JP2007077191A - Adhesive composition for nonporous film type moisture-permeation and waterproofing and method for producing moisture-permeable and waterproofing fabric - Google Patents
Adhesive composition for nonporous film type moisture-permeation and waterproofing and method for producing moisture-permeable and waterproofing fabric Download PDFInfo
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- JP2007077191A JP2007077191A JP2005263748A JP2005263748A JP2007077191A JP 2007077191 A JP2007077191 A JP 2007077191A JP 2005263748 A JP2005263748 A JP 2005263748A JP 2005263748 A JP2005263748 A JP 2005263748A JP 2007077191 A JP2007077191 A JP 2007077191A
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- adhesive composition
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- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 239000004744 fabric Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000004078 waterproofing Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920005862 polyol Polymers 0.000 claims abstract description 29
- 150000003077 polyols Chemical class 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- -1 polyoxyethylene group Polymers 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 18
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 14
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 32
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 26
- 229920005749 polyurethane resin Polymers 0.000 claims description 23
- 229920005906 polyester polyol Polymers 0.000 claims description 20
- 239000001361 adipic acid Substances 0.000 claims description 16
- 235000011037 adipic acid Nutrition 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 10
- 239000005871 repellent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012209 synthetic fiber Substances 0.000 claims description 4
- 229920002994 synthetic fiber Polymers 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 72
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 239000010410 layer Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 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 3
- 239000004970 Chain extender Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 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 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XVWXTEGZTKSUQZ-UHFFFAOYSA-N 4-hydroxybutyl hydrogen carbonate Chemical compound OCCCCOC(O)=O XVWXTEGZTKSUQZ-UHFFFAOYSA-N 0.000 description 1
- BSKLKCJVOHJWHU-UHFFFAOYSA-N 6-hydroxyhexyl hydrogen carbonate Chemical compound OCCCCCCOC(O)=O BSKLKCJVOHJWHU-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 239000004835 fabric adhesive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、水系ポリウレタン樹脂を用いた、透湿性、耐水性、耐洗濯性に優れ、加工風合いにも優れた無孔質膜型透湿防水加工用接着剤組成物及びそれを用いた無孔質膜型透湿防水加工布帛の製造方法に関する。 The present invention relates to a non-porous membrane-type moisture-permeable and waterproof adhesive composition using a water-based polyurethane resin, excellent in moisture permeability, water resistance, washing resistance, and excellent in processing feeling, and non-porous using the same The present invention relates to a method for producing a membrane-type moisture permeable waterproof fabric.
従来より、アウトドア用の衣類などには、無孔質膜型透湿防水加工を施した布帛が使用されたものがある。この無孔質膜型透湿防水加工布帛は、ポリウレタン樹脂からなる透湿性の皮膜を接着剤を用いて撥水性の布帛上に形成する等により製造されている。透湿性皮膜や接着剤の形成に用いられるポリウレタン樹脂としては、これまで溶剤系のものが使用されており、例えば、ポリウレタン樹脂中にポリオキシエチレングリコールやポリオキシエチレン/ポリオキシプロピレンをランダム又はブロック共重合したものを用いることは広く知られている(例えば、特許文献1〜4)。 2. Description of the Related Art Conventionally, some outdoor clothing and the like have been used a fabric that has been subjected to a non-porous membrane-type moisture-permeable waterproof process. This non-porous membrane-type moisture-permeable waterproof fabric is manufactured by forming a moisture-permeable film made of a polyurethane resin on a water-repellent fabric using an adhesive. As polyurethane resins used for forming moisture-permeable films and adhesives, solvent-based polyurethane resins have been used so far. For example, polyoxyethylene glycol or polyoxyethylene / polyoxypropylene is randomly or blocked in the polyurethane resin. It is widely known to use a copolymer (for example, Patent Documents 1 to 4).
しかしながら、溶剤系のポリウレタン樹脂を使用すると、ジメチルホルムアミド(DMF)、トルエン、メチルエチルケトン(MEK)などの有機溶剤が製品中に含まれることとなり、この有機溶剤が布帛への加工中に大気に排出されたり、布帛中に残存し、大気汚染や水質汚染に大きな影響を及ぼしている。 However, when a solvent-based polyurethane resin is used, organic products such as dimethylformamide (DMF), toluene, and methyl ethyl ketone (MEK) are contained in the product, and this organic solvent is discharged into the atmosphere during processing into a fabric. Or remains in the fabric and has a great influence on air pollution and water pollution.
一方、近年、地球環境、安全、衛生などの観点から有機溶剤を含有しない水系ポリウレタン樹脂が注目されるに至っている。無孔質膜型透湿防水加工剤に於いても有機溶剤系ポリウレタン樹脂から水系ポリウレタン樹脂への転換が検討され、種々の無孔質型透湿防水加工剤が提案されている(例えば、特許文献5及び6)。この水系ウレタン樹脂は、環境への悪影響を低減できるという大きな特徴を有するものの、風合い、耐水性、透湿性、耐洗濯性等の点で、溶剤系樹脂を用いた無孔質型透湿防水加工剤に比較して大きく劣っているのが実情である。
本発明は上記のような従来技術の問題点を解決するために為されたものであり、本発明の目的は、風合い、耐水性、透湿性、耐洗濯性等の点で優れた無孔質膜型透湿防水加工用接着剤組成物及びそれを用いた無孔質膜型透湿防水加工布帛の製造方法を提供することである。 The present invention has been made in order to solve the above-mentioned problems of the prior art, and the object of the present invention is a nonporous material which is excellent in terms of texture, water resistance, moisture permeability, washing resistance and the like. It is an object to provide an adhesive composition for membrane-type moisture-permeable and waterproof processing and a method for producing a nonporous membrane-type moisture-permeable and waterproof fabric using the same.
本発明の無孔質膜型透湿防水加工用接着剤組成物は、(A成分)有機ポリイソシアネート成分と、(B成分)4個以上のオキシエチレン単位からなるポリオキシエチレン基を含有するとともにNCO基と反応性のある活性水素を少なくとも2個以上含有する第1のポリオール成分と、(C成分)NCO基と反応性のある活性水素を少なくとも2個以上含有する第2のポリオール成分とを構成成分として、NCO/OH比(モル比)=0.65〜0.99の範囲になるように反応させて得られた(P)末端水酸基を有するポリウレタンプレポリマーの水分散体に対して、更に、(D成分)水分散型ポリイソシアネート系架橋剤を配合して得られることを特徴とする。 The non-porous membrane-type moisture-permeable and waterproof adhesive composition of the present invention contains (A component) an organic polyisocyanate component and (B component) a polyoxyethylene group composed of 4 or more oxyethylene units. A first polyol component containing at least two active hydrogens reactive with NCO groups; and (component C) a second polyol component containing at least two active hydrogens reactive with NCO groups. As a constituent component, an aqueous dispersion of a polyurethane prepolymer having a (P) terminal hydroxyl group obtained by reacting to have a NCO / OH ratio (molar ratio) = 0.65 to 0.99, Further, it is obtained by blending (component D) a water-dispersed polyisocyanate crosslinking agent.
