JP6528915B1 - Urethane resin composition, film, and synthetic leather - Google Patents
Urethane resin composition, film, and synthetic leather Download PDFInfo
- Publication number
- JP6528915B1 JP6528915B1 JP2018558260A JP2018558260A JP6528915B1 JP 6528915 B1 JP6528915 B1 JP 6528915B1 JP 2018558260 A JP2018558260 A JP 2018558260A JP 2018558260 A JP2018558260 A JP 2018558260A JP 6528915 B1 JP6528915 B1 JP 6528915B1
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- Japan
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- mass
- parts
- urethane resin
- resin composition
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 47
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 239000002649 leather substitute Substances 0.000 title claims abstract description 18
- 239000010408 film Substances 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920005862 polyol Polymers 0.000 claims abstract description 47
- 150000003077 polyols Chemical class 0.000 claims abstract description 47
- 239000004417 polycarbonate Substances 0.000 claims abstract description 30
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 29
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 glycol compound Chemical group 0.000 claims abstract description 25
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 6
- 125000003003 spiro group Chemical group 0.000 claims abstract description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009864 tensile test Methods 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 24
- 239000005642 Oleic acid Substances 0.000 abstract description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 24
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 16
- 230000018044 dehydration Effects 0.000 description 16
- 238000006297 dehydration reaction Methods 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 229920005749 polyurethane resin Polymers 0.000 description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 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 7
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 150000002334 glycols Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- 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
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002335 surface treatment layer Substances 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- JFRQLKNEDLLXOQ-UHFFFAOYSA-N 1,3-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC=C(N=C=O)C(C)=C1N=C=O JFRQLKNEDLLXOQ-UHFFFAOYSA-N 0.000 description 1
- BQHPNDYUVBBCQF-UHFFFAOYSA-N 1,3-diisocyanato-5-methylbenzene Chemical compound CC1=CC(N=C=O)=CC(N=C=O)=C1 BQHPNDYUVBBCQF-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- XCYAYYRYTNCXQL-UHFFFAOYSA-N 1,4-diisocyanato-2,5-dimethylbenzene Chemical compound CC1=CC(N=C=O)=C(C)C=C1N=C=O XCYAYYRYTNCXQL-UHFFFAOYSA-N 0.000 description 1
- DKBHJZFJCDOGOY-UHFFFAOYSA-N 1,4-diisocyanato-2-methylbenzene Chemical compound CC1=CC(N=C=O)=CC=C1N=C=O DKBHJZFJCDOGOY-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- PEXHKGHSBFTDNM-UHFFFAOYSA-N 1-[3-(2-hydroxypropyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]propan-2-ol Chemical compound C1OC(CC(O)C)OCC21COC(CC(C)O)OC2 PEXHKGHSBFTDNM-UHFFFAOYSA-N 0.000 description 1
- FHGPADAQQRYSEH-UHFFFAOYSA-N 1-ethyl-2,4-diisocyanatobenzene Chemical compound CCC1=CC=C(N=C=O)C=C1N=C=O FHGPADAQQRYSEH-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VXQILLTWRZPRQF-UHFFFAOYSA-N 2,4-diisocyanato-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1N=C=O VXQILLTWRZPRQF-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- MCKAQHVVZBTPFO-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylbutan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylbutan-1-ol Chemical compound C1OC(C(C)(CO)CC)OCC21COC(C(C)(CC)CO)OC2 MCKAQHVVZBTPFO-UHFFFAOYSA-N 0.000 description 1
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 1
- FVHGFTBRFNRRBN-UHFFFAOYSA-N 2-[3-(1-hydroxybutan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]butan-1-ol Chemical compound C1OC(C(CO)CC)OCC21COC(C(CC)CO)OC2 FVHGFTBRFNRRBN-UHFFFAOYSA-N 0.000 description 1
- VKQPHJLIVKHAQA-UHFFFAOYSA-N 2-[3-(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]ethanol Chemical compound C1OC(CCO)OCC21COC(CCO)OC2 VKQPHJLIVKHAQA-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- ZOSYCXNYZHSSGZ-UHFFFAOYSA-N 3-[3-(2-hydroxypentan-3-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]pentan-2-ol Chemical compound C1OC(C(C(C)O)CC)OCC21COC(C(CC)C(C)O)OC2 ZOSYCXNYZHSSGZ-UHFFFAOYSA-N 0.000 description 1
- KEHWNDPDEHPHEQ-UHFFFAOYSA-N 3-[3-(3-hydroxybutan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]butan-2-ol Chemical compound C1OC(C(C)C(O)C)OCC21COC(C(C)C(C)O)OC2 KEHWNDPDEHPHEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- TXZNWLHNUIBVAI-UHFFFAOYSA-N C1OC(C(CO)C)OCC21COC(C(C)CO)OC2 Chemical compound C1OC(C(CO)C)OCC21COC(C(C)CO)OC2 TXZNWLHNUIBVAI-UHFFFAOYSA-N 0.000 description 1
- VKIGKZXZHLNIAG-UHFFFAOYSA-N CCC1=CC(CC)=CC(C)=C1.CC(C)C1=C(C(C)C)C=CC=C1.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CCC1=CC(CC)=CC(C)=C1.CC(C)C1=C(C(C)C)C=CC=C1.N=C=O.N=C=O.N=C=O.N=C=O VKIGKZXZHLNIAG-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 229920000297 Rayon Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- QCIYAEYRVFUFAP-UHFFFAOYSA-N hexane-2,3-diol Chemical compound CCCC(O)C(C)O QCIYAEYRVFUFAP-UHFFFAOYSA-N 0.000 description 1
- TXGJTWACJNYNOJ-UHFFFAOYSA-N hexane-2,4-diol Chemical compound CCC(O)CC(C)O TXGJTWACJNYNOJ-UHFFFAOYSA-N 0.000 description 1
- POFSNPPXJUQANW-UHFFFAOYSA-N hexane-3,4-diol Chemical compound CCC(O)C(O)CC POFSNPPXJUQANW-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
本発明が解決しようとする課題は、耐オレイン酸性、低温屈曲性、及び機械的強度に優れるウレタン樹脂組成物を提供することである。本発明は、ブタンジオール及びヘキサンジオールを原料とするポリカーボネートポリオール（Ａ）と、単環脂肪族グリコール（ｂ−１）、スピロ環を有するグリコール（ｂ−２）、及び、芳香族グリコール（ｂ−３）からなる群より選ばれる１種以上のグリコール化合物（Ｂ）とを含むポリオール（Ｘ）、及び、ポリイソシアネート（Ｙ）を必須原料としたウレタン樹脂（Ｚ）を含有することを特徴とするウレタン樹脂組成物を提供するものである。また、本発明は、前記ウレタン樹脂組成物により形成されたことを特徴とする皮膜、及び、その皮膜を有することを特徴とする合成皮革を提供することである。The problem to be solved by the present invention is to provide a urethane resin composition excellent in oleic acid resistance, low temperature flexibility, and mechanical strength. The present invention provides a polycarbonate polyol (A) using butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-) 3) A polyol (X) containing at least one glycol compound (B) selected from the group consisting of 3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is intended to provide a urethane resin composition. Another object of the present invention is to provide a film formed of the above urethane resin composition, and a synthetic leather characterized by having the film.
Description
本発明は、ウレタン樹脂組成物に関する。 The present invention relates to a urethane resin composition.
ウレタン樹脂は、合成皮革、成型加工用シート等様々な分野で広く利用されている。が、特に、車輛内装材用の合成皮革等長期間使用される部材に使用される場合においては、より高い耐久性が要求される。 Urethane resin is widely used in various fields such as synthetic leather and sheets for molding processing. However, higher durability is required particularly when used for long-term members such as synthetic leather for vehicle interior materials.
