WO2022176582A1 - ポリウレタン樹脂組成物、硬化物、繊維積層体及び人工皮革 - Google Patents
ポリウレタン樹脂組成物、硬化物、繊維積層体及び人工皮革 Download PDFInfo
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- WO2022176582A1 WO2022176582A1 PCT/JP2022/003481 JP2022003481W WO2022176582A1 WO 2022176582 A1 WO2022176582 A1 WO 2022176582A1 JP 2022003481 W JP2022003481 W JP 2022003481W WO 2022176582 A1 WO2022176582 A1 WO 2022176582A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane resin
- resin composition
- polyol
- less
- molecular weight
- Prior art date
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 52
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 239000000835 fiber Substances 0.000 title claims description 15
- 239000002649 leather substitute Substances 0.000 title claims description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 59
- 150000003077 polyols Chemical class 0.000 claims abstract description 59
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 27
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 27
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 27
- 125000000524 functional group Chemical group 0.000 claims abstract description 23
- 239000004417 polycarbonate Substances 0.000 claims abstract description 20
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000000129 anionic group Chemical group 0.000 claims abstract description 13
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 5
- -1 diaminobenzoic acid Chemical class 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 239000004970 Chain extender Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 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 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 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
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-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
- 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
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- XAQCYASNAMYTQA-UHFFFAOYSA-N 2,4-diamino-5-methylbenzenesulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=C(N)C=C1N XAQCYASNAMYTQA-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-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
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 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
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 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 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
- D06N3/145—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 two or more layers of polyurethanes
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- 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
- D06N3/146—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 characterised by the macromolecular diols used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2437/00—Clothing
Definitions
- the present invention relates to polyurethane resin compositions, cured products, fiber laminates and artificial leathers.
- water-based polyurethane resin compositions have been used for leather-like sheets such as suede-like artificial leather because they can impart durability (for example, Patent Document 1).
- Patent Document 1 discloses a reaction product of a polycarbonate diol containing a structural unit derived from 1,10-decanediol and a polyol containing a polyhydric alcohol having a molecular weight of 400 or less containing only a hydroxyl group as a functional group and an organic polyisocyanate.
- a urethane prepolymer having an isocyanate group at the end, which is a substance, is chained with a polyamine compound containing two or more amino groups per molecule of at least one kind selected from the group consisting of primary amino groups and secondary amino groups.
- An elongated water-dispersible polycarbonate-based polyurethane resin composition is described.
- the present invention has been made to solve the above problems, and can be realized as the following forms.
- a polyurethane resin composition comprises a polycarbonate polyol having a structural unit derived from 1,10-decanediol, a polyhydric alcohol having a number average molecular weight of 420 or more and 2000 or less having only three or more hydroxy groups as functional groups, and an anionic A reaction product of a polyol containing a polyol having a hydrophilic group and a polyisocyanate is chain-extended with a polyamine.
- the polyurethane resin composition of this form it has excellent durability and excellent flexibility at low temperatures.
- the polyol may further include a polyether polyol having structural units derived from ethylene glycol.
- the proportion of the polycarbonate polyol having a structural unit derived from 1,10-decanediol in the polyol may be 50% by mass or more and 97% by mass or less.
- the polyurethane resin composition of this form it has excellent durability and flexibility at low temperatures.
- the proportion of the polyhydric alcohol in the total polyols may be 3% by mass or more and 20% by mass or less.
- the polyurethane resin composition of this form it has excellent durability and flexibility at low temperatures.
- the polyhydric alcohol may have a number average molecular weight of 500 or more and 1000 or less.
- the polyurethane resin composition of this form it has excellent durability and flexibility at low temperatures.
- a fiber laminate comprising a skin layer formed using the polyurethane resin composition of the above aspect, and a fiber fabric layer.
- an artificial leather comprising the fiber laminate of the above aspect.
- a polyurethane resin composition according to an embodiment of the present invention comprises a polycarbonate polyol having a structural unit derived from 1,10-decanediol and a poly(polyurethane) having a number average molecular weight of 420 or more and 2000 or less and having three or more hydroxy groups as functional groups.
- a polyol containing a polyol having an anionic hydrophilic group and a polyisocyanate is chain-extended with a polyamine. Characterized by The polyurethane resin composition of this embodiment can exist in the form of an aqueous dispersion.
- the polyurethane resin composition of the present embodiment has excellent durability and excellent flexibility at low temperatures.
- the polyol component (A) used in the polyurethane resin composition of the present embodiment comprises a polycarbonate polyol having a structural unit derived from 1,10-decanediol (hereinafter also referred to as "decanediol-derived polycarbonate polyol") and a functional group. and a polyhydric alcohol having a number average molecular weight of 420 or more and 2000 or less having only three or more hydroxy groups, and a polyol having an anionic hydrophilic group.
- the number average molecular weight of the decanediol-derived polycarbonate polyol is not particularly limited, but is preferably 800 or more, more preferably 900 or more, and even more preferably 950 or more, from the viewpoint of excellent flexibility at low temperatures.
- the number average molecular weight of the decanediol-derived polycarbonate polyol is preferably 3400 or less, more preferably 3200 or less, and even more preferably 3100 or less, from the viewpoint of excellent handling.
- decanediol-derived polycarbonate polyol is not particularly limited, examples thereof include BENEBiOL (registered trademark) NL1010DB, BENEBiOL (registered trademark) NL2010DB, and BENEBiOL (registered trademark) NL3010DB manufactured by Mitsubishi Chemical Corporation.
- polyhydric alcohol The polyhydric alcohol having a number average molecular weight of 420 or more and 2000 or less and having only three or more hydroxy groups as functional groups is not particularly limited, and examples thereof include polyether polyols and polyester polyols. As the polyhydric alcohol of the present embodiment, polyether polyol is preferable from the viewpoint of excellent durability and flexibility at low temperatures.
- the polyhydric alcohol of this embodiment has 3 or more hydroxy groups. From the viewpoint of excellent durability and flexibility at low temperatures, the number of hydroxy groups possessed by the polyhydric alcohol is preferably 4 or more, preferably 8 or less, more preferably 7 or less, and 6 or less. More preferred.
- the polyhydric alcohol of this embodiment has a number average molecular weight of 420 or more and 2000 or less.
- the number average molecular weight of the polyhydric alcohol is preferably 450 or more, more preferably 500 or more, still more preferably 520 or more, and preferably 1500 or less, and 1000 or less, from the viewpoint of excellent durability and low-temperature flexibility. More preferably, 800 or less is even more preferable.
- the polyhydric alcohol of the present embodiment is not particularly limited, but examples include SANNIX GP-600 manufactured by Sanyo Kasei Co., Ltd., and EXENOL 430, EXENOL 1030, EXENOL 410NE, EXENOL 3030 manufactured by Asahi Glass Co., Ltd., and the like.
- an anionic hydrophilic group means a carboxy group or a salt thereof, a sulfonic acid group or a salt thereof.
- polyols having a carboxyl group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4 -Carboxylic acid-containing compounds such as diaminobenzoic acid, derivatives thereof, salts thereof, polyester polyols using these, and the like.
- Polyols having a sulfonic acid group include, for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6-disulfone