本発明では、(B成分)と(C成分)の2種類のポリオール成分を使用することにより、親水性と疎水性とのバランスが調整され、透湿防水加工布帛の接着剤として優れた風合い、耐水性、透湿性、耐洗濯性等が発揮される。 In the present invention, by using two types of polyol components (B component) and (C component), the balance between hydrophilicity and hydrophobicity is adjusted, and an excellent texture as an adhesive for moisture-permeable waterproof fabrics, Water resistance, moisture permeability, washing resistance, etc. are exhibited.
上記に於いては、前記(B成分)の第1のポリオール成分に含まれるオキシエチレン単位の合計の含有量が、水系ポリウレタン樹脂中の固形分を100重量%として、15〜60重量%であることが好ましい。 In the above, the total content of oxyethylene units contained in the first polyol component (component B) is 15 to 60% by weight, where the solid content in the aqueous polyurethane resin is 100% by weight. It is preferable.
上記に於いて、前記(C成分)の第2のポリオール成分が、1,4−ブタンジオール及びアジピン酸から成るポリエステルポリオール、並びに/又は1,6−ヘキサンジオール及びアジピン酸から成るポリエステルポリオールを含有していることが好ましい。 In the above, the (C component) second polyol component contains a polyester polyol composed of 1,4-butanediol and adipic acid and / or a polyester polyol composed of 1,6-hexanediol and adipic acid It is preferable.
また、前記(P)の末端水酸基を有するポリウレタンプレポリマーの水分散体と、(D成分)の水分散型ポリイソシアネート系架橋剤との配合比が、有効成分比で100:1〜100:10であることが好ましい。 The blend ratio of the aqueous dispersion of the polyurethane prepolymer having a terminal hydroxyl group (P) and the water-dispersed polyisocyanate crosslinking agent (component D) is 100: 1 to 100: 10 in terms of the active ingredient ratio. It is preferable that
本発明の透湿防水加工布帛の製造方法は、無孔質膜型透湿防水加工用の水系ポリウレタン樹脂組成物を含有する塗工液を離型紙に塗布し、乾燥処理して透湿層を得、該透湿層の上に、請求項1〜4の水系接着剤組成物を含有する接着剤を塗布し、乾燥した後、撥水処理した合成繊維布帛を貼り合わせるドライラミネート法により得られることを特徴とする。 In the method for producing a moisture-permeable waterproof fabric of the present invention, a moisture-permeable layer is formed by applying a coating liquid containing a water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproof processing to a release paper, and drying it. Obtained by a dry laminating method in which an adhesive containing the aqueous adhesive composition of claims 1 to 4 is applied onto the moisture permeable layer, dried, and then a synthetic fiber fabric subjected to water-repellent treatment is bonded. It is characterized by that.
また、無孔質膜型透湿防水加工用の水系ポリウレタン樹脂組成物を含有する塗工液を離型紙に塗布し、乾燥処理して透湿層を得、該透湿層の上に、請求項1〜4の水系接着剤組成物を含有する接着剤を塗布し、乾燥を行い、合成繊維布帛を貼り合わせた後に、撥水処理を行ってもよい。 In addition, a coating liquid containing a water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproof processing is applied to a release paper, and dried to obtain a moisture-permeable layer, on the moisture-permeable layer, The water-repellent treatment may be performed after applying an adhesive containing the water-based adhesive composition of Items 1 to 4, drying, and bonding the synthetic fiber fabric.
本発明によれば、従来の水系ポリウレタン樹脂では得ることが難しかった、透湿性、耐水性、耐洗濯性に優れ、加工風合いにも優れた無孔型透湿防水加工を可能とする透湿防水加工用接着剤、及びこれを用いた透湿防水加工布帛の製造方法が提供される。 According to the present invention, moisture permeation and waterproofing, which is difficult to obtain with a conventional water-based polyurethane resin, is excellent in moisture permeability, water resistance, washing resistance, and has a non-porous moisture permeation waterproofing process with excellent processing texture. A processing adhesive and a method for producing a moisture-permeable and waterproof fabric using the same are provided.
本発明において使用されるA成分の有機ポリイソシアネート成分としては、特に制限はなく、ウレタン工業の分野において周知のものを使用することができる。例えば、トリレンジイソシアネート(TDI)、ジフェニルメタンジイソシアネート(MDI)、ポリメリックMDI、ヘキサメチレンジイソシアネート(HMDI)、キシリレンジイソシアネート(XDI)、テトラメチルキシリレンジイソシアネート(TMXDI)、イソホロンジイソシアネート(IPDI)、水素添加MDI(H12MDI)などの有機ポリイソシアネート化合物が挙げられるが、無黄変性を要求される場合には、HMDIなどの脂肪族イソシアネート,IPDI、H12MDIなどの脂環族イソシアネート、XDI,TMXDIなどの芳脂環族イソシアネートが好ましい。 There is no restriction | limiting in particular as an organic polyisocyanate component of A component used in this invention, A well-known thing can be used in the field | area of the urethane industry. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated MDI Organic polyisocyanate compounds such as (H12MDI) can be mentioned, but when non-yellowing is required, aliphatic isocyanates such as HMDI, alicyclic isocyanates such as IPDI and H12MDI, and alicyclic rings such as XDI and TMXDI Group isocyanates are preferred.
本発明において使用されるB成分である第1のポリオール成分としては、4個以上のオキシエチレン単位からなるポリオキシエチレン基を含有するものであれば、ウレタン工業の分野において周知のものを使用することができ、例えば、ポリエーテルポリオールを挙げることができる。 As the first polyol component, which is the B component used in the present invention, those known in the field of the urethane industry are used as long as they contain a polyoxyethylene group composed of 4 or more oxyethylene units. For example, mention may be made of polyether polyols.
本発明に於けるB成分として使用し得るポリエーテルポリオールとしては、ポリオキシエチレングリコール、ポリオキシエチレンポリオキシプロピレンブロック共重合ポリオールが挙げられる。ポリオキシエチレンポリオキシプロピレンブロック共重合ポリオールを得るための出発物質として、グリセリン、ヘキサントリオール、トリメチロールエタン、トリメチロールプロパンなどのトリオール類や、トリエタノールアミン、トリイソプロパノールアミン、トリブタノールアミンなどのアルカノールアミン類などが挙げられる。また四官能アルコール成分としてはペンタエリスリトールが挙げられる。これら多価アルコールを出発物質とし塩基性触媒の存在下アルキレンオキサイドを重付加してポリエーテルポリオールを合成する。 Examples of the polyether polyol that can be used as the component B in the present invention include polyoxyethylene glycol and polyoxyethylene polyoxypropylene block copolymer polyol. Starting materials for obtaining polyoxyethylene polyoxypropylene block copolymer polyols include triols such as glycerin, hexanetriol, trimethylolethane, trimethylolpropane, and alkanols such as triethanolamine, triisopropanolamine, and tributanolamine. Examples include amines. An example of the tetrafunctional alcohol component is pentaerythritol. Using these polyhydric alcohols as starting materials, a polyether polyol is synthesized by polyaddition of alkylene oxide in the presence of a basic catalyst.