前記耐久性の評価項目は多岐に渡っており、耐熱性、耐湿熱性、耐光性、耐薬品性、耐摩耗性等が挙げられるが、特に、近年では、人体と頻繁に接触する合成皮革部材には耐オレイン酸性や耐サンオイル性などの耐薬品性が求められている。前記耐オレイン酸性等に優れる材料としては、例えば、ポリカーボネート系ポリウレタン樹脂、ポリエーテル系ポリウレタン樹脂、及びアクリル樹脂からなる樹脂組成物が開示されている（例えば、特許文献１を参照。）。 The above-mentioned evaluation items of durability are various and include heat resistance, moist heat resistance, light resistance, chemical resistance, abrasion resistance and the like, and in particular, in recent years, synthetic leather members frequently in contact with the human body. Are required to have chemical resistance such as oleic acid resistance and sun oil resistance. As a material excellent in oleic acid resistance and the like, for example, a resin composition comprising a polycarbonate-based polyurethane resin, a polyether-based polyurethane resin, and an acrylic resin is disclosed (see, for example, Patent Document 1).
しかしながら、合成皮革用の材料としては、前記耐オレイン酸性等だけでなく、寒冷地域での使用を想定し低温での屈曲性の要求レベルも上がっており、更に、優れた耐摩耗性を得るための優れた機械的強度も必要となってきている。しかしながら、これらの特性を全て兼ね備える材料は未だ見出されていない。 However, as a material for synthetic leather, not only the above-mentioned oleic acid resistance, etc., but also the demand level of flexibility at low temperature is increased assuming use in cold regions, and furthermore, excellent abrasion resistance is obtained The excellent mechanical strength of is also needed. However, no material has yet been found that combines all of these properties.
本発明が解決しようとする課題は、耐オレイン酸性、低温屈曲性、及び機械的強度に優れるウレタン樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a urethane resin composition excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.
本発明は、ブタンジオール及びヘキサンジオールを原料とするポリカーボネートポリオール（Ａ）と、単環脂肪族グリコール（ｂ−１）、スピロ環を有するグリコール（ｂ−２）、及び、芳香族グリコール（ｂ−３）からなる群より選ばれる１種以上のグリコール化合物（Ｂ）とを含むポリオール（Ｘ）、及び、ポリイソシアネート（Ｙ）を必須原料としたウレタン樹脂（Ｚ）を含有することを特徴とするウレタン樹脂組成物を提供するものである。 The present invention provides a polycarbonate polyol (A) using butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-) 3) A polyol (X) containing at least one glycol compound (B) selected from the group consisting of 3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is intended to provide a urethane resin composition.
また、本発明は、前記ウレタン樹脂組成物により形成されたことを特徴とする皮膜、及び、その皮膜を有することを特徴とする合成皮革を提供することである。 Another object of the present invention is to provide a film formed of the above urethane resin composition, and a synthetic leather characterized by having the film.
本発明のウレタン樹脂組成物は、耐オレイン酸性、低温屈曲性、及び機械的強度に優れるものである。 The urethane resin composition of the present invention is excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.
よって、本発明のウレタン樹脂組成物は、合成皮革、衣料、支持パッド、研磨パッド等の製造に使用される材料として好適に使用することができ、合成皮革の材料として特に好適に使用することができる。 Therefore, the urethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, support pads, polishing pads and the like, and particularly preferably used as a material of synthetic leather it can.
本発明のウレタン樹脂組成物は、ブタンジオール及びヘキサンジオールを原料とするポリカーボネートポリオール（Ａ）と、単環脂肪族グリコール（ｂ−１）、スピロ環を有するグリコール（ｂ−２）、及び、芳香族グリコール（ｂ−３）からなる群より選ばれる１種以上のグリコール化合物（Ｂ）とを含むポリオール（Ｘ）、及び、ポリイソシアネート（Ｙ）を必須原料としたウレタン樹脂（Ｚ）を含有するものである。 The urethane resin composition of the present invention comprises a polycarbonate polyol (A) having butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aroma A polyol (X) containing at least one glycol compound (B) selected from the group consisting of group glycols (b-3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is a thing.
前記ポリカーボネートポリオール（Ａ）は、優れた耐オレイン酸性と低温屈曲性とを維持しながら、非常に優れた機械的強度を得るうえで、ブタンジオール及びヘキサンジオールを原料とすることが必須である。 In order to obtain very excellent mechanical strength while maintaining excellent oleic acid resistance and low temperature flexibility, the polycarbonate polyol (A) is essential to use butanediol and hexanediol as raw materials.
前記ブタンジオールとしては、例えば、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール等を用いることができる。これらのブタンジオールは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた機械的強度が得られる点から、１，４−ブタンジオールを用いることが好ましい。 As the butanediol, for example, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and the like can be used. These butanediols may be used alone or in combination of two or more. Among these, it is preferable to use 1,4-butanediol from the viewpoint of obtaining further excellent mechanical strength.
前記ヘキサンジオールとしては、例えば、１，２−ヘキサンジオール、１，３−ヘキサンジオール、１，４−ヘキサンジオール、１，５−ヘキサンジオール、１，６−ヘキサンジオール、２，３−ヘキサンジオール、２，４−ヘキサンジオール、３，４−ヘキサンジオール等を用いることができる。これらのヘキサンジオールは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた機械的強度が得られる点から、１，６−ヘキサンジオールを用いることが好ましい。 Examples of the hexanediol include 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, and 2,3-hexanediol. 2,4-hexanediol, 3,4-hexanediol, etc. can be used. These hexanediols may be used alone or in combination of two or more. Among these, it is preferable to use 1,6-hexanediol from the viewpoint that much higher mechanical strength is obtained.
前記ブタンジオール（Ｃ４）及びヘキサンジオールジオール（Ｃ６）のモル比［Ｃ４／Ｃ６］としては、より一層優れた機械的強度が得られる点から、６０／４０〜９５／５の範囲であることが好ましく、６５／３５〜９３／７の範囲であることが好ましい。 The molar ratio [C4 / C6] of the butanediol (C4) and the hexanediol diol (C6) is in the range of 60/40 to 95/5 from the viewpoint of obtaining even more excellent mechanical strength. It is preferably in the range of 65/35 to 93/7.
前記ポリカーボネートジオール（Ａ）は、具体的には、前記ブタンジオール及びヘキサンジオールと、炭酸エステル及び／又はホスゲンとを公知の方法により反応させたものを用いることができる。 As the polycarbonate diol (A), specifically, one obtained by reacting the butanediol and hexanediol with a carbonate and / or phosgene according to a known method can be used.
前記炭酸エステルとしては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、プロピレンカーボネート等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 As said carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate etc. can be used, for example. These compounds may be used alone or in combination of two or more.
前記ポリカーボネートジオール（Ａ）の数平均分子量としては、より一層優れた機械的強度が得られる点から、１，５００〜３，５００の範囲であることが好ましい。なお、前記ポリカーボネートポリオール（Ａ）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the polycarbonate diol (A) is preferably in the range of 1,500 to 3,500, from the viewpoint of obtaining even more excellent mechanical strength. The number average molecular weight of the polycarbonate polyol (A) is a value measured by gel permeation chromatography (GPC).
前記ポリカーボネートポリオール（Ａ）の使用量としては、より一層優れた耐オレイン酸性、低温屈曲性、及び機械的強度が得られる点から、ポリオール（Ｘ）中３０質量％以上であることが好ましく、４０〜９９質量％の範囲がより好ましく、５０〜９５質量％の範囲が更に好ましい。 The amount of the polycarbonate polyol (A) used is preferably 30% by mass or more in the polyol (X), from the viewpoint of obtaining even more excellent oleic acid resistance, low temperature flexibility and mechanical strength. The range of -99 mass% is more preferable, and the range of 50-95 mass% is further preferable.
本発明で用いるポリオール（Ｘ）としては、単環脂肪族グリコール（ｂ−１）、スピロ環を有するグリコール（ｂ−２）、及び、芳香族グリコール（ｂ−３）からなる群より選ばれる１種以上のグリコール化合物（Ｂ）を用いることが必須である。この特定のグリコール化合物（Ｂ）を前記ポリカーボネートポリオール（Ｂ）と併用することによって、トレードオフの関係にある耐オレイン酸性、低温屈曲性、及び機械的強度の優れた両立を図ることができる。 The polyol (X) used in the present invention is selected from the group consisting of a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-3) It is essential to use a glycol compound (B) of a kind or more. By using this specific glycol compound (B) in combination with the polycarbonate polyol (B), it is possible to achieve excellent compatibility between oleic acid resistance, low temperature flexibility and mechanical strength which are in a trade-off relationship.
