fluorine-based water repellent content in the solid content of 3% by mass, and is oil-soluble. The fluorosurfactant content of was 0.5% by mass.
<Prescription 2>
Ester-type polyurethane resin solution 100 parts by mass ("Rezamin CU4555" manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 27% by mass)
Isocyanate compound (crosslinking agent) 2 parts by mass ("Rezamin X" manufactured by Dainichi Seika Kogyo Co., Ltd.)
Fluorine-based water repellent emulsion 3 parts by mass (“NUVA N2114 LIQ” manufactured by Clariant Japan Ltd.,
(Solid content 31% by mass)
Oil-soluble fluorosurfactant 0.15 parts by mass (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.)
N, N-dimethylformamide 45 parts by mass The preparation was performed by the following method. First, after dissolving an oil-soluble fluorosurfactant in N, N-dimethylformamide, a fluororesin repellent emulsion is added and dispersed, and after mixing other components, a disper type stirrer Was mixed with stirring while vacuum degassing.
［透湿防水性布帛の製造］
前記布帛本体の鏡面ロールでカレンダーされた面を塗布面として、前記微多孔膜形成用樹脂組成物をコンマコーターを用いて塗布量１００ｇ／ｍ2にて塗布後、濃度１０質量％のＮ，Ｎ−ジメチルホルムアミド水溶液（液温２０℃）の凝固浴に２分間浸漬して、微多孔膜形成用樹脂組成物を凝固させた。その後、５０℃で５分間の湯洗を行い、布帛本体をマングルで絞り、続いて、１３０℃で２分間の乾燥を行い、微多孔膜を形成した。続いて、１７０℃で１分間のセット加工を行って、透湿防水性布帛を得た。
[Manufacture of moisture-permeable and waterproof fabrics]
Using the surface calendered by the mirror roll of the fabric body as the coating surface, the resin composition for forming a microporous film is applied at a coating amount of 100 g / m 2 using a comma coater, and then N, N having a concentration of 10% by mass. -The resin composition for forming a microporous film was coagulated by immersing in a coagulation bath of a dimethylformamide aqueous solution (liquid temperature 20 ° C) for 2 minutes. Thereafter, washing with hot water at 50 ° C. for 5 minutes was performed, and the fabric body was squeezed with mangle, followed by drying at 130 ° C. for 2 minutes to form a microporous film. Subsequently, set processing was performed at 170 ° C. for 1 minute to obtain a moisture-permeable and waterproof fabric.
実施例２
処方２の微多孔膜形成用樹脂組成物に代えて、下記処方３の微多孔膜形成用樹脂組成物を用いる他は、実施例１と同一の方法で透湿防水性布帛を得た。処方３の微多孔膜形成用樹脂組成物は、固形分濃度が２５質量％で粘度が１００００ｍＰａ・ｓ／２５℃であり、固形分中のフッ素系撥水剤含有量が４質量％であり、油溶性のフッ素系界面活性剤含有量が０．５質量％であった。
〈処方３〉
エステル型ポリウレタン樹脂溶液 １００質量部
（大日精化工業株式会社製「レザミン ＣＵ４８３６」、固形分２５質量％）
炭酸カルシウム ７質量部
（日東粉化工業株式会社製「ＮＳ ♯４００」）
イソシアネート化合物（架橋剤） ２質量部
（大日精化工業株式会社製「レザミンＸ」）
酸化チタン系着色剤 ２質量部
（ＤＩＣ株式会社製「ダイラックカラー Ｌ−１５００」）
フッ素系撥水剤エマルジョン ５質量部
（クラリアントジャッパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」、
固形分３１質量％）
油溶性のフッ素系界面活性剤 ０．２質量部
（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）
Ｎ，Ｎ−ジメチルホルムアミド ３０質量部
Example 2
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 1, except that the microporous film-forming resin composition of the following formulation 3 was used instead of the microporous film-forming resin composition of the formulation 2. The resin composition for forming a microporous film of Formula 3 has a solid content concentration of 25% by mass and a viscosity of 10,000 mPa · s / 25 ° C., and the fluorine-based water repellent content in the solid content is 4% by mass, The oil-soluble fluorosurfactant content was 0.5% by mass.
<Prescription 3>
Ester-type polyurethane resin solution 100 parts by mass (“Rezamin CU4836” manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 25% by mass)
7 parts by weight of calcium carbonate (“NS # 400” manufactured by Nitto Flour Chemical Co., Ltd.)
Isocyanate compound (crosslinking agent) 2 parts by mass ("Rezamin X" manufactured by Dainichi Seika Kogyo Co., Ltd.)