オキシエチレン基を有するB成分の第1のポリオールの数平均分子量は、300〜5000であることが好ましく、500〜2000であることがより好ましい。この数平均分子量が上記範囲を下回ると、透湿性が低下し、上記範囲を上回ると、粘度が高くなり、製品中の有効成分が低下するため、接着強度が低下する傾向が生じる。 The number average molecular weight of the first component B polyol having an oxyethylene group is preferably 300 to 5,000, more preferably 500 to 2,000. When this number average molecular weight is less than the above range, moisture permeability decreases, and when it exceeds the above range, the viscosity increases and the active ingredient in the product decreases, so that the adhesive strength tends to decrease.
B成分の第1のポリオール成分に含まれるオキシエチレン単位の合計の含有量は、水系ポリウレタン樹脂中の固形分を100重量%として、15〜60重量%であることが好ましい。この含有量が15重量%より小さいと十分な透湿性が得られず、60重量%を超えると、樹脂の親水性が高くなり過ぎて洗濯によって脱落し、洗濯後の透湿性及び耐水圧の低下を引き起こしてしまうことがあるので好ましくない。 The total content of oxyethylene units contained in the first polyol component of component B is preferably 15 to 60% by weight, with the solid content in the aqueous polyurethane resin being 100% by weight. If this content is less than 15% by weight, sufficient moisture permeability cannot be obtained, and if it exceeds 60% by weight, the hydrophilicity of the resin becomes too high and falls off by washing, resulting in a decrease in moisture permeability and water pressure resistance after washing. This is not preferable because it may cause
本発明において使用されるC成分である第2のポリオール成分としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオールを挙げることができる。 As a 2nd polyol component which is C component used in this invention, polyether polyol, polyester polyol, and polycarbonate polyol can be mentioned, for example.
本発明に於けるC成分として使用し得るポリエーテルポリオールとしては、ポリオキシプロピレングリコール、ポリオキシテトラメチレングリコールなどが挙げられる。これらのポリエーテルポリオールは、出発物質として、グリセリン、ヘキサントリオール、トリメチロールエタン、トリメチロールプロパンなどのトリオール類や、トリエタノールアミン、トリイソプロパノールアミン、トリブタノールアミンなどのアルカノールアミン類など、またペンタエリスリトール等の四官能アルコールを用い、これら多価アルコールに、塩基性触媒の存在下、プロピレンオキサイド、ブチレンオキサイドなどを重付加することにより得られる。 Examples of the polyether polyol that can be used as the component C in the present invention include polyoxypropylene glycol and polyoxytetramethylene glycol. These polyether polyols are starting materials such as glycerol, hexanetriol, trimethylolethane, trimethylolpropane and other triols, triethanolamine, triisopropanolamine, tributanolamine and other alkanolamines, and pentaerythritol. It is obtained by polyaddition of propylene oxide, butylene oxide, etc. to these polyhydric alcohols in the presence of a basic catalyst.
本発明に於けるC成分として使用し得るポリエステルポリオールを構成する二塩基酸成分としては、コハク酸、マロン酸、アジピン酸、リンゴ酸、セバチン酸、無水マレイン酸、のような脂肪族二塩基酸が挙げられる。ポリエステルポリオールを構成する二価アルコール成分としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタジオールなどの脂肪族グリコールが挙げられる。これら二塩基酸成分と二価アルコール成分とを縮合反応させてポリエステルポリオールが得られる。 Examples of the dibasic acid component constituting the polyester polyol that can be used as the C component in the present invention include aliphatic dibasic acids such as succinic acid, malonic acid, adipic acid, malic acid, sebacic acid, and maleic anhydride. Is mentioned. As the dihydric alcohol component constituting the polyester polyol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1 And aliphatic glycols such as 5-pentadiol. A polyester polyol is obtained by subjecting these dibasic acid component and dihydric alcohol component to a condensation reaction.
これらの組み合わせの中でも、結晶性を有する脂肪族系ポリエステルである、1,4−ブタンジオール/アジピン酸のポリエステルポリオール、1,6−ヘキサンジオール/アジピン酸のポリエステルポリオールが好ましい成分であり、これらの両方の成分を含んでいてもよい。 Among these combinations, 1,4-butanediol / adipic acid polyester polyol and 1,6-hexanediol / adipic acid polyester polyol, which are aliphatic polyesters having crystallinity, are preferable components. Both components may be included.
その他のポリエステルポリオールも本発明の効果を損なわない範囲で使用することができる。 Other polyester polyols can also be used as long as the effects of the present invention are not impaired.
本発明に於けるC成分として使用し得るポリカーボネートポリオールとしては、1,4−ブタンジオールのカーボネート、1,6−ヘキサンジオールのカーボネート、3−メチル−1,5−ペンタジオールのカーボネート、ポリ−1,4−シクロヘキサンジメタノールのカーボネート等のポリカーボネートジオールが挙げられ、本発明の効果を損なわない範囲で使用することができる。 Polycarbonate polyols that can be used as the component C in the present invention include 1,4-butanediol carbonate, 1,6-hexanediol carbonate, 3-methyl-1,5-pentadiol carbonate, poly-1 Polycarbonate diols such as carbonate of 1,4-cyclohexanedimethanol can be mentioned and can be used within the range not impairing the effects of the present invention.
本発明の水系ポリウレタン樹脂組成物を調製するに際して、本発明の効果を損なわない範囲内で鎖伸張剤を併用してもよい。鎖伸張剤としては、エチレングリコール、ジエチレングリコール、ブタンジオール、プロピレングリコール、ヘキサンジオール等の低分子鎖伸張剤を使用することができる。 In preparing the aqueous polyurethane resin composition of the present invention, a chain extender may be used in combination as long as the effects of the present invention are not impaired. As the chain extender, low molecular chain extenders such as ethylene glycol, diethylene glycol, butanediol, propylene glycol, and hexanediol can be used.