前記単環脂肪族グリコール（ｂ−１）としては、例えば、シクロペンタンジオール、シクロヘキサンジオール、シクロヘキサンジメタノール、水素化ビスフェノールＡ；これらのアルキレンオキサイド付加物等を用いることができる。これらのグリコールは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れ耐オレイン酸性、低温屈曲性、及び機械的強度が得られる点から、シクロヘキサンジメタノール、水素化ビスフェノールＡ、及び、水素化ビスフェノールＡのアルキレンオキサイド付加物からなる群より選ばれる１種以上のグリコールを用いることが好ましい。 As the monocyclic aliphatic glycol (b-1), for example, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and alkylene oxide adducts of these, etc. can be used. These glycols may be used alone or in combination of two or more. Among these, cyclohexane dimethanol, hydrogenated bisphenol A, and an alkylene oxide adduct of hydrogenated bisphenol A are selected from the viewpoint that oleic acid resistance, low temperature flexibility and mechanical strength can be further improved. Preferably, one or more glycols are used.
前記スピロ環を有するグリコール（ｂ−２）としては、例えば、３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１−メチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１−エチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１−エチル−１−メチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（２−ヒドロキシエチル−２−メチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１−メチル−２−ヒドロキシ−２−メチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１−エチル−２−ヒドロキシ−２−メチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１，１−ジメチル−２−ヒドロキシ−２−メチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（１−エチル−１−メチル−２−ヒドロキシ−２−メチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、３，９−ビス（２−ヒドロキシプロピル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン等を用いることができる。これらのグリコールは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた耐オレイン酸性、低温屈曲性、及び機械的強度が得られる点から、３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンを用いることが好ましい。 As the glycol (b-2) having a spiro ring, for example, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] Undecane, 3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-methyl-2-hydroxyethyl) -2, 4,8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-1-methyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-hydroxyethyl-2) -Methyl) -2,4,8, 0-tetraoxaspiro [5,5] undecane, 3,9-bis (1-methyl-2-hydroxy-2-methylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-2-hydroxy-2-methylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1,1-dimethyl-) 2-hydroxy-2-methylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-1-methyl-2-hydroxy-2-methylethyl) ) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-hydroxypropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Can be used. These glycols may be used alone or in combination of two or more. Among these, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8, from the viewpoint that oleic acid resistance, low temperature flexibility and mechanical strength can be further improved. It is preferred to use 10-tetraoxaspiro [5,5] undecane.
前記芳香族グリコールとしては、例えば、ビスフェノールＡ、４，４’−ジヒドロキシジフェニル、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルスルホン、ヒドロキノン；これらのアルキレンオキサイド付加物等を用いることができる。これらのグリコールは単独で用いても２種以上を併用してもよい。 As the aromatic glycol, for example, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydroquinone, and alkylene oxide adducts thereof may be used. it can. These glycols may be used alone or in combination of two or more.
前記グリコール化合物（Ｂ）の含有率としては、より一層優れた耐オレイン酸性、低温屈曲性、及び機械的強度が得られる点から、ポリオール（Ｘ）中１０質量％未満であることが好ましく、１〜９質量％の範囲がより好ましく、２〜７質量％の範囲が更に好ましい。 The content of the glycol compound (B) is preferably less than 10% by mass in the polyol (X) from the viewpoint of obtaining even more excellent oleic acid resistance, low temperature flexibility and mechanical strength. The range of -9% by mass is more preferable, and the range of 2 to 7% by mass is more preferable.
前記ポリオール（Ｘ）は、前記ポリカーボネートポリオール（Ａ）、及び、前記グリコール化合物（Ｂ）を必須成分として含有するが、必要に応じて、その他ポリオールを更に含有してもよい。 Although the said polyol (X) contains the said polycarbonate polyol (A) and the said glycol compound (B) as an essential component, you may further contain other polyols as needed.
前記その他のポリオールとしては、例えば、前記（Ａ）以外のポリカーボネートポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリアクリルポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。これらの中でも、前記ポリカーボネートポリオール（Ａ）と併用することにより、より一層優れた耐オレイン酸性、低温屈曲性、及び機械的強度が得られる点から、前記（Ａ）以外のポリカーボネートポリオールを用いることが好ましい。 As said other polyol, polycarbonate polyol other than said (A), polyether polyol, polyester polyol, polyacryl polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol etc. can be used, for example. These polyols may be used alone or in combination of two or more. Among them, polycarbonate polyols other than the above (A) can be used from the viewpoint that even more excellent oleic acid resistance, low temperature flexibility and mechanical strength can be obtained by using in combination with the polycarbonate polyol (A). preferable.
前記（Ａ）以外のポリカーボネートポリオールとしては、カーボネート構造をもっていれば特に制限はないが、例えば、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキサンジオール、デカンジオール、カプロラクトン、シクロヘキサンジメタノール、３−メチル−１，５−ペンタンジオール、ネオペンチルグリコール、イソソルビド等を原料とするポリカーボネートポリオール等を用いることができる。これらの原料は、水酸基を有する原料として単独で用いても２種以上を併用してもよい。 The polycarbonate polyols other than the above (A) are not particularly limited as long as they have a carbonate structure, but, for example, propanediol, butanediol, pentanediol, hexanediol, decanediol, caprolactone, cyclohexanedimethanol, 3-methyl-1 A polycarbonate polyol etc. which use 5-pentanediol, neopentyl glycol, isosorbide etc. as a raw material can be used. These raw materials may be used singly as a raw material having a hydroxyl group or in combination of two or more.
前記（Ａ）以外のポリカーボネートポリオールを用いる場合の使用量としては、より一層優れた耐オレイン酸性、低温屈曲性、及び機械的強度が得られる点から、ポリオール（Ｘ）中４０質量％未満であることが好ましく、１〜３５質量％の範囲がより好ましく、３〜３３質量％の範囲が更に好ましい。 The amount used when using polycarbonate polyols other than the above (A) is less than 40% by mass in the polyol (X) from the viewpoint of obtaining more excellent oleic acid resistance, low temperature flexibility and mechanical strength. The range of 1 to 35% by mass is more preferable, and the range of 3 to 33% by mass is further preferable.
前記ポリオール（Ｘ）には、必要に応じて、その他の鎖伸長剤（数平均分子量が４０〜５５０のもの。）を併用してもよい。 If necessary, other chain extenders (having a number average molecular weight of 40 to 550) may be used in combination with the polyol (X).
前記その他鎖伸長剤としては、例えば、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、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ヘキサメチレングリコール、トリメチロールプロパン、グリセリン等の水酸基を有する鎖伸長剤；エチレンジアミン、１，２−プロパンジアミン、１，６−ヘキサメチレンジアミン、ピペラジン、２−メチルピペラジン、２，５−ジメチルピペラジン、イソホロンジアミン、４，４’−ジシクロヘキシルメタンジアミン、３，３’−ジメチル−４，４’−ジシクロヘキシルメタンジアミン、１，２−シクロヘキサンジアミン、１，４−シクロヘキサンジアミン、アミノエチルエタノールアミン、ヒドラジン、ジエチレントリアミン、トリエチレンテトラミン等のアミノ基を有する鎖伸長剤を用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。これらの中でも、皮膜の継時的な変色を抑制しやすい点から、アミノ基を有する鎖伸長剤を用いることが好ましく、アミノ基及び脂環構造を有する鎖伸長剤を用いることがより好ましい。 Examples of the other chain extender include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and trimethylolpropane. , A chain extender having a hydroxyl group such as glycerol; ethylene diamine, 1,2-propane diamine, 1,6-hexamethylene diamine, piperazine, 2-methyl piperazine, 2,5-dimethyl piperazine, isophorone diamine, 4,4'- Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethyl ethanolamine, hydrazine, diethylene oxide Amines, can be used a chain extender having an amino group such as triethylene tetramine. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having an amino group, and it is more preferable to use a chain extender having an amino group and an alicyclic structure, from the viewpoint of easily suppressing the discoloration of the film over time.