Titanium oxide-based colorant 2 parts by mass (“DIRAC color L-1500” manufactured by DIC Corporation)
Fluorine-based water repellent emulsion 5 parts by mass (“NUVA N2114 LIQ” manufactured by Clariant Japan Ltd.,
(Solid content 31% by mass)
0.2 part by mass of oil-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.)
N, N-dimethylformamide 30 parts by mass
実施例３
［微多孔膜形成用樹脂組成物の調製］
下記処方４の微多孔膜形成用樹脂組成物を調液した。処方４の微多孔膜形成用樹脂組成物は、固形分濃度が３１質量％で粘度が８０００ｍＰａ・ｓ／２５℃であり、固形分中のフッ素系撥水剤含有量が５質量％であり、油溶性のフッ素系界面活性剤含有量が１．２質量％であった。
〈処方４〉
水性ポリカーボネート系ウレタンエマルジョン ７５質量部
（大原パラヂウム化学株式会社製「パラゾール ＰＮＡ−１２０」、
固形分３０質量％）
水溶性ポリウレタン樹脂 ２５質量部
（大原パラヂウム株式会社製「パラミリオン ＡＦ−５０」、固形分５０質量％）
ブロックイソシアネート ５質量部
（大原パラヂウム株式会社製「パラキャット ＰＧＷ−４」）
フッ素系撥水剤エマルジョン ７質量部
（クラリアントジャッパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」、
固形分３１質量％）
油溶性のフッ素系界面活性剤 ０．５質量部
（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）
イソプロピルアルコール ５質量部
水 ２０質量部
なお、調液は以下の手法で行った。まず、油溶性のフッ素系界面活性剤をイソプロピルアルコールに溶解させた溶液と、フッ素系撥水剤エマルジョンに水１０質量部を添加した分散液とを混合した。続いて、「パラミリオン ＡＦ−５０」に水１０質量部を添加した溶液と、「パラゾール ＰＮＡ−１２０」と、「パラキャット ＰＧＷ−４」とを添加してから、ディスパー型攪拌機を用いて、真空脱泡しながら攪拌し調液した。
Example 3
[Preparation of resin composition for forming microporous film]
A resin composition for forming a microporous film having the following formulation 4 was prepared. The resin composition for forming a microporous film of Formula 4 has a solid content concentration of 31% by mass and a viscosity of 8000 mPa · s / 25 ° C., and the fluorine-based water repellent content in the solid content is 5% by mass, The oil-soluble fluorosurfactant content was 1.2% by mass.
<Prescription 4>
75 parts by mass of an aqueous polycarbonate urethane emulsion (“Parasol PNA-120” manufactured by Ohara Palladium Chemical Co., Ltd.,
(Solid content 30% by mass)
25 parts by mass of water-soluble polyurethane resin (“Paramilion AF-50” manufactured by Ohara Palladium Co., Ltd., solid content: 50% by mass)
Block isocyanate 5 parts by mass (Ohara Palladium Co., Ltd. “Paracat PGW-4”)
Fluorine-based water repellent emulsion 7 parts by mass (“NUVA N2114 LIQ” manufactured by Clariant Japan Co., Ltd.,
(Solid content 31% by mass)
0.5 part by mass of oil-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.)
Isopropyl alcohol 5 parts by mass Water 20 parts by mass The preparation was carried out by the following method. First, a solution obtained by dissolving an oil-soluble fluorine-based surfactant in isopropyl alcohol and a dispersion obtained by adding 10 parts by mass of water to a fluorine-based water repellent emulsion were mixed. Subsequently, a solution in which 10 parts by mass of water was added to “Paramilion AF-50”, “Parazole PNA-120”, and “Paracat PGW-4” were added. The mixture was stirred and mixed with vacuum degassing.
［透湿防水性布帛の製造］
実施例１で用いた布帛本体の鏡面ロールでカレンダーされた面を塗布面として、処方４の微多孔膜形成用樹脂組成物をコンマコーターを用いて塗布量１００ｇ／ｍ2にて塗布した。その後、１２０℃で３分間乾燥した後、１７０℃で２分間のセット加工を行った。続いて、家庭用洗濯機を用いて６０℃で１０分間ソーピングすることにより、水溶性ポリウレタン樹脂（「パラミリオン ＡＦ−５０」の固形分）を溶出させた。そして、すすぎを行った後、６０℃で２０分間タンブル乾燥し、透湿防水性布帛を得た。この透湿防水性布帛の微多孔膜は、水溶性ポリウレタン樹脂が溶出しているため、固形分中のフッ素系撥水剤含有量が７質量％であり、油溶性のフッ素系界面活性剤含有量が１．７質量％であった。
[Manufacture of moisture-permeable and waterproof fabrics]
Using the surface calendared by the mirror roll of the fabric body used in Example 1 as the coating surface, the resin composition for forming a microporous film of Formula 4 was coated at a coating amount of 100 g / m 2 using a comma coater. Then, after drying at 120 degreeC for 3 minutes, the set process for 2 minutes was performed at 170 degreeC. Subsequently, the water-soluble polyurethane resin (solid content of “Paramilion AF-50”) was eluted by soaping at 60 ° C. for 10 minutes using a household washing machine. Then, after rinsing, tumble drying was performed at 60 ° C. for 20 minutes to obtain a moisture-permeable and waterproof fabric. Since the water-soluble polyurethane resin is eluted from the microporous membrane of this moisture-permeable and waterproof fabric, the fluorine-based water repellent content in the solid content is 7% by mass, and the oil-soluble fluorine-containing surfactant is contained. The amount was 1.7% by mass.