上記A成分の有機ポリイソシアネートと、上記B成分及びC成分のポリオールとの反応は、公知の方法により行うことができ、その反応の際のNCO基/活性水素基のモル比は、0.65〜0.99の範囲であり、反応は30〜130℃で30分〜50時間行うことにより、P成分の末端水酸基を有するポリウレタンプレポリマーが得られる。このP成分の末端水酸基を有するポリウレタンプレポリマーは、多くとも0.2重量%以下の遊離イソシアネート基を含有していることが好ましい。NCO/OH比(モル比)が0.65より小さいとP成分のプレポリマーの分子量が小さくて浸透性が高くなり、繊維に貼り付けた際に接着剤成分が繊維表面に滲み出してきてしまう。NCO/OH比(モル比)が0.99より大きいと、ポリウレタンプレポリマー製造時に、分子量が伸張してゲル化する場合があるので好ましくない。 The reaction of the organic polyisocyanate of component A with the polyols of component B and component C can be carried out by a known method, and the molar ratio of NCO groups / active hydrogen groups during the reaction is 0.65. A polyurethane prepolymer having a P component terminal hydroxyl group is obtained by carrying out the reaction at 30 to 130 ° C. for 30 minutes to 50 hours. The polyurethane prepolymer having a terminal hydroxyl group of the P component preferably contains at most 0.2% by weight of free isocyanate groups. When the NCO / OH ratio (molar ratio) is less than 0.65, the molecular weight of the P component prepolymer is small and the permeability is high, and the adhesive component oozes out to the fiber surface when attached to the fiber. . If the NCO / OH ratio (molar ratio) is larger than 0.99, the molecular weight may be stretched and gelled in the production of the polyurethane prepolymer, which is not preferable.
なお、上記ウレタンプレポリマーの合成に際し、イソシアネートに対して不活性で、かつ、ウレタンプレポリマーを溶解し得る溶剤を用いてもよい。使用し得る溶剤として、ジオキサン、メチルエチルケトン、ジメチルホルムアミド、テトラヒドロフラン、N−メチル−2−ピロリドン、トルエン、プロピレングリコールモノメチルエーテルアセテートなどが挙げられる。またウレタンプレポリマー水溶液の中に、酸化防止剤又は耐光剤の溶液又はエマルジョンを併用しても良い。 In the synthesis of the urethane prepolymer, a solvent which is inactive with respect to isocyanate and can dissolve the urethane prepolymer may be used. Examples of the solvent that can be used include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, and propylene glycol monomethyl ether acetate. Moreover, you may use together the solution or emulsion of antioxidant or a light-resistant agent in urethane prepolymer aqueous solution.
酸化防止剤としてはヒンダードフェノール系又はセミカルバジド系などの酸化防止剤の溶液又はエマルジョンが挙げられる。耐光剤としてはヒンダードアミン(HALS)系、ベンゾフェノン系、ベンゾトリアゾール系などの耐光剤の溶液又はエマルジョンが挙げられる。 Examples of the antioxidant include a solution or emulsion of an antioxidant such as a hindered phenol type or a semicarbazide type. Examples of the light fastener include solutions or emulsions of light fasteners such as hindered amine (HALS), benzophenone, and benzotriazole.
本発明のD成分の水分散型イソシアネート架橋剤としては、ポリイソシアネートに親水基を導入した水分散可能なタイプで、日本ポリウレタン工業(株)製の「アクアネート」シリーズが好適である。 The water-dispersible isocyanate crosslinking agent of component D of the present invention is a water-dispersible type in which a hydrophilic group is introduced into polyisocyanate, and “Aquanate” series manufactured by Nippon Polyurethane Industry Co., Ltd. is suitable.
上記P成分の末端水酸基を有するポリウレタンプレポリマーの水分散体と、D成分の水分散型ポリイソシアネート系架橋剤との配合比は、有効成分比で100:1〜100:10である。水分散型ポリイソシアネート系架橋剤が、末端水酸基を有するポリウレタンプレポリマーの水分散体100部に対して、1部以下では十分な剥離強度が得られない。また、10部以上では配合系でのポットライフが低下し、さらに得られる繊維積層体の風合いが硬くなってしまうので好ましくない。 The mixing ratio of the aqueous dispersion of the polyurethane prepolymer having a terminal hydroxyl group of the P component and the water-dispersed polyisocyanate-based crosslinking agent of the D component is 100: 1 to 100: 10 in terms of the effective component ratio. If the water-dispersed polyisocyanate-based crosslinking agent is 1 part or less with respect to 100 parts of an aqueous dispersion of a polyurethane prepolymer having a terminal hydroxyl group, sufficient peel strength cannot be obtained. On the other hand, if it is 10 parts or more, the pot life in the blending system is lowered, and the texture of the resulting fiber laminate becomes hard, which is not preferable.
本発明の透湿防水加工布帛の製造方法は、上記無孔質膜型透湿防水加工用接着剤組成物を使用し、ドライラミネート法により透湿防水加工布帛を得るものである。即ち、無孔質膜型透湿防水加工用の水系ポリウレタン樹脂組成物を離型紙に塗布し、ピンテンターなどを用いて加熱乾燥処理を行うことにより透湿層が形成される。その後、この透湿層の上に、本発明の無孔質膜型透湿防水加工用接着剤組成物を塗布し、ピンテンターなどを用いて乾燥させた後、撥水処理した布帛を貼り合わせ、ピンテンターなどを用いて加熱する。次に、離型紙を剥がすことにより、透湿防水加工布帛が得られる。 The method for producing a moisture-permeable and waterproof fabric of the present invention uses the nonporous membrane moisture-permeable and waterproof adhesive composition and obtains a moisture-permeable and waterproof fabric by a dry laminating method. That is, a moisture-permeable layer is formed by applying a water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing to a release paper and performing a heat-drying treatment using a pin tenter or the like. Then, on this moisture permeable layer, the nonporous membrane type moisture permeable waterproofing adhesive composition of the present invention was applied, dried using a pin tenter or the like, and then bonded with a water repellent treated fabric. Heat using a pin tenter. Next, the moisture-permeable and waterproof fabric is obtained by removing the release paper.
また、本発明の透湿防水加工布帛の製造方法によれば、上記の無孔質膜型透湿防水加工用接着剤組成物を塗布し乾燥させた後、撥水処理しない布帛を貼り合わせ、離型紙を剥がした後に撥水処理してもよい。 Further, according to the method for producing a moisture-permeable and waterproof fabric of the present invention, after applying and drying the nonporous membrane-type moisture-permeable and waterproof adhesive composition, a fabric that is not subjected to a water-repellent treatment is bonded, You may perform a water-repellent treatment after peeling off a release paper.