前記その他の鎖伸長剤を用いる場合の使用量としては、皮膜の継時的な変色を抑制しやすい点から、前記ポリオール（Ｘ）１００質量部に対して、１〜５０質量部の範囲が好ましく、３〜２０質量部の範囲がより好ましい。 The amount of use of the other chain extender is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the polyol (X) from the viewpoint of easily suppressing the successive color change of the film. The range of 3 to 20 parts by mass is more preferable.
ポリイソシアネート（Ｙ）としては、例えば、１，３−及び１，４−フェニレンジイソシアネート、１−メチル−２，４−フェニレンジイソシアネート、１−メチル−２，６−フェニレンジイソシアネート、１−メチル−２，５−フェニレンジイソシアネート、１−メチル−２，６−フェニレンジイソシアネート、１−メチル−３，５−フェニレンジイソシアネート、１−エチル−２，４−フェニレンジイソシアネート、１−イソプロピル−２，４−フェニレンジイソシアネート、１，３−ジメチル−２，４−フェニレンジイソシアネート、１，３−ジメチル−４，６−フェニレンジイソシアネート、１，４−ジメチル−２，５−フェニレンジイソシアネート、ジエチルベンゼンジイソシアネート、ジイソプロピルベンゼンジイソシアネート、１−メチル−３，５−ジエチルベンゼンジイソシアネート、３−メチル−１，５−ジエチルベンゼン−２，４−ジイソシアネート、１，３，５−トリエチルベンゼン−２，４−ジイソシアネート、ナフタレン−１，４−ジイソシアネート、ナフタレン−１，５−ジイソシアネート、１−メチル−ナフタレン−１，５−ジイソシアネート、ナフタレン−２，６−ジイソシアネート、ナフタレン−２，７−ジイソシアネート、１，１−ジナフチル−２，２’−ジイソシアネート、ビフェニル−２，４’−ジイソシアネート、ビフェニル−４，４’−ジイソシアネート、３−３’−ジメチルビフェニル−４，４’−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、２，２’−ジフェニルメタンジイソシアネート、ジフェニルメタン−２，４−ジイソシアネート等の芳香族ポリイソシアネート；テトラメチレンジイソシアネート、１，５−ペンタメチレンジイソシアネート、１，６−ヘキサメチレンジイソシアネート、ドデカメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、１，３−シクロペンチレンジイソシアネート、１，３−シクロヘキシレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、１，３−ジ（イソシアネートメチル）シクロヘキサン、１，４−ジ（イソシアネートメチル）シクロヘキサン、リジンジイソシアネート、イソホロンジイソシアネート、４，４−ジシクロヘキシルメタンジイソシアネート、２，４’−ジシクロヘキシルメタンジイソシアネート、２，２’−ジシクロヘキシルメタンジイソシアネート、３，３’−ジメチル−４，４’−ジシクロヘキシルメタンジイソシアネート等の脂肪族又は脂環式ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた耐久性確保が得られ、かつ、耐光性、耐オレイン酸性、及び低温屈曲性を向上できる点から、脂肪族及び／又は脂環式ポリイソシアネートを用いることが好ましく、脂肪族ポリイソシアネートと脂環式ポリイソシアネートとを併用することが好ましい。 As polyisocyanate (Y), for example, 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2, 5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1 , 3-Dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate 1-methyl-3,5-diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, Naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl 2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane Aromatic polyisocyanates such as 2,4-diisocyanate; tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene Isocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, 1,4-di (isocyanatemethyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4- Dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate And aliphatic or alicyclic polyisocyanates such as 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aliphatic and / or alicyclic polyisocyanates are preferably used from the viewpoint of obtaining further excellent durability and improving light resistance, oleic acid resistance, and low temperature flexibility. It is preferable to use an aliphatic polyisocyanate and a cycloaliphatic polyisocyanate in combination.
前記脂肪族ポリイソシアネートと脂環式ポリイソシアネートとを併用する場合の質量比［脂肪族ＮＣＯ／脂環式ＮＣＯ］としては、より一層優れた耐オレイン酸性、及び低温屈曲性が得られる点から、その質量比［脂肪族ＮＣＯ／脂環式ＮＣＯ］としては、５／９５〜６０／４０の範囲であることが好ましく、１０／９０〜５０／５０の範囲がより好ましく、１５／８５〜４５／５５の範囲が更に好ましい。 As mass ratio [aliphatic NCO / alicyclic NCO] in the case of using the aliphatic polyisocyanate and the alicyclic polyisocyanate in combination, further excellent oleic acid resistance and low temperature flexibility are obtained, The mass ratio [aliphatic NCO / alicyclic NCO] is preferably in the range of 5/95 to 60/40, more preferably in the range of 10/90 to 50/50, and 15/85 to 45/50. A range of 55 is more preferred.
前記ポリイソシアネート（Ｙ）の使用量としては、優れた機械的強度、反応性が得られる点から、ポリオール（Ｘ）とポリイソシアネート（Ｙ）との合計質量中１０〜６０質量％の範囲であることが好ましく、１５〜４５質量％の範囲がより好ましい。 The amount of the polyisocyanate (Y) used is in the range of 10 to 60% by mass in the total mass of the polyol (X) and the polyisocyanate (Y), from the viewpoint of obtaining excellent mechanical strength and reactivity. Is preferable, and the range of 15 to 45% by mass is more preferable.
前記ウレタン樹脂（Ｚ）の製造方法としては、例えば、前記ポリオール（Ｘ）と前記ポリイソシアネート（Ｙ）とを一括で仕込み、反応させることによって製造する方法が挙げられ、反応は、例えば、３０〜１００℃の温度で、３〜１０時間行うことが好ましい。また、前記反応は、後述する溶剤中で行ってもよい。 Examples of the method for producing the urethane resin (Z) include a method in which the polyol (X) and the polyisocyanate (Y) are charged at one time and reacted, and the reaction is carried out, for example, It is preferable to carry out at a temperature of 100 ° C. for 3 to 10 hours. Also, the reaction may be carried out in a solvent described later.
前記ポリオール（Ｘ）が有する水酸基と前記ポリイソシアネート（Ｙ）が有するイソシアネート基とのモル比［（イソシアネート基）／（水酸基及びアミノ基）］としては、０．６〜２の範囲であることが好ましく、０．８〜１．２の範囲であることがより好ましい。 The molar ratio [(isocyanate group) / (hydroxy group and amino group)] between the hydroxyl group of the polyol (X) and the isocyanate group of the polyisocyanate (Y) is in the range of 0.6 to 2 Preferably, it is more preferably in the range of 0.8 to 1.2.
以上の方法により得られるウレタン樹脂（Ｚ）の数平均分子量としては、皮膜の機械的強度及び柔軟性をより一層向上できる点から、５，０００〜１，０００、０００の範囲であることが好ましく、１０，０００〜５００，０００の範囲がより好ましい。なお、前記ウレタン樹脂（Ｚ）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the urethane resin (Z) obtained by the above method is preferably in the range of 5,000 to 1,000,000 in that the mechanical strength and flexibility of the film can be further improved. The range of 10,000 to 500,000 is more preferable. In addition, the number average molecular weight of the said urethane resin (Z) shows the value measured by gel permeation chromatography (GPC) method.
前記ウレタン樹脂組成物は、前記ウレタン樹脂（Ｚ）を必須成分として含有するが、必要に応じてその他の成分を含有してもよい。 Although the said urethane resin composition contains the said urethane resin (Z) as an essential component, you may contain another component as needed.