実施例４
［無孔膜形成用樹脂組成物の調製］
下記処方５の無孔膜形成用樹脂組成物を調液した。処方５の無孔膜形成用樹脂組成物は、固形分濃度が２０質量％で粘度が８０００ｍＰａ・ｓ／２５℃であった。
〈処方５〉
エーテルタイプポリウレタン樹脂 １００質量部
（大日精化工業株式会社製「ハイレムン Ｙ１２８ＮＳ」、固形分２５質量％）
イソシアネート化合物 ２質量部
（日本ポリウレタン工業株式会社製「コロネート ＨＸ」）
撥水剤エマルジョン ２質量部
（クラリアントジャッパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」、
固形分３１質量％）
フッ素系界面活性剤 ０．３質量部
（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）
トルエン ３０質量部
水 ５質量部
なお、調液は以下の手法で行った。まず、フッ素系界面活性剤をトルエンに溶解させた後、「ハイレムン Ｙ１２８ＮＳ」及び「コロネート ＨＸ」を添加混合し、ディスパー型攪拌機を用いて攪拌しながら、水と「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」の混合液を添加し調液した。
Example 4
[Preparation of non-porous film-forming resin composition]
The resin composition for nonporous film formation of the following prescription 5 was prepared. The resin composition for forming a nonporous film of Formula 5 had a solid content concentration of 20% by mass and a viscosity of 8000 mPa · s / 25 ° C.
<Prescription 5>
100 parts by mass of ether type polyurethane resin (manufactured by Dainichi Seika Kogyo Co., Ltd. “Haylem Y128NS”, solid content 25% by mass)
Isocyanate compound 2 parts by mass (Nippon Polyurethane Industry Co., Ltd. “Coronate HX”)
2 parts by weight of water repellent emulsion (“NUVA N2114 LIQ” manufactured by Clariant Japan Co., Ltd.,
(Solid content 31% by mass)
Fluorosurfactant 0.3 part by mass (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.)
Toluene 30 parts by mass Water 5 parts by mass The preparation was performed by the following method. First, after dissolving the fluorosurfactant in toluene, “Haylemun Y128NS” and “Coronate HX” are added and mixed, and the mixture of water and “NUVA N2114 LIQ” is added while stirring using a disper-type stirrer. Added and prepared.
［微多孔膜形成用樹脂組成物の調製］
下記処方６の微多孔膜形成用樹脂組成物を調液した。処方６の微多孔膜形成用樹脂組成物は、固形分濃度が１８質量％で粘度が４０００ｍＰａ・ｓ／２５℃であり、固形分中のフッ素系撥水剤含有量が５質量％であり、油溶性のフッ素系界面活性剤含有量が０．９質量％であった。
〈処方６〉
溶剤型ポリウレタン樹脂 １００質量部
（大日精化工業株式会社製「ハイレムン Ｘ−３０４０」、固形分３０質量％）
フッ素系撥水剤エマルジョン ５質量部
（クラリアントジャッパン株式会社製「ＮＵＶＡ Ｎ２１１４ ＬＩＱ」、
固形分３１質量％）
油溶性のフッ素系界面活性剤 ０．３質量部
（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）
イソシアネート化合物（架橋剤） ２質量部
（大日精化工業株式会社製「レザミン Ｘ」）
メチルエチルケトン ２０質量部
トルエン ２０質量部
水 ４０質量部
なお、調液は以下の手法で行った。まず、油溶性のフッ素系界面活性剤をメチルエチルケトンとトルエンの混合溶剤に溶解させた溶液に、「ハイレムン Ｘ−３０４０」及び「レザミン Ｘ」を混合して、ディスパー型攪拌機で攪拌しながら、フッ素系撥水剤エマルジョンと水の混合分散溶液を徐々に添加して、調液した。得られた微多孔膜形成用樹脂組成物の性状は、Ｗ／Ｏ型エマルジョンであった。
[Preparation of resin composition for forming microporous film]
A resin composition for forming a microporous film having the following formulation 6 was prepared. The resin composition for forming a microporous film of Formulation 6 has a solid content concentration of 18% by mass and a viscosity of 4000 mPa · s / 25 ° C., and a fluorine-based water repellent content in the solid content is 5% by mass, The oil-soluble fluorosurfactant content was 0.9% by mass.