以下に実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
(合成例1…ウレタンプレポリマーの水分散体の調製)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、日本ポリウレタン工業(株)製、Mw=2000、水酸基価=56.1)160.0部、ポリオキシエチレングリコール(第一工業製薬(株)製、Mw=1000、水酸基価=112.2)300.0部、メチルエチルケトン180.0部、3−メチル−1,5−ペンタンジオール4.8部、トリレンジイソシアネート(日本ポリウレタン工業(株)製、TDI−80)70.5部、を添加し、70〜75℃で90分間反応させた(NCO/OH=0.87)。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、メチルエチルケトン124部を添加し、系の温度を40℃とし、このプレポリマーを撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性ポリウレタンプレポリマー水分散体Aを得た(ポリオキシエチレン基含有量56.0重量%)。
Synthesis Example 1 Preparation of Urethane Prepolymer Water Dispersion
160.0 parts of polyester polyol (1,4-butanediol / adipic acid, manufactured by Nippon Polyurethane Industry Co., Ltd., Mw = 2000, hydroxyl value = 56.1), polyoxyethylene glycol (produced by Daiichi Kogyo Seiyaku Co., Ltd.) , Mw = 1000, hydroxyl value = 112.2) 300.0 parts, methyl ethyl ketone 180.0 parts, 3-methyl-1,5-pentanediol 4.8 parts, tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., 70.5 parts of TDI-80) was added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 0.87). At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, 124 parts of methyl ethyl ketone was added, the temperature of the system was 40 ° C., this prepolymer was diluted with diluting water with stirring, methyl ethyl ketone was distilled off, and a nonionic polyurethane prepolymer aqueous dispersion having a pure content of 25% was distilled off. Body A was obtained (polyoxyethylene group content 56.0% by weight).
(合成例2…ウレタンプレポリマーの水分散体の調製)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、豊国製油(株)製、Mw=2500、水酸基価=44.9)219.4部、ポリオキシエチレングリコール(第一工業製薬(株)製、Mw=600、水酸基価=187.03)197.4部、1,4−ブタンジオール4.0部、トリレンジイソシアネート(日本ポリウレタン工業(株)製、TDI−80)77.4部、メチルエチルケトン300部、及びジオクチル錫ジラウレート0.05部を添加し、70〜75℃で90分間反応させた(NCO/OH=0.97)。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーを撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性ポリウレタンプレポリマー水分散体Bを得た(ポリオキシエチレン基を有するポリオール成分39.5重量%含有)。
(Synthesis Example 2 Preparation of Aqueous Dispersion of Urethane Prepolymer)
Polyester polyol (1,4-butanediol / adipic acid, Toyokuni Oil Co., Ltd., Mw = 2500, hydroxyl value = 44.9) 219.4 parts, polyoxyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd.) Mw = 600, hydroxyl value = 187.03) 197.4 parts, 1,4-butanediol 4.0 parts, tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., TDI-80), 77.4 parts, methyl ethyl ketone 300 And 0.05 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 0.97). At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., and this prepolymer was diluted with diluted water under stirring, and methyl ethyl ketone was distilled off to obtain a nonionic polyurethane prepolymer aqueous dispersion B having a pure content of 25% (polyester). (Contains 39.5% by weight of a polyol component having an oxyethylene group).
(合成例3…ウレタンプレポリマーの水分散体の調製)
ポリエステルポリオール(1,6−ヘキサンジオール/アジピン酸、日本ポリウレタン工業(株)製、Mw=1000、水酸基価=112.2)170.0部、ポリオキシエチレンプロピレンランダム共重合グリコール(第一工業製薬(株)製、Mw=3400、水酸基価=33.0、ポリオキシエチレン基含有率78%)289.0部、3−メチル−1,5−ペンタンジオール1.0部、トリレンジイソシアネート(日本ポリウレタン工業(株)製、TDI−80)41.3部、メチルエチルケトン110部、及びジオクチル錫ジラウレート0.02部を添加し、70〜75℃で90分間反応させた(NCO/OH=0.90)。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーに、撹拌下においてハイテノールNF−13(アニオン性界面活性剤、第一工業製薬(株)製)を10.0部添加し、十分に混合した後、引き続き希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性/アニオン性ポリウレタンプレポリマー水分散体Cを得た(ポリオキシエチレン基含有量45.0重量%)。
Synthesis Example 3 Preparation of Aqueous Dispersion of Urethane Prepolymer
170.0 parts of polyester polyol (1,6-hexanediol / adipic acid, manufactured by Nippon Polyurethane Industry Co., Ltd., Mw = 1000, hydroxyl value = 112.2), polyoxyethylene propylene random copolymer glycol (Daiichi Kogyo Seiyaku) Mw = 3400, hydroxyl value = 33.0, polyoxyethylene group content 78%) 289.0 parts, 3-methyl-1,5-pentanediol 1.0 part, tolylene diisocyanate (Japan) 41.3 parts of Polyurethane Industry Co., Ltd., TDI-80), 110 parts of methyl ethyl ketone, and 0.02 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 0.90). ). At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., and 10.0 parts of Hytenol NF-13 (anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to the prepolymer under stirring. After mixing, the mixture was subsequently diluted with dilution water, and methyl ethyl ketone was distilled off to obtain a nonionic / anionic polyurethane prepolymer aqueous dispersion C having a pure content of 25% (polyoxyethylene group content: 45.0% by weight) ).
(合成例4…ウレタンプレポリマーの水分散体の調製)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、日本ポリウレタン工業(株)製、Mw=1000、水酸基価=112.2)132.9部、ポリエステルポリオール(3−メチル−1,5−ペンタジオール/アジピン酸、クラレ(株)製、Mw=1000、水酸基価=112.2)50.0部、ポリオキシエチレングリコール(第一工業製薬(株)製、Mw=600、水酸基価=187.0)60.0部、1,6−ヘキサンジオール10.6部、イソホロンジイソシアネート78.5部、メチルエチルケトン110部、及びジオクチル錫ジラウレート0.2部を添加し、70〜75℃で90分間反応させた(NCO/OH=0.95)。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーに、撹拌下においてハイテノールNF−13(アニオン性界面活性剤、第一工業製薬(株)製)を6.6部添加し、十分混合した後、引き続き撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性/アニオン性ポリウレタンプレポリマー水分散体Dを得た(ポリオキシエチレン基含有量18.0重量%)。
(Synthesis Example 4 ... Preparation of water dispersion of urethane prepolymer)
Polyester polyol (1,4-butanediol / adipic acid, manufactured by Nippon Polyurethane Industry Co., Ltd., Mw = 1000, hydroxyl value = 112.2) 132.9 parts, polyester polyol (3-methyl-1,5-pentadiol / Adipic acid, Kuraray Co., Ltd., Mw = 1000, hydroxyl value = 112.2) 50.0 parts, polyoxyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = 600, hydroxyl value = 187.0) ) 60.0 parts, 10.6-parts of 1,6-hexanediol, 78.5 parts of isophorone diisocyanate, 110 parts of methyl ethyl ketone, and 0.2 part of dioctyltin dilaurate were added and reacted at 70-75 ° C. for 90 minutes. (NCO / OH = 0.95). At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., and 6.6 parts of Hytenol NF-13 (anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to this prepolymer under stirring, and mixed sufficiently Thereafter, the mixture was diluted with diluting water under stirring, and methyl ethyl ketone was distilled off to obtain a nonionic / anionic polyurethane prepolymer aqueous dispersion D having a pure content of 25% (polyoxyethylene group content 18.0). weight%).