前記その他の成分としては、例えば、溶剤、顔料、難燃剤、可塑剤、軟化剤、安定剤、ワックス、消泡剤、分散剤、浸透剤、界面活性剤、フィラー、防黴剤、抗菌剤、紫外線吸収剤、酸化防止剤、耐候安定剤、蛍光増白剤、老化防止剤、増粘剤等を用いることができる。これらの成分は単独で用いても２種以上を併用してもよい。 Examples of the other components include solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, antifoaming agents, dispersants, penetrants, surfactants, fillers, mildewproofing agents, antibacterial agents, A UV absorber, an antioxidant, a weathering stabilizer, a fluorescent whitening agent, an antiaging agent, a thickener and the like can be used. These components may be used alone or in combination of two or more.
前記溶剤としては、例えば、水、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、メチルエチルケトン、メチル−ｎ−プロピルケトン、アセトン、メチルイソブチルケトン等のケトン溶剤；ギ酸メチル、ギ酸エチル、ギ酸プロピル、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸イソブチル、酢酸イソブチル、酢酸第２ブチル等のエステル溶剤；メタノール、エタノール、イソプロピルアルコール、ブタノール等アルコール溶剤などを用いることができる。これらの溶剤は単独で用いても２種以上を併用してもよい。 Examples of the solvent include ketone solvents such as water, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; Ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate and sec-butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol can be used . These solvents may be used alone or in combination of two or more.
前記溶剤の含有量としては、作業性及び粘度の点から、ウレタン樹脂組成物中３０〜９０質量％の範囲であることが好ましい。 The content of the solvent is preferably in the range of 30 to 90% by mass in the urethane resin composition from the viewpoint of workability and viscosity.
本発明のウレタン樹脂組成物は基材に塗布し乾燥させることにより皮膜が得られる。 The urethane resin composition of the present invention is coated on a substrate and dried to obtain a film.
前記基材としては、例えば、不織布、織布、編み物等からなる繊維状基材；樹脂フィルムなどを用いることができる。前記繊維状基材を構成するものとしては、例えば、ポリエステル繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維等の化学繊維；綿、麻、絹、羊毛、これらの混紡繊維などを用いることができる。 As said base material, the fibrous base material which consists of a nonwoven fabric, woven fabric, knitting etc., resin film etc. can be used, for example. Examples of the fibrous base material include chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, etc .; cotton, hemp, silk, wool, etc. Blended fibers can be used.
前記樹脂フィルムとしては、例えば、ポリエチレンテレフタラートフィルム、ポリカーボネートフィルム、アクリル樹脂フィルム、ＣＯＰ（シクロオレフィンポリマー）フィルム、ＴＡＣ（トリアセチルセルロース）フィルム等を用いることができる。 As the resin film, for example, a polyethylene terephthalate film, a polycarbonate film, an acrylic resin film, a COP (cycloolefin polymer) film, a TAC (triacetyl cellulose) film or the like can be used.
前記基材の表面には、必要に応じて、制電加工、離型処理加工、撥水加工、吸水加工、抗菌防臭加工、制菌加工、紫外線遮断加工等の処理が施されていてもよい。 The surface of the substrate may be subjected to treatments such as antistatic treatment, mold release treatment, water repellent treatment, water absorption treatment, antibacterial deodorizing treatment, antibacterial treatment, ultraviolet blocking treatment, etc., as necessary. .
前記基材に本発明のウレタン樹脂組成物を塗布する方法としては、例えば、アプリケーター、バーコーター、ナイフコーター、Ｔ−ダイコーター、ロールコーター等による塗布方法が挙げられる。 As a method of apply | coating the urethane resin composition of this invention to the said base material, the application method by an applicator, a bar coater, a knife coater, a T-die coater, a roll coater etc. is mentioned, for example.
前記塗布されたウレタン樹脂組成物を乾燥させる方法としては、例えば、５０〜１４０℃の温度で、３０秒〜１０分間乾燥させる方法が挙げられる。 As a method of drying the applied urethane resin composition, for example, a method of drying at a temperature of 50 to 140 ° C. for 30 seconds to 10 minutes can be mentioned.
得られる皮膜の厚さとしては、使用される用途に応じて適宜決定されるが、例えば、０．００１〜１０ｍｍの範囲である。 The thickness of the obtained film is appropriately determined in accordance with the application to be used, and is, for example, in the range of 0.001 to 10 mm.
前記皮膜としては、皮革様シートに使用される場合には、より一層優れた耐摩耗性が得られる点から、クロスヘッドスピード１０ｍｍ／秒の条件での引張試験で得られる１００％モジュラスが、９ＭＰａ以上であることが好ましく、１１〜２０ＭＰａの範囲がより好ましい。なお、前記皮膜の前記１００％モジュラス値の測定方法は、実施例にて記載する。 When the film is used for a leather-like sheet, the 100% modulus obtained by the tensile test at a crosshead speed of 10 mm / sec is 9 MPa, from the viewpoint that even better abrasion resistance can be obtained. It is preferable that it is more than, and the range of 11-20 Mpa is more preferable. In addition, the measuring method of the said 100% modulus value of the said film is described in the Example.
前記皮膜を用いて合成皮革を得るうえでは、前記皮膜を合成皮革の表皮層又はトップコート層とすることが好ましい。 In order to obtain a synthetic leather using the film, it is preferable to use the film as the skin layer or top coat layer of the synthetic leather.
前記合成皮革の製造方法としては、例えば、離型紙上に形成した表面処理層と、前記皮膜とを公知の方法で貼りあわせる方法が挙げられる。前記表面処理層を形成する材料としては、例えば、溶剤系ウレタン樹脂、水系ウレタン樹脂、水系アクリル樹脂等を用いることができる。また、前記貼りあわせには、必要に応じて、公知の接着剤を用いてもよい。 Examples of the method for producing the synthetic leather include a method of bonding the surface treatment layer formed on a release paper and the film by a known method. As a material which forms the said surface treatment layer, solvent-type urethane resin, water-based urethane resin, water-based acrylic resin etc. can be used, for example. Moreover, you may use a well-known adhesive agent for the said bonding as needed.
以上、本発明のウレタン樹脂組成物は、耐オレイン酸性、低温屈曲性、及び機械的強度に優れるものである。よって、本発明のウレタン樹脂組成物は、合成皮革、衣料、支持パッド、研磨パッド等の製造に使用される材料として好適に使用することができ、合成皮革の材料として特に好適に使用することができる。 As described above, the urethane resin composition of the present invention is excellent in oleic acid resistance, low temperature flexibility, and mechanical strength. Therefore, the urethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, support pads, polishing pads and the like, and particularly preferably used as a material of synthetic leather it can.
以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail by way of examples.
［実施例１］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ポリカーボネートジオール（１，４−ブタンジオール及び１，６−ヘキサンジオールを原料とするもの、［Ｃ４／Ｃ６］（以下、モル比）＝７０／３０、数平均分子量；２，０００、以下「ＰＣ１」と略記する。）を１１７質量部、ポリカーボネートジオール（１，６−ヘキサンジオールを原料とするもの、［Ｃ６］＝１００、数平均分子量；２，０００、以下「他ＰＣ１」と略記する。）を１４質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、Ｎ，Ｎ−ジメチルホルムアミド（以下、「ＤＭＦ」と略記する。）を１０１質量部と水素化ビスフェノールＡ（以下、「ＨＢＰＡ」と略記する。）７質量部を加え、十分に撹拌した。撹拌後、イソホロンジイソシアネート（以下、「ＩＰＤＩ」と略記する。）３３質量部とヘキサメチレンジイソシアネート（以下、「ＨＤＩ」と略記する。）１７質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２４３質量部、酢酸エチル１１０質量部を加え、３５℃に冷却し、イソホロンジアミン（以下、「ＩＰＤＡ」と略記する。）２１質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．３質量部、イソプロピルアルコール１１０質量部を加え、混合することによって、ウレタン樹脂組成物を得た。Example 1
A polycarbonate diol (having 1,4-butanediol and 1,6-hexanediol as a raw material, [C4 / C6] (hereinafter, referred to as “C4 / C6”), was added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer. Molar ratio: 70/30, number average molecular weight; 2,000, hereinafter abbreviated as "PC1") 117 parts by mass, polycarbonate diol (having 1,6-hexanediol as a raw material, [C6] = 100 Number average molecular weight; 2,000 (hereinafter abbreviated as "other PC 1") 14 parts by mass) was added, and dehydration was performed at 120 to 130 ° C at a degree of reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 101 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”) and 7 parts by mass of hydrogenated bisphenol A (hereinafter abbreviated as “HBPA”) Was thoroughly stirred. After stirring, 33 parts by mass of isophorone diisocyanate (hereinafter abbreviated as "IPDI"), 17 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as "HDI") and 0.1 parts by mass of stannous octoate are added. The reaction was conducted at 75 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal. Subsequently, 243 parts by mass of DMF and 110 parts by mass of ethyl acetate are added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., and 21 parts by mass of isophorone diamine (hereinafter abbreviated as “IPDA”) is added. The polyurethane resin was elongated by stirring and mixing. Then, a urethane resin composition was obtained by adding 0.3 parts by mass of N, N-dibutylamine and 110 parts by mass of isopropyl alcohol and mixing.