<Prescription 6>
Solvent-type polyurethane resin 100 parts by mass (“Haimun X-3040” manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 30% by mass)
Fluorine-based water repellent emulsion 5 parts by mass (“NUVA N2114 LIQ” manufactured by Clariant Japan Ltd.,
(Solid content 31% by mass)
0.3 part by mass of oil-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.)
Isocyanate compound (crosslinking agent) 2 parts by mass ("Rezamin X" manufactured by Dainichi Seika Kogyo Co., Ltd.)
Methyl ethyl ketone 20 parts by mass Toluene 20 parts by mass Water 40 parts by mass In addition, preparation was performed by the following method. First, “Hiremun X-3040” and “Rezamine X” are mixed in a solution obtained by dissolving an oil-soluble fluorosurfactant in a mixed solvent of methyl ethyl ketone and toluene, and stirred with a disperse type stirrer. A mixed dispersion solution of a water repellent emulsion and water was gradually added to prepare a solution. The property of the obtained resin composition for forming a microporous film was a W / O type emulsion.
［透湿防水性布帛の製造］
実施例１で用いた布帛本体の鏡面ロールでカレンダーされた面を塗布面として、処方５の無孔膜形成用樹脂組成物をナイフコーターを用いて塗布量１５ｇ／ｍ2にて塗布した。その後、１２０℃で２分間乾燥して、布帛本体表面に無孔膜を形成した。この無孔膜表面に、処方６の微多孔膜形成用樹脂組成物をコンマコーターを用いて塗布量１００ｇ／ｍ2にて塗布した。そして、１３０℃で２分間乾燥し、引き続いて１７０℃で１分間のセット加工を行い、無孔膜表面に微多孔膜が形成された透湿防水性布帛を得た。
[Manufacture of moisture-permeable and waterproof fabrics]
Using the surface calendered by the mirror roll of the fabric body used in Example 1 as the coating surface, the nonporous film-forming resin composition of Formula 5 was applied at a coating amount of 15 g / m 2 using a knife coater. Then, it dried at 120 degreeC for 2 minute (s), and the nonporous film was formed in the fabric main body surface. The resin composition for forming a microporous film of Formula 6 was applied to the surface of the nonporous film at a coating amount of 100 g / m 2 using a comma coater. Then, it was dried at 130 ° C. for 2 minutes and subsequently set at 170 ° C. for 1 minute to obtain a moisture-permeable and waterproof fabric having a microporous film formed on the nonporous film surface.
実施例５
［無孔膜形成用樹脂組成物の調製］
下記処方７の無孔膜形成用樹脂組成物を調液した。処方７の無孔膜形成用樹脂組成物は、固形分濃度が１６質量％で粘度が３０００ｍＰａ・ｓ／２５℃であった。
〈処方７〉
無黄変型ポリウレタン樹脂 ５０質量部
（セイコー化成株式会社製「ラックスキン Ｕ２５２４」、固形分２５質量％）
無黄変型ポリウレタン樹脂用マット剤 ５０質量部
（セイコー化成株式会社製「ラックスキン Ｕ２５２５Ｍ」、固形分２０質量％）
イソプロピルアルコール ２０質量部
トルエン ２０質量部
Example 5
[Preparation of non-porous film-forming resin composition]
The resin composition for nonporous film formation of the following prescription 7 was prepared. The resin composition for forming a nonporous film of Formulation 7 had a solid content concentration of 16% by mass and a viscosity of 3000 mPa · s / 25 ° C.
<Prescription 7>
Non-yellowing polyurethane resin 50 parts by mass (“Lackskin U2524” manufactured by Seiko Chemical Co., Ltd., solid content 25% by mass)
50 parts by weight of matting agent for non-yellowing polyurethane resin (“Lackskin U2525M” manufactured by Seiko Chemical Co., Ltd., solid content 20% by mass)
Isopropyl alcohol 20 parts by mass Toluene 20 parts by mass
［透湿防水性布帛の製造］
実施例２で得られた透湿防水性布帛の微多孔膜表面に、処方７の無孔膜形成用樹脂組成物をナイフコーターを用いて塗布量２０ｇ／ｍ2にて塗布した。その後、１２０℃で２分間乾燥して、微多孔膜表面に厚さ約３μｍの無孔膜を形成し、透湿防水性布帛を得た。
[Manufacture of moisture-permeable and waterproof fabrics]
The nonporous film-forming resin composition of Formula 7 was applied to the surface of the microporous film of the moisture-permeable and waterproof fabric obtained in Example 2 at a coating amount of 20 g / m 2 using a knife coater. Then, it dried at 120 degreeC for 2 minute (s), the nonporous film | membrane about 3 micrometers thick was formed in the microporous film surface, and the moisture-permeable waterproof fabric was obtained.