(合成例5…ウレタンプレポリマーの水分散体の調製)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、豊国製油(株)製、Mw=2500、水酸基価=44.9)282.5部、ポリエチレングリコール(第一工業製薬(株)製、Mw=600、水酸基価=187.0)67.8部、ポリエチレングリコール(第一工業製薬(株)製、Mw=1000、水酸基価=112.2)113.0部、ヘキサメチレンジイソシアネート38.0部、メチルエチルケトン250部、及びジオクチル錫ジラウレート0.05部を添加し、70〜75℃で90分間反応させた(NCO/OH=0.67)。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーを撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性ポリウレタンプレポリマー水分散体Eを得た(ポリオキシエチレン基を含有するポリオール成分36.1重量%含有)。
(Synthesis Example 5: Preparation of water dispersion of urethane prepolymer)
282.5 parts of polyester polyol (1,4-butanediol / adipic acid, Toyokuni Oil Co., Ltd., Mw = 2500, hydroxyl value = 44.9), polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = 600, hydroxyl value = 187.0) 67.8 parts, polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = 1000, hydroxyl value = 112.2) 113.0 parts, hexamethylene diisocyanate 38.0 parts, 250 parts of methyl ethyl ketone and 0.05 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 0.67). At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., this prepolymer was diluted with diluting water under stirring, and methyl ethyl ketone was distilled off to obtain a nonionic polyurethane prepolymer aqueous dispersion E having a pure content of 25% (polyester). (Contains 36.1% by weight of polyol component containing oxyethylene group).
(合成例6…ウレタンプレポリマー水分散体調製,ポリオキシエチレン12.5重量%)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、日本ポリウレタン工業(株)製、Mw=1000、水酸基価=112.2)182.9部、ポリオキシエチレングリコール(第一工業製薬(株)製、Mw=600、水酸基価=187.0)36.0部、トリレンジイソシアネート57.8部、メチルエチルケトン110部、及びジオクチル錫ジラウレート0.02部を添加し、70〜75℃で90分間反応させた(NCO/OH=0.95)。このときの遊離イソシアネート基含有量(固形分換算)は3.50重量%であった。次に、ジメチロールプロピオン酸12.0部、トリエチルアミン6.3部添加し、60〜65℃で60分間反応させた。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーを撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性/アニオン性ポリウレタンプレポリマー水分散体Fを得た(ポリオキシエチレン基含有量12.5重量%)。
(Synthesis Example 6 ... Preparation of water dispersion of urethane prepolymer, 12.5% by weight of polyoxyethylene)
182.9 parts of polyester polyol (1,4-butanediol / adipic acid, manufactured by Nippon Polyurethane Industry Co., Ltd., Mw = 1000, hydroxyl value = 112.2), polyoxyethylene glycol (produced by Daiichi Kogyo Seiyaku Co., Ltd.) , Mw = 600, hydroxyl value = 187.0) 36.0 parts, tolylene diisocyanate 57.8 parts, methyl ethyl ketone 110 parts, and dioctyltin dilaurate 0.02 parts, and reacted at 70-75 ° C. for 90 minutes. (NCO / OH = 0.95). The free isocyanate group content (in terms of solid content) at this time was 3.50% by weight. Next, 12.0 parts of dimethylolpropionic acid and 6.3 parts of triethylamine were added and reacted at 60 to 65 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., this prepolymer was diluted with diluting water under stirring, and methyl ethyl ketone was distilled off to obtain a nonionic / anionic polyurethane prepolymer aqueous dispersion F having a pure content of 25%. (Polyoxyethylene group content 12.5% by weight).
(比較合成例1…ウレタンプレポリマーの水分散体の調製、NCO/OH=0.6)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、豊国製油(株)製、Mw=2500、水酸基価=44.9)227.3部、ポリオキシエチレングリコール(第一工業製薬(株)製、Mw=600、水酸基価=187.03)204.5部、1,4−ブタンジオール4.1部、トリレンジイソシアネート(日本ポリウレタン工業(株)製、TDI−80)64.1部、メチルエチルケトン300部、及びジオクチル錫ジラウレート0.02部を添加し、70〜75℃で90分間反応させた(NCO/OH=0.60)。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーを撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%の非イオン性ポリウレタンプレポリマー水分散体aを得た(ポリオキシエチレン基を含有するポリオール成分40.9重量%含有)。
(Comparative Synthesis Example 1 Preparation of Aqueous Dispersion of Urethane Prepolymer, NCO / OH = 0.6)
227.3 parts of polyester polyol (1,4-butanediol / adipic acid, Toyokuni Oil Co., Ltd., Mw = 2500, hydroxyl value = 44.9), polyoxyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd.) Mw = 600, hydroxyl value = 187.03) 204.5 parts, 1,4-butanediol 4.1 parts, tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., TDI-80), methyl ethyl ketone 300 Part and 0.02 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 0.60). At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., this prepolymer was diluted with diluting water under stirring, and methyl ethyl ketone was distilled off to obtain a nonionic polyurethane prepolymer aqueous dispersion a having a pure content of 25% (polyester). 40.9% by weight of polyol component containing oxyethylene group).
(比較合成例2…接着層、非イオン成分なし)
ポリエステルポリオール(1,4−ブタンジオール/アジピン酸、日本ポリウレタン工業(株)製、Mw=1000、水酸基価=112.2)182.9部、トリレンジイソシアネート45.1部、メチルエチルケトン110部、及びジオクチル錫ジラウレート0.02部を添加し、70〜75℃で90分間反応させた。このときの遊離イソシアネート基含有量(固形分換算)は3.00重量%であった。次に、ジメチロールプロピオン酸12.0部、トリエチルアミン6.3部添加し、60〜65℃で60分間反応させた。このときの遊離イソシアネート基含有量(固形分換算)は0.10重量%であった。次に、系の温度を40℃とし、このプレポリマーを撹拌下において希釈水で希釈し、メチルエチルケトンを留去し、純分25%のアニオン性ポリウレタンプレポリマー水分散体cを得た(NCO/OH=0.95)。
(Comparative Synthesis Example 2 ... Adhesive layer, no non-ionic component)
182.9 parts of polyester polyol (1,4-butanediol / adipic acid, manufactured by Nippon Polyurethane Industry Co., Ltd., Mw = 1000, hydroxyl value = 112.2), 45.1 parts of tolylene diisocyanate, 110 parts of methyl ethyl ketone, and Dioctyltin dilaurate 0.02 part was added, and it was made to react at 70-75 degreeC for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 3.00% by weight. Next, 12.0 parts of dimethylolpropionic acid and 6.3 parts of triethylamine were added and reacted at 60 to 65 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, the temperature of the system was set to 40 ° C., the prepolymer was diluted with diluted water under stirring, and methyl ethyl ketone was distilled off to obtain an anionic polyurethane prepolymer aqueous dispersion c having a pure content of 25% (NCO / OH = 0.95).