［実施例２］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ＰＣ１を１１７質量部、他ＰＣ１を８質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを９７質量部とシクロヘキサンジメタノール（以下、「ＣＨＤＭ」と略記する。）５質量部を加え、十分に撹拌した。撹拌後、ＩＰＤＩを３８質量部、及び、ＨＤＩを１２質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを１９９質量部、酢酸エチル８９質量部を加え、３５℃に冷却し、４，４’−ジシクロヘキシルメタンジアミン（以下、「Ｈ１２ＭＤＡ」と略記する。）２１質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．８質量部、イソプロピルアルコール８９質量部を加え、混合することによって、ウレタン樹脂組成物を得た。Example 2
117 parts by mass of PC1 and 8 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 97 parts by mass of DMF and 5 parts by mass of cyclohexanedimethanol (hereinafter abbreviated as “CHDM”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 38 parts by mass of IPDI, 12 parts by mass of HDI, and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Next, 199 parts by mass of DMF and 89 parts by mass of ethyl acetate are added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., and abbreviated as 4,4′-dicyclohexylmethanediamine (hereinafter, “H12 MDA”). 21) The polyurethane resin was elongated by adding 21 parts by mass and stirring and mixing. Next, a urethane resin composition was obtained by adding and mixing 0.8 parts by mass of N, N-dibutylamine and 89 parts by mass of isopropyl alcohol.
［実施例３］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ポリカーボネートジオール（１，４−ブタンジオール及び１，６−ヘキサンジオールを原料とするもの、［Ｃ４／Ｃ６］＝９０／１０、数平均分子量；２，０００、以下「ＰＣ２」と略記する。）を１１７質量部、他ＰＣ１を２１質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを１０１質量部と水素化ビスフェノールＡのエチレンオキサイド１モル付加物（以下、「ＰＯＥＢＡ」と略記する。）７質量部を加え、十分に撹拌した。撹拌後、４，４’−ジシクロヘキシルメタンジイソシアネート（以下、「Ｈ１２ＭＤＩ」と略記する。）３０質量部、及び、ＨＤＩを１９質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２２５質量部、酢酸エチル８９質量部を加え、３５℃に冷却し、ＩＰＤＡ１８質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．６質量部、イソプロピルアルコール１０２質量部を加え、混合することによって、ウレタン樹脂組成物を得た。[Example 3]
A polycarbonate diol (having 1,4-butanediol and 1,6-hexanediol as a raw material, [C4 / C6] = 90 /) in a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer 10, number average molecular weight; 2,000, hereinafter abbreviated as "PC2") 117 parts by mass, 21 parts by mass of another PC 1 were added, and dehydration was performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, 101 parts by mass of DMF and 7 parts by mass of ethylene oxide 1 mol adduct of hydrogenated bisphenol A (hereinafter abbreviated as “POEBA”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 30 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (hereinafter abbreviated as "H12MDI"), 19 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and the mixture is stirred at 75.degree. By making it react, the organic solvent solution of the urethane prepolymer which has an isocyanate group at the molecular terminal was obtained. Subsequently, 225 parts by mass of DMF and 89 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 18 parts by mass of IPDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.6 parts by mass of N, N-dibutylamine and 102 parts by mass of isopropyl alcohol and mixing.
［実施例４］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ＰＣ２を９１質量部、（１，３−プロパンジオール及び１，４−ブタンンジオールを原料とするもの、［Ｃ３／Ｃ４］＝５０／５０、数平均分子量；２，０００、以下「他ＰＣ２」と略記する。）を４２質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを１００質量部とスピログリコール（三菱ガス化学株式会社製、以下、「ＳＰＧ」と略記する。）７質量部を加え、十分に撹拌した。撹拌後、ＩＰＤＩ３２質量部、及び、ＨＤＩを１３質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２６１質量部、酢酸エチル１１８質量部を加え、３５℃に冷却し、Ｈ１２ＭＤＡ２４質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．３質量部、イソプロピルアルコール１１８質量部を加え、混合することによって、ウレタン樹脂組成物を得た。Example 4
Into a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, 91 parts by mass of PC2 (using 1,3-propanediol and 1,4-butanediol as a raw material, [C3 / C4] = 50/50, number average molecular weight; 2,000, hereinafter 42 parts by mass of "other PC2" are added, and dehydration is performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, 100 parts by mass of DMF and 7 parts by mass of spiroglycol (Mitsubishi Gas Chemical Co., Ltd., hereinafter abbreviated as “SPG”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 32 parts by mass of IPDI, 13 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic solvent solution of urethane prepolymer having isocyanate group at molecular terminal I got Subsequently, 261 parts by mass of DMF and 118 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 24 parts by mass of H12 MDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.3 parts by mass of N, N-dibutylamine and 118 parts by mass of isopropyl alcohol and mixing.
［実施例５］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ＰＣ１を１０２質量部、他ＰＣ１を２９質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを９８質量部とＳＰＧ５質量部を加え、十分に撹拌した。撹拌後、ＩＰＤＩ３９質量部、及び、ＨＤＩを７質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２３３質量部、酢酸エチル１０５質量部を加え、３５℃に冷却し、Ｈ１２ＭＤＡ２２質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．９質量部、イソプロピルアルコール１０５質量部を加え、混合することによって、ウレタン樹脂組成物を得た。[Example 5]
102 parts by mass of PC1 and 29 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 98 parts by mass of DMF and 5 parts by mass of SPG were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 39 parts by mass of IPDI, and 7 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic solvent solution of urethane prepolymer having isocyanate group at molecular terminal I got Subsequently, 233 parts by mass of DMF and 105 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 22 parts by mass of H12 MDA was added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.9 parts by mass of N, N-dibutylamine and 105 parts by mass of isopropyl alcohol and mixing.
［実施例６］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ＰＣ１を１２０質量部、（１，４−ブタンンジオール及び１，１０−デカンジオ−ルを原料とするもの、［Ｃ４／Ｃ１０］＝９０／１０、数平均分子量；３，０００、以下「他ＰＣ３」と略記する。）を７質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを１００質量部とＨＢＰＡ７質量部を加え、十分に撹拌した。撹拌後、Ｈ１２ＭＤＩを３６質量部、及び、ＨＤＩを１５質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２１４質量部、酢酸エチル９７質量部を加え、３５℃に冷却し、ＩＰＤＡ１７質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．５質量部、イソプロピルアルコール９７質量部を加え、混合することによって、ウレタン樹脂組成物を得た。[Example 6]
A nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and 120 parts by mass of PC1 (having 1,4-butanediol and 1,10-decanediol as a raw material, [C4 / C10] = 90/10, number average molecular weight; 3,000, hereinafter, 7 parts by mass of "other PC 3" are added, and dehydration is performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, 100 parts by mass of DMF and 7 parts by mass of HBPA were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 36 parts by mass of H12 MDI, and 15 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C., thereby forming an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Subsequently, 214 parts by mass of DMF and 97 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 17 parts by mass of IPDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, 0.5 parts by mass of N, N-dibutylamine and 97 parts by mass of isopropyl alcohol were added and mixed to obtain a urethane resin composition.