実施例６
［柄印刷用組成物の調製］
下記処方８の柄印刷用組成物を調液した。この柄印刷用組成物の粘度は１００ｍＰａ・ｓ／２５℃であった。
［柄印刷用組成物Ａ］
ポリウレタン系グラビアインキ １００質量部
（サカタインクス（株）製「ＸＧＬ−０１０ グレー」）
グラビアインキ用硬化剤 ３質量部
トルエン／メチルエチルケトン（１／１） ５０重量部
Example 6
[Preparation of pattern printing composition]
A pattern printing composition having the following formulation 8 was prepared. The viscosity of the pattern printing composition was 100 mPa · s / 25 ° C.
[Composition A for pattern printing]
100 parts by mass of polyurethane-based gravure ink (“XGL-010 Gray” manufactured by Sakata Inx Co., Ltd.)
Curing agent for gravure ink 3 parts by weight Toluene / methyl ethyl ketone (1/1) 50 parts by weight
［透湿防水性布帛の製造］
実施例２で得られた透湿防水性布帛の微多孔膜表面に、処方８の柄印刷用組成物を、格子柄が彫刻されたグラビアロール（深度；３８μｍ、格子占有面積：４５％）を用いて、塗布量６ｇ/ ｍ2にてグラビアコーティングを行った。その後、１２０℃で３０秒間乾燥し、格子柄を形成した。引き続き、１７０℃で１分間のセット加工を行い、格子柄を表面に持つ透湿防水性布帛を得た。
[Manufacture of moisture-permeable and waterproof fabrics]
A gravure roll (depth: 38 μm, lattice occupation area: 45%) engraved with a lattice pattern is applied to the surface of the microporous membrane of the moisture-permeable and waterproof fabric obtained in Example 2 with the pattern printing composition. Using, gravure coating was performed at a coating amount of 6 g / m 2 . Then, it dried at 120 degreeC for 30 second, and formed the lattice pattern. Subsequently, set processing was performed at 170 ° C. for 1 minute to obtain a moisture-permeable and waterproof fabric having a lattice pattern on the surface.
実施例７
実施例５で得られた表面に無孔膜を持つ透湿防水性布帛の無孔膜表面に、処方８の柄印刷用組成物を実施例６と同一の方法で、格子柄を表面に持つ透湿防水性布帛を得た。
Example 7
In the same manner as in Example 6, the pattern printing composition of Formula 8 is provided on the surface of the nonporous film of the moisture-permeable waterproof fabric having a nonporous film on the surface obtained in Example 5. A moisture permeable waterproof fabric was obtained.
実施例８
処方３において、フッ素系界面活性剤（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）に代えて、フッ素系界面活性剤（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−６５１」）を用いる他は、実施例２と同一の方法により、透湿防水性布帛を得た。なお、「ＳＵＲＦＬＯＮ Ｓ−３８６」は油溶性かつ水溶性であり、「ＳＵＲＦＬＯＮ Ｓ−６５１」は油溶性ではあるが水溶性ではない。
Example 8
In Formulation 3, instead of using a fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), a fluorosurfactant (“SURFLON S-651” manufactured by AGC Seimi Chemical Co., Ltd.) is used. By the same method as in Example 2, a moisture-permeable and waterproof fabric was obtained. “SURFLON S-386” is oil-soluble and water-soluble, and “SURFLON S-651” is oil-soluble but not water-soluble.
実施例９
［裏地の準備］
ナイロンフィラメント２２デシテックス／7 フィラメントを用いて、２８ゲージのトリコット地を編成し、通常の方法により、精練を行い、裏地を準備した。
Example 9
[Preparing the lining]
Using a nylon filament 22 dtex / 7 filament, a 28-gauge tricot fabric was knitted and scoured by a conventional method to prepare a lining.
実施例２で得られた透湿防水性布帛の微多孔膜表面に、ドット柄が彫刻されたグラビアロール（２０メッシュ）を用いて、湿気硬化型ポリウレタン樹脂系ホットメルト接着剤（三井武田ケミカル株式会社製「タケメルト ＭＡ３２２９」）を塗布量１０ｇ/ ｍ2にて塗布した。そして、塗布面に前記裏地を積層し、圧力３００ｋＰａで圧着した。以上の方法で、裏地が貼合された透湿防水性布帛を得た。 Moisture curable polyurethane resin hot melt adhesive (Mitsui Takeda Chemical Co., Ltd.) using a gravure roll (20 mesh) engraved with a dot pattern on the surface of the microporous membrane of the moisture permeable waterproof fabric obtained in Example 2 “Takemelt MA3229” manufactured by the company was applied at a coating amount of 10 g / m 2 . And the said lining was laminated | stacked on the application surface, and it crimped | bonded by the pressure of 300 kPa. By the above method, the moisture-permeable waterproof fabric with which the lining was bonded was obtained.