(透湿層用の水系ポリウレタン樹脂組成物の調製)
ポリプロピレングリコール(「PML S−X4001」旭硝子(株)製、Mw=2000、水酸基価=56.1)82.0部、ポリエチレングリコール(第一工業製薬(株)製、Mw=約10000、水酸基価=11.2)56.2部、3−メチル−1,5−ペンタンジオール9.7部、トリメチロールプロパン1.3部、4,4’−ジシクロヘキシルメタンジイソシアネート41.1部、メチルエチルケトン100部、ジオクチル錫ジラウレート0.02部を添加し、70〜75℃で90分間反応させた(NCO/OH=1.03)。このときの遊離イソシアネート基含有量(固形分換算)は1.50重量%であった。次に、メチルエチルケトン60部、ジメチロールプロピオン酸0.8部、トリエチルアミン0.6部を添加し、65〜70℃で1時間反応させた。このときの遊離イソシアネート基含有量(固形分換算)は1.20重量%であった。系を冷却しさらにメチルエチルケトンを50部添加し系の温度を40℃とし、撹拌下において、このプレポリマーにγ−アミノプロピルトリエトキシシラン(信越化学工業(株)製、KBE−903)を4.1部添加した後、水で希釈し、さらにジプロピレントリアミン1.5部を添加し、遊離NCO(重量%)の消失を確認した。その後、メチルエチルケトンを留去し、純分20重量%の水系ポリウレタン樹脂組成物Tを得た(水系ポリウレタン樹脂組成物D中の固形分に対するポリエチレングリコール(Mw=約10000)の含有量34.4重量%(理論値)、アルコシシランの含有量=2.5重量%(理論値)、酸価1.9mgKOH/g)。
(Preparation of water-based polyurethane resin composition for moisture permeable layer)
Polypropylene glycol ("PML S-X4001" manufactured by Asahi Glass Co., Ltd., Mw = 2000, hydroxyl value = 56.1) 82.0 parts, polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = approximately 10,000, hydroxyl value) = 11.2) 56.2 parts, 9.7 parts of 3-methyl-1,5-pentanediol, 1.3 parts of trimethylolpropane, 41.1 parts of 4,4′-dicyclohexylmethane diisocyanate, 100 parts of methyl ethyl ketone, Dioctyltin dilaurate 0.02 part was added, and it was made to react for 90 minutes at 70-75 degreeC (NCO / OH = 1.03). At this time, the free isocyanate group content (in terms of solid content) was 1.50% by weight. Next, 60 parts of methyl ethyl ketone, 0.8 part of dimethylolpropionic acid and 0.6 part of triethylamine were added and reacted at 65 to 70 ° C. for 1 hour. At this time, the content of free isocyanate groups (in terms of solid content) was 1.20% by weight. The system was cooled and 50 parts of methyl ethyl ketone was added to bring the temperature of the system to 40 ° C. Under stirring, γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this prepolymer. After adding 1 part, it diluted with water, and also 1.5 parts of dipropylene triamines were added, and the loss | disappearance of free NCO (weight%) was confirmed. Thereafter, methyl ethyl ketone was distilled off to obtain an aqueous polyurethane resin composition T having a pure content of 20% by weight (the content of polyethylene glycol (Mw = about 10,000) with respect to the solid content in the aqueous polyurethane resin composition D was 34.4%. % (Theoretical value), content of alkoxysilane = 2.5% by weight (theoretical value), acid value 1.9 mgKOH / g).
(接着剤の調製…実施例1〜7、比較例1〜6)
表1及び表2に示す配合で、各実施例及び各比較例の接着剤を調製した。
(Preparation of adhesives ... Examples 1-7, Comparative Examples 1-6)
With the formulations shown in Tables 1 and 2, adhesives of each Example and each Comparative Example were prepared.
<ドライラミネート法による透湿防水布帛の作成>
(透湿フィルムの作成)
上記で得られた透湿層用の水系ポリウレタン樹脂組成物Tを離型紙上に、乾燥膜厚が15μmになるように塗布した。続けて80℃×3分間で乾燥処理後、さらに150℃×3分熱処理し、透湿層を得た。
<Creation of moisture permeable waterproof fabric by dry lamination method>
(Creating a moisture permeable film)
The water-based polyurethane resin composition T for a moisture permeable layer obtained above was applied on a release paper so that the dry film thickness was 15 μm. Subsequently, after drying at 80 ° C. for 3 minutes, heat treatment was further performed at 150 ° C. for 3 minutes to obtain a moisture permeable layer.
(透湿防水布帛の作成)
透湿層の上に、各実施例及び各比較例の接着剤を塗布厚80μm(Wet)で塗布した。続いて乾燥処理70℃×2分を行った後、撥水処理したポリエステル繊維布帛(タフタ)を貼り付け、圧力0.20MPa、温度120℃×10秒の処理を実施し、さらに70℃×24時間熟成した。次に、離型紙を剥がして各実施例及び各比較例の透湿防水布帛を得た。
(Creation of moisture permeable waterproof fabric)
On the moisture permeable layer, the adhesives of each Example and each Comparative Example were applied at a coating thickness of 80 μm (Wet). Subsequently, after drying treatment at 70 ° C. for 2 minutes, a water-repellent polyester fiber fabric (taffeta) was attached, treatment at a pressure of 0.20 MPa and a temperature of 120 ° C. for 10 seconds was performed, and further 70 ° C. × 24 Aged for hours. Next, the release paper was peeled off to obtain moisture permeable and waterproof fabrics of Examples and Comparative Examples.
(性能試験)
接着剤のポットライフ、並びに透湿防水布帛の剥離強度、剥離部分の性状、加工布風合い、透湿性、耐水圧及び耐洗濯性について調べた。その結果を表3及び表4に示す。各性能試験方法及び評価基準は、以下のとおりである。
(performance test)
The pot life of the adhesive, the peel strength of the moisture permeable waterproof fabric, the properties of the peeled portion, the texture of the processed cloth, the moisture permeability, the water pressure resistance and the wash resistance were examined. The results are shown in Tables 3 and 4. Each performance test method and evaluation criteria are as follows.
<接着剤のポットライフ>
各接着剤を35℃×8時間放置した後の状態を肉眼観察した。
<Adhesive pot life>
The state after each adhesive was left at 35 ° C. for 8 hours was visually observed.