［比較例１］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ＰＣ２を１０９質量部、他ＰＣ１を２６質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを１００質量部とエチレングリコール（以下、「ＥＧ」と略記する。）１質量部を加え、十分に撹拌した。撹拌後、Ｈ１２ＭＤＩを３８質量部、及び、ＨＤＩを１１質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２７１質量部、酢酸エチル１２４質量部を加え、３５℃に冷却し、ＩＰＤＡ２０質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．７質量部、イソプロピルアルコール１２４質量部を加え、混合することによって、ウレタン樹脂組成物を得た。Comparative Example 1
109 parts by mass of PC2 and 26 parts by mass of other PC1 were added to a nitrogen-replaced four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, while cooling to 50 ° C., 100 parts by mass of DMF and 1 part by mass of ethylene glycol (hereinafter abbreviated as “EG”) were added and sufficiently stirred. After stirring, 38 parts by mass of H12MDI, 11 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C., thereby forming an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Next, 271 parts by mass of DMF and 124 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 20 parts by mass of IPDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, 0.7 parts by mass of N, N-dibutylamine and 124 parts by mass of isopropyl alcohol were added and mixed to obtain a urethane resin composition.
［比較例２］
攪拌機、還流冷却管及び温度計を有する窒素置換された４ツ口フラスコに、ＰＣ２を８８質量部、他ＰＣ１を５９質量部加え、減圧度０．０９５ＭＰａにて１２０〜１３０℃で脱水を行った。脱水後、５０℃まで冷却しながら、ＤＭＦを１０１質量部を加え、十分に撹拌した。撹拌後、ＩＰＤＩを３４質量部、及び、ＨＤＩを６質量部とオクチル酸第一錫０．１質量部を加え、７５℃で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。次いで、前記ウレタンプレプレポリマーの有機溶剤溶液に、ＤＭＦを２７８質量部、酢酸エチル１２６質量部を加え、３５℃に冷却し、Ｈ１２ＭＤＡ２３質量部を加え、撹拌混合することによって、ポリウレタン樹脂を伸長させた。次いで、Ｎ，Ｎ−ジブチルアミン０．３質量部、イソプロピルアルコール１２６質量部を加え、混合することによって、ウレタン樹脂組成物を得た。Comparative Example 2
88 parts by mass of PC2 and 59 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 101 parts by mass of DMF was added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 34 parts by mass of IPDI, and 6 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Subsequently, 278 parts by mass of DMF and 126 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 23 parts by mass of H12 MDA was added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.3 parts by mass of N, N-dibutylamine and 126 parts by mass of isopropyl alcohol and mixing.
［数平均分子量の測定方法］
実施例及び比較例で用いたポリオール等の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。[Method of measuring number average molecular weight]
The number average molecular weights of the polyol and the like used in Examples and Comparative Examples are values measured under the following conditions by gel permeation chromatography (GPC).
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ−８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−５５０」(Standard polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"
［機械的強度の測定方法］
実施例及び比較例で得られたウレタン樹脂組成物１００質量部に、ＤＭＦ４０質量部を配合した配合液を、フラット離型紙（リンテック株式会社製「ＥＫ−１００Ｄ」）上に乾燥後の膜厚が３０ミクロンとなるように塗布し、９０℃で２分間、更に１２０℃で２分間乾燥させて皮膜を作製した。次いで、得られた皮膜を幅５ｍｍ、長さ５０ｍｍの短冊状に裁断し、引張試験機「オートグラフＡＧ−Ｉ」（株式会社島津製作所製）を用いて、温度２３℃の雰囲気下で、クロスヘッドスピード１０ｍｍ／秒の条件で引張り、試験片の１００％モジュラス（ＭＰａ）を測定した。この時のチャック間距離は４０ｍｍとした。得られた１００％モジュラス値から、機械的強度を以下のように評価した。
「Ａ」：１１ＭＰａ以上２０ＭＰａ未満
「Ｂ」：９ＭＰａ以上１１ＭＰａ未満
「Ｃ」：９ＭＰａ未満[Method of measuring mechanical strength]
100 parts by mass of the urethane resin composition obtained in Examples and Comparative Examples were mixed with 40 parts by mass of DMF and dried on a flat release paper ("EK-100D" manufactured by LINTEC Corporation). The coating was applied to 30 microns, dried at 90 ° C. for 2 minutes, and further dried at 120 ° C. for 2 minutes to prepare a film. Then, the obtained film is cut into strips of width 5 mm and length 50 mm, and a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation) is used to cross at an atmosphere of temperature 23 ° C. The sample was pulled at a head speed of 10 mm / sec, and the 100% modulus (MPa) of the test piece was measured. The distance between chucks at this time was 40 mm. From the obtained 100% modulus value, mechanical strength was evaluated as follows.
"A": 11 MPa or more and less than 20 MPa "B": 9 MPa or more and less than 11 MPa "C": less than 9 MPa
［耐オレイン酸性の測定方法］
前記［機械的強度の測定方法］と同様の方法にて皮膜を作製した。次いで、この皮膜を幅５ｍｍ、長さ５０ｍｍの短冊状に試験片を裁断し、常温でオレイン酸に２４時間浸漬した後取り出し、表面に付着したオレイン酸を紙ウエスで軽く拭き取った。その後、引張試験機「オートグラフＡＧ−Ｉ」（株式会社島津製作所製）を用いて、温度２３℃の雰囲気下で、クロスヘッドスピード１０ｍｍ／秒、チャック間距離４０ｍｍの条件で引張り、試験片が１００％伸張した際の応力を測定した。この応力を前記［機械的強度の測定方法］にて測定した１００％モジュラス値で除した値を１００％モジュラス値の保持率として、耐オレイン酸性を以下のように評価した。
「Ａ」：保持率が４０％以上
「Ｂ」：保持率が３０％以上４０％未満
「Ｃ」：保持率が３０％未満[Method for measuring oleic acid resistance]
A film was produced in the same manner as the above-mentioned [Method of measuring mechanical strength]. Subsequently, the film was cut into strips of 5 mm in width and 50 mm in length, immersed in oleic acid at normal temperature for 24 hours and then taken out, and oleic acid adhering to the surface was lightly wiped off with a paper waste. Then, using a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation), the specimen is pulled under the conditions of a crosshead speed of 10 mm / sec and a chuck distance of 40 mm under an atmosphere of temperature 23 ° C. The stress at 100% elongation was measured. The oleic acid resistance was evaluated as follows using the value obtained by dividing this stress by the 100% modulus value measured in the above-mentioned [Method for measuring mechanical strength] as the retention of the 100% modulus value.