実施例１０
実施例５で得られた透湿防水性布帛の無孔膜表面に、実施例９と同一の方法で裏地を積層し圧着して、裏地が貼合された透湿防水性布帛を得た。
Example 10
On the surface of the non-permeable membrane of the moisture permeable waterproof fabric obtained in Example 5, a lining was laminated and pressure-bonded by the same method as in Example 9 to obtain a moisture permeable waterproof fabric with the lining bonded.
比較例１
処方２において、フッ素系撥水剤エマルジョン及び油溶性のフッ素系界面活性剤を除く他は、実施例１と同一の方法で透湿防水性布帛を得た。
Comparative Example 1
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 1, except that in the formulation 2, except for the fluorine-based water repellent emulsion and the oil-soluble fluorine-based surfactant.
比較例２
処方３において、フッ素系撥水剤エマルジョン及び油溶性のフッ素系界面活性剤を除く他は、実施例２と同一の方法で透湿防水性布帛を得た。
Comparative Example 2
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 2, except that in the formulation 3, except for the fluorine-based water repellent emulsion and the oil-soluble fluorine-based surfactant.
比較例３
処方４において、フッ素系撥水剤エマルジョン及び油溶性のフッ素系界面活性剤を除く他は、実施例３と同一の方法で透湿防水性布帛を得た。
Comparative Example 3
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 3, except that in the formulation 4, except for the fluorine-based water repellent emulsion and the oil-soluble fluorine-based surfactant.
比較例４
処方５において、撥水剤エマルジョン及びフッ素系界面活性剤を除き、かつ、処方６において、フッ素系撥水剤エマルジョン及び油溶性のフッ素系界面活性剤を除く他は、実施例４と同一の方法で透湿防水性布帛を得た。
Comparative Example 4
The same method as in Example 4 except that the water-repellent emulsion and the fluorosurfactant were removed from the formulation 5 and the water-repellent emulsion and the oil-soluble fluorosurfactant were removed from the formulation 6. A moisture permeable waterproof fabric was obtained.
比較例５
処方３において、フッ素系撥水剤エマルジョンを除く他は、実施例２と同一の方法で透湿防水性布帛を得た。
Comparative Example 5
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 2 except that the fluorine-based water repellent emulsion was excluded in Formulation 3.
比較例６
処方３において、油溶性のフッ素系界面活性剤を除く他は、実施例２と同一の方法で透湿防水性布帛を得た。
Comparative Example 6
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 2 except that the oil-soluble fluorosurfactant was removed from formulation 3.
比較例７
処方３において、フッ素系撥水剤エマルジョンの配合量を２０質量部に変更した他は、実施例２と同一の方法で透湿防水性布帛を得た。変更された処方３の微多孔膜形成用樹脂組成物は、固形分中のフッ素系撥水剤含有量が１５質量％であり、油溶性のフッ素系界面活性剤含有量が０．５質量％であった。
Comparative Example 7
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 2, except that in Formulation 3, the blending amount of the fluorine-based water repellent emulsion was changed to 20 parts by mass. The resin composition for forming a microporous film of the modified formulation 3 has a fluorine-based water repellent content in the solid content of 15% by mass, and an oil-soluble fluorine-based surfactant content of 0.5% by mass. Met.
比較例８
処方３において、油溶性のフッ素系界面活性剤の配合量を１質量部に変更した他は、実施例２と同一の方法で透湿防水性布帛を得た。変更された処方３の微多孔膜形成用樹脂組成物は、固形分中のフッ素系撥水剤含有量が４質量％であり、油溶性のフッ素系界面活性剤含有量が２．６質量％であった。
Comparative Example 8
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 2, except that in Formulation 3, the blending amount of the oil-soluble fluorosurfactant was changed to 1 part by mass. The resin composition for forming a microporous film of the modified formulation 3 has a fluorine-based water repellent content in the solid content of 4% by mass and an oil-soluble fluorine-based surfactant content of 2.6% by mass. Met.