<剥離強度>
2.5cm幅のホットメルトテープを試料表面(表皮面)においてアイロンで加熱し、ホットメルトテープを接着した。このテープ幅に沿って試料を切断し、試料の一部を剥離し、基材とテープをチャックではさみ、オートグラフで剥離強度を測定した。
<Peel strength>
A hot melt tape having a width of 2.5 cm was heated with an iron on the sample surface (skin surface), and the hot melt tape was bonded. The sample was cut along this tape width, a part of the sample was peeled off, the substrate and the tape were sandwiched with a chuck, and the peel strength was measured by an autograph.
<剥離部分の性状>
剥離強度試験後の剥離部分を目視で観察した。
<Properties of peeling part>
The peeled portion after the peel strength test was visually observed.
<加工布風合い>
加工布の風合いを触感により評価した。評価基準は、以下のとおりである。
<Fabric texture>
The texture of the work cloth was evaluated by tactile sensation. The evaluation criteria are as follows.
○:柔らかい
△:やや硬さがある
×:硬い。
○: Soft Δ: Somewhat hard ×: Hard
<透湿性>
透湿性試験は、JIS L−1099 4.1.1B−1(酢酸カリウム法)に準じて行った。
<Moisture permeability>
The moisture permeability test was performed according to JIS L-1099 4.1.1B-1 (potassium acetate method).
<耐水圧>
耐水圧試験は、JIS L−1092 B法(高水圧法)に準じて測定を実施した。
<Water pressure resistance>
The water pressure test was measured according to JIS L-1092 B method (high water pressure method).
<耐洗濯性>
JIS L 0217の103法に準じて、洗濯前と洗濯10回後の透湿性及び耐水圧を測定した。
<Washing resistance>
According to method 103 of JIS L 0217, moisture permeability and water pressure resistance before and after washing 10 times were measured.
本発明の無孔質膜型透湿防水加工用接着剤組成物及び透湿防水加工布帛の製造方法によれば、透湿性、耐水性、耐洗濯性に優れ、加工風合いにも優れた透湿防水加工布帛が得られるので、繊維加工の分野で利用可能である。
According to the non-porous membrane-type moisture-permeable waterproof fabric adhesive composition and the method for producing a moisture-permeable waterproof fabric of the present invention, the moisture permeability is excellent in moisture permeability, water resistance and washing resistance, and in the processing texture. Since a waterproof fabric can be obtained, it can be used in the field of fiber processing.
Claims (6)
(B成分)4個以上のオキシエチレン単位からなるポリオキシエチレン基を含有するとともにNCO基と反応性のある活性水素を少なくとも2個以上含有する第1のポリオール成分と、
(C成分)NCO基と反応性のある活性水素を少なくとも2個以上含有する第2のポリオール成分と
を構成成分として、NCO/OH比(モル比)=0.65〜0.99の範囲になるように反応させて得られた(P)末端水酸基を有するポリウレタンプレポリマーの水分散体に対して、更に、
(D成分)水分散型ポリイソシアネート系架橋剤
を配合して得られる無孔質膜型透湿防水加工用接着剤組成物。 (Component A) an organic polyisocyanate component;
(Component B) a first polyol component containing a polyoxyethylene group composed of four or more oxyethylene units and containing at least two active hydrogens reactive with NCO groups;
(Component C) NCO / OH ratio (molar ratio) = 0.65 to 0.99, with the second polyol component containing at least two active hydrogens reactive with NCO groups For the aqueous dispersion of the polyurethane prepolymer having a (P) terminal hydroxyl group obtained by the reaction as described above,
(D component) A nonporous membrane-type moisture-permeable and waterproof adhesive composition obtained by blending a water-dispersed polyisocyanate-based crosslinking agent.
A coating liquid containing a water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproofing is applied to a release paper, dried to obtain a moisture-permeable layer, and the moisture-permeable layer is formed on the moisture-permeable layer. A method for producing a moisture-permeable and waterproof fabric, which is subjected to a water-repellent treatment after applying an adhesive containing a water-based adhesive composition of ~ 4, drying and bonding a synthetic fiber fabric.
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Cited By (5)
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JP2009242675A (en) * | 2008-03-31 | 2009-10-22 | Komatsu Seiren Co Ltd | Adhesive for moisture permeable water proofing cloth |
JP2015078353A (en) * | 2013-09-13 | 2015-04-23 | 三洋化成工業株式会社 | Adhesive for moisture-permeable waterproof material |
KR20180072796A (en) | 2015-12-16 | 2018-06-29 | 디아이씨 가부시끼가이샤 | A moisture-curing urethane hot-melt resin composition, and a laminate |
CN111690360A (en) * | 2020-06-22 | 2020-09-22 | 万华化学(北京)有限公司 | Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof |
CN114258442A (en) * | 2019-09-20 | 2022-03-29 | Dic株式会社 | Moisture-permeable waterproof fabric |
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JPH0214078A (en) * | 1989-05-25 | 1990-01-18 | Teijin Ltd | Production of heat insulating moisture-permeable and waterproof fabric |
JP2003336028A (en) * | 2002-05-21 | 2003-11-28 | Dainippon Ink & Chem Inc | Aqueous dry laminate adhesive composition for synthetic leather and method for manufacturing synthetic leather using the same |
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JPH01124687A (en) * | 1988-10-21 | 1989-05-17 | Teijin Ltd | Production of humidity permeable waterproof fabric |
JPH0214078A (en) * | 1989-05-25 | 1990-01-18 | Teijin Ltd | Production of heat insulating moisture-permeable and waterproof fabric |
JP2003336028A (en) * | 2002-05-21 | 2003-11-28 | Dainippon Ink & Chem Inc | Aqueous dry laminate adhesive composition for synthetic leather and method for manufacturing synthetic leather using the same |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009242675A (en) * | 2008-03-31 | 2009-10-22 | Komatsu Seiren Co Ltd | Adhesive for moisture permeable water proofing cloth |
JP2015078353A (en) * | 2013-09-13 | 2015-04-23 | 三洋化成工業株式会社 | Adhesive for moisture-permeable waterproof material |
KR20180072796A (en) | 2015-12-16 | 2018-06-29 | 디아이씨 가부시끼가이샤 | A moisture-curing urethane hot-melt resin composition, and a laminate |
CN114258442A (en) * | 2019-09-20 | 2022-03-29 | Dic株式会社 | Moisture-permeable waterproof fabric |
CN114258442B (en) * | 2019-09-20 | 2023-09-15 | Dic株式会社 | Moisture-permeable waterproof fabric |
CN111690360A (en) * | 2020-06-22 | 2020-09-22 | 万华化学(北京)有限公司 | Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof |
CN111690360B (en) * | 2020-06-22 | 2023-03-03 | 万华化学(北京)有限公司 | Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof |
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