"A": retention rate is 40% or more "B": retention rate is 30% or more and less than 40% "C": retention rate is less than 30%
［低温屈曲性の測定方法］
実施例及び比較例で得られたウレタン樹脂組成物１００質量部に、ＤＭＦを４０質量部、メチルエチルケトンを３０質量部及びＤＩＣ株式会社製着色剤「ダイラックＬ−１７７０Ｓ」を２０質量部からなる配合液を離型紙上に乾燥後の膜厚が３０ミクロンとなるように塗布し、９０℃で２分間、更に１２０℃で２分間乾燥させ、離型紙上に皮膜を作製した。次いで、この皮膜上に、ＤＩＣ株式会社製ウレタン樹脂「クリスボンＴＡ−２０５ＦＴ」を１００質量部、ＤＭＦを６０質量部、及びＤＩＣ株式会社製ポリイソシアネート架橋剤「バーノックＤＮ−９５０」を１２質量部、ＤＩＣ株式会社製錫触媒「アクセルＴ−８１Ｅ」を１質量部からなる配合液を乾燥後の膜厚が６０ミクロンとなるように塗布し、１００℃で１分間乾燥させた。次いで、ポリエステル基布を載せ、１２０℃のラミネーターで圧着させたのち、４０℃で３日間熟成し、離型紙を剥離して合成皮革を得た。
この合成皮革をフレキソメーター（株式会社安田精機製作所製「低温槽付フレキシオメーター」）での屈曲性試験（−１０℃、１００回／毎分）を行い、合成皮革の表面に割れが生じるまでの回数を測定し、以下のように評価した。
「Ａ」：２０，０００回以上
「Ｂ」：１０，０００回以上２０，０００回未満
「Ｃ」：１０，０００回未満[Method of measuring low temperature flexibility]
100 parts by mass of the urethane resin composition obtained in Examples and Comparative Examples, 40 parts by mass of DMF, 30 parts by mass of methyl ethyl ketone, and 20 parts by mass of a coloring agent “Dylac L-1770S” manufactured by DIC Corporation Were coated on a release paper so that the film thickness after drying was 30 microns, dried at 90 ° C. for 2 minutes, and further dried at 120 ° C. for 2 minutes to prepare a film on release paper. Then, on this film, 100 parts by mass of a urethane resin “Kurisbon TA-205FT” manufactured by DIC Corporation, 60 parts by mass of DMF, and 12 parts by mass of polyisocyanate crosslinking agent “Burnock DN-950” manufactured by DIC Corporation A mixed solution consisting of 1 part by mass of a tin catalyst "Accel T-81E" manufactured by DIC Corporation was applied so that the film thickness after drying would be 60 microns, and dried at 100 ° C for 1 minute. Next, a polyester base was placed thereon and pressure-bonded with a 120 ° C. laminator, and then aged at 40 ° C. for 3 days, and the release paper was peeled off to obtain a synthetic leather.
This synthetic leather is subjected to a flexibility test (-10 ° C, 100 times / minute) with a flexometer (“low temperature bath-equipped flexiometer” manufactured by Yasuda Seiki Co., Ltd.) until the surface of the synthetic leather is cracked The number of times was measured and evaluated as follows.
"A": 20,000 or more "B": 10,000 or more and less than 20,000 "C": less than 10,000
表１〜２中における略語について説明する。
「Ｍｎ」；数平均分子量
「Ｃ３」；１，３−プロパンジオール
「Ｃ４」；１，４−ブタンジオール
「Ｃ１０」：１，１０−デカンジオール
「Ｃ６」：１，６−ヘキサンジオール
「Ｃ５」：１，５−ペンタンジオールThe abbreviations in Tables 1 and 2 will be described.
"Mn"; number average molecular weight "C3"; 1,3-propanediol "C4"; 1,4-butanediol "C10": 1, 10-decanediol "C6": 1, 6-hexanediol "C5" : 1,5-pentanediol
本発明のウレタン樹脂組成物である実施例１〜６は、耐オレイン酸性、低温屈曲性、及び機械的強度に優れることが分かった。 Examples 1 to 6, which are the urethane resin compositions of the present invention, were found to be excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.
一方、比較例１は、グリコール化合物（Ｂ）の代わりに、エチレングリコールを用いた態様であるが、耐オレイン酸性が不良であった。 On the other hand, Comparative Example 1 was an embodiment in which ethylene glycol was used instead of the glycol compound (B), but oleic acid resistance was poor.
比較例２は、グリコール化合物（Ｂ）及びその代替も使用しない態様であるが、機械的強度、及び耐オレイン酸性が不良であった。 Although the comparative example 2 is an aspect which does not use a glycol compound (B) and its substitute, either, mechanical strength and oleic acid resistance were inferior.
Claims (8)
Polycarbonate polyol (A) having butanediol and hexanediol as raw materials, and polycarbonate polyols other than the above (A) (polycarbonate polyols having 1,6-hexanediol as raw materials, 1,3-propanediol and 1,4-butane Polycarbonate polyol having diol as a raw material, or polycarbonate polyol (excluding aromatic polycarbonate polyol) having 1,4-butanediol and 1,10-decanediol as raw materials, and monocyclic aliphatic glycol (b-1) A polyol (X) comprising a glycol (b-2) having a spiro ring, and at least one glycol compound (B) selected from the group consisting of an aromatic glycol (b-3), and a polyisocyanate Urethane resin (Y) is an essential raw material ( ) Containing the (amount of polycarbonate polyol other than A) is a urethane resin composition, wherein the der Rukoto in less than 40 wt% polyol (X).
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| JP2017208157 | 2017-10-27 | ||
| JP2017208157 | 2017-10-27 | ||
| PCT/JP2018/029888 WO2019082475A1 (en) | 2017-10-27 | 2018-08-09 | Urethane resin composition, coating film and synthetic leather |
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| JP6528915B1 true JP6528915B1 (en) | 2019-06-12 |
| JPWO2019082475A1 JPWO2019082475A1 (en) | 2019-11-14 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051766A (en) * | 1983-08-31 | 1985-03-23 | Negami Kogyo Kk | Polycarbonate-modified urethane acrylate adhesive |
| JPH055280A (en) * | 1990-11-20 | 1993-01-14 | Asahi Chem Ind Co Ltd | Synthetic leather |
| JP2001187811A (en) * | 1999-10-22 | 2001-07-10 | Dainippon Ink & Chem Inc | Polyurethane resin and method for producing the same, and resin composition and sheet shape article produced by using the same |
| JP2007092195A (en) * | 2005-09-27 | 2007-04-12 | Dai Ichi Kogyo Seiyaku Co Ltd | Aqueous resin composition for fiber laminate skin, method for producing fiber laminate, and synthetic leather |
| JP2009149810A (en) * | 2007-12-21 | 2009-07-09 | Asahi Kasei Chemicals Corp | Porous sheet-like product |
| WO2014208567A1 (en) * | 2013-06-27 | 2014-12-31 | 旭化成ケミカルズ株式会社 | Polyisocyanate composition and method for production thereof, block polyisocyanate composition and method for production thereof, resin composition, curable resin composition, and cured article |
| CN104356348A (en) * | 2014-10-29 | 2015-02-18 | 合肥安利聚氨酯新材料有限公司 | Hard hydrolysis-resistant, low-pitting performance and strong-peel strength polyurethane resin and preparation method thereof |
-
2018
- 2018-08-09 JP JP2018558260A patent/JP6528915B1/en active Active
- 2018-08-09 WO PCT/JP2018/029888 patent/WO2019082475A1/en active Application Filing
- 2018-09-05 TW TW107131084A patent/TW201922831A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051766A (en) * | 1983-08-31 | 1985-03-23 | Negami Kogyo Kk | Polycarbonate-modified urethane acrylate adhesive |
| JPH055280A (en) * | 1990-11-20 | 1993-01-14 | Asahi Chem Ind Co Ltd | Synthetic leather |
| JP2001187811A (en) * | 1999-10-22 | 2001-07-10 | Dainippon Ink & Chem Inc | Polyurethane resin and method for producing the same, and resin composition and sheet shape article produced by using the same |
| JP2007092195A (en) * | 2005-09-27 | 2007-04-12 | Dai Ichi Kogyo Seiyaku Co Ltd | Aqueous resin composition for fiber laminate skin, method for producing fiber laminate, and synthetic leather |
| JP2009149810A (en) * | 2007-12-21 | 2009-07-09 | Asahi Kasei Chemicals Corp | Porous sheet-like product |
| WO2014208567A1 (en) * | 2013-06-27 | 2014-12-31 | 旭化成ケミカルズ株式会社 | Polyisocyanate composition and method for production thereof, block polyisocyanate composition and method for production thereof, resin composition, curable resin composition, and cured article |
| CN104356348A (en) * | 2014-10-29 | 2015-02-18 | 合肥安利聚氨酯新材料有限公司 | Hard hydrolysis-resistant, low-pitting performance and strong-peel strength polyurethane resin and preparation method thereof |
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| JPWO2019082475A1 (en) | 2019-11-14 |
| WO2019082475A1 (en) | 2019-05-02 |
| TW201922831A (en) | 2019-06-16 |
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