比較例９
処方３において、フッ素系界面活性剤（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）に代えて、フッ素系界面活性剤（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−２４１」）を用いる他は、実施例２と同一の方法により、透湿防水性布帛を得た。なお、「ＳＵＲＦＬＯＮ Ｓ−３８６」は油溶性かつ水溶性であり、「ＳＵＲＦＬＯＮ Ｓ−２４１」は油溶性ではないが水溶性である。
Comparative Example 9
In Formulation 3, instead of using a fluorosurfactant ("SURFLON S-386" manufactured by AGC Seimi Chemical Co., Ltd.), a fluorosurfactant ("SURFLON S-241" manufactured by AGC Seimi Chemical Co., Ltd.) is used. By the same method as in Example 2, a moisture-permeable and waterproof fabric was obtained. “SURFLON S-386” is oil-soluble and water-soluble, and “SURFLON S-241” is not oil-soluble but water-soluble.
比較例１０
処方３において、フッ素系界面活性剤（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−３８６」）に代えて、フッ素系界面活性剤（ＡＧＣセイミケミカル株式会社製「ＳＵＲＦＬＯＮ Ｓ−４２０」）を用いる他は、実施例２と同一の方法により、透湿防水性布帛を得た。なお、「ＳＵＲＦＬＯＮ Ｓ−３８６」は油溶性かつ水溶性であり、「ＳＵＲＦＬＯＮ Ｓ−４２０」は油溶性でも水溶性でもない。
Comparative Example 10
In Formulation 3, instead of using a fluorosurfactant ("SURFLON S-386" manufactured by AGC Seimi Chemical Co., Ltd.), a fluorosurfactant ("SURFLON S-420" manufactured by AGC Seimi Chemical Co., Ltd.) is used. By the same method as in Example 2, a moisture-permeable and waterproof fabric was obtained. “SURFLON S-386” is oil-soluble and water-soluble, and “SURFLON S-420” is neither oil-soluble nor water-soluble.
実施例１〜１０及び比較例１〜１０で得られた透湿防水性布帛に関して、耐水圧、洗濯耐久性及び透湿度を、以下の方法で測定した。そして、その結果を表１に示した。
（１）耐水圧（ｋＰａ）
ＪＩＳ Ｌ−１０９２（高水圧法）に準じて測定した。
（２）洗濯耐久性（％）
ＪＩＳ Ｌ−０２１７（１０３法）に準じた洗濯を１００回繰り返した後の透湿防水性布帛の耐水圧（Ｂ）を測定し、下記式に準じて洗濯前の耐水圧（Ａ）に対する洗濯後の耐水圧（Ｂ）の保持率を算出し、この値を透湿防水性布帛の洗濯耐久性（％）とした。
洗濯耐久性（％）＝（Ｂ／Ａ）×１００
（３）透湿度（ｇ／ｍ2・２４ｈｒｓ）
ＪＩＳ Ｌ−１０９９ Ａ−１法（塩化カルシウム法）に準じて測定した。
With respect to the moisture-permeable and waterproof fabrics obtained in Examples 1 to 10 and Comparative Examples 1 to 10, water resistance, washing durability and moisture permeability were measured by the following methods. The results are shown in Table 1.
(1) Water pressure resistance (kPa)
It measured according to JIS L-1092 (high water pressure method).
(2) Washing durability (%)
After the washing according to JIS L-0217 (Method 103) was repeated 100 times, the water pressure resistance (B) of the moisture permeable waterproof fabric was measured, and after washing against the water pressure resistance (A) before washing according to the following formula The water pressure resistance (B) retention rate was calculated, and this value was defined as the washing durability (%) of the moisture-permeable and waterproof fabric.
Washing durability (%) = (B / A) × 100
(3) Moisture permeability (g / m 2 · 24 hrs)
It measured according to JIS L-1099 A-1 method (calcium chloride method).
［表１］
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
耐 水 圧
━━━━━━━━━━━━━━
洗濯前 １００回洗濯後 洗濯耐久性 透湿度
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ８０ ６０ ７５ ９２８９
実施例２ １０４ ７９ ７６ １０１２６
実施例３ ３６ ２６ ７２ １０１２４
実施例４ ４２ ３２ ７６ ９４８９
実施例５ １８２ １４２ ７８ ８１２３
実施例６ １１０ ７８ ７１ ９６２４
実施例７ １８４ １４３ ７８ ７７２２
実施例８ ９５ ７１ ７５ １０３５０
実施例９ １２５ ９８ ７８ ９１１３
実施例１０ ２０２ １６１ ８０ ７３１２
───────────────────────────────────
比較例１ ８３ ５０ ６０ ８５２１
比較例２ １０５ ４１ ３９ ９６３２
比較例３ １４ ７ ５０ １０２２３
比較例４ ３５ １７ ４９ ９２７６
比較例５ ７８ ３１ ４０ ９９８７
比較例６ ６８ ４２ ６２ ９７６３
比較例７ ６３ ３７ ５９ １０５３９
比較例８ ５７ ２３ ４０ １０３６８
比較例９ ７８ ３９ ５０ １０２３５
比較例１０ ８４ ４３ ５１ １０２４９
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Water pressure
━━━━━━━━━━━━━━
Before washing After washing 100 times Washing durability Moisture permeability ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 80 60 75 9289
Example 2 104 79 76 10126
Example 3 36 26 72 10124
Example 4 42 32 76 9489
Example 5 182 142 78 8123
Example 6 110 78 71 9624
Example 7 184 143 78 7722
Example 8 95 71 75 10350
Example 9 125 98 78 9113
Example 10 202 161 80 7312
───────────────────────────────────
Comparative Example 1 83 50 60 8521
Comparative Example 2 105 41 39 9632
Comparative Example 3 14 7 50 10223
Comparative Example 4 35 17 49 9276
Comparative Example 5 78 31 40 9987
Comparative Example 6 68 42 62 9763
Comparative Example 7 63 37 59 10539
Comparative Example 8 57 23 40 10368
Comparative Example 9 78 39 50 10235
Comparative Example 10 84 43 51 10249
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１〜１０と比較例１〜１０とを対比すると、実施例に係る透湿防水性布帛は、比較例に係るものに比べて、いずれも洗濯耐久性が良好であることが分かる。この理由は、以下のとおりであると考えられる。比較例１〜４に係る方法で得られた透湿防水性布帛は、微多孔膜中にフッ素系撥水剤及び油溶性のフッ素系界面活性剤の両者が含有されていないため、洗濯耐久性に劣る。比較例５に係る方法で得られた透湿防水性布帛は、微多孔膜中にフッ素系撥水剤が含有されていないため、洗濯耐久性に劣る。比較例６に係る方法で得られた透湿防水性布帛は、微多孔膜形成用樹脂組成物中に油溶性のフッ素系界面活性剤が含有されていないため、洗濯耐久性に劣る。比較例７に係る方法で得られた透湿防水性布帛は、微多孔膜中にフッ素系撥水剤が過剰に含有されているため、微多孔膜形成時に班が生じる。この結果、微多孔膜が均一に形成されないので、洗濯耐久性に劣る。比較例８に係る方法で得られた透湿防水性布帛は、微多孔膜中に油溶性の界面活性剤が過剰に含有されているため、洗剤を保持しやすくなるためか、洗濯耐久性に劣る。比較例９に係る方法で得られた透湿防水性布帛は、油溶性ではなく水溶性のフッ素系界面活性剤が含有されているので、洗濯時に洗い流されてしまうためか、洗濯耐久性に劣る。比較例１０に係る方法で得られた透湿防水性布帛は、油溶性でも水溶性でもないフッ素系界面活性剤が含有されているので、洗剤を脱離させにくいためか、洗濯耐久性に劣る。すなわち、微多孔膜に所定量のフッ素系撥水剤と油溶性のフッ素系界面活性剤が存在すると、得られた透湿防水性布帛の洗濯耐久性が向上するのである。 Comparing Examples 1 to 10 and Comparative Examples 1 to 10, it can be seen that the moisture-permeable and waterproof fabrics according to the examples all have better washing durability than those according to the comparative examples. The reason for this is considered as follows. The moisture-permeable and waterproof fabrics obtained by the methods according to Comparative Examples 1 to 4 do not contain both a fluorine-based water repellent and an oil-soluble fluorine-based surfactant in the microporous membrane, so that the washing durability Inferior to The moisture permeable and waterproof fabric obtained by the method according to Comparative Example 5 is inferior in washing durability because the microporous film does not contain a fluorine-based water repellent. The moisture-permeable and waterproof fabric obtained by the method according to Comparative Example 6 is inferior in washing durability because an oil-soluble fluorosurfactant is not contained in the resin composition for forming a microporous film. The moisture-permeable and waterproof fabric obtained by the method according to Comparative Example 7 contains a fluorinated water repellent in the microporous film, and thus a patch is formed when the microporous film is formed. As a result, since the microporous film is not formed uniformly, the washing durability is poor. The moisture permeable and waterproof fabric obtained by the method according to Comparative Example 8 contains an oil-soluble surfactant in the microporous membrane, so that it is easy to hold the detergent, or the washing durability is improved. Inferior. The moisture permeable and waterproof fabric obtained by the method according to Comparative Example 9 contains a water-soluble fluorosurfactant, not oil-soluble, so that it is washed away during washing or is inferior in washing durability. . The moisture permeable and waterproof fabric obtained by the method according to Comparative Example 10 contains a fluorosurfactant that is neither oil-soluble nor water-soluble, so that it is difficult to remove the detergent or is inferior in washing durability. . That is, when a predetermined amount of a fluorine-based water repellent and an oil-soluble fluorine-based surfactant are present in the microporous film, the washing durability of the obtained moisture-permeable and waterproof fabric is improved.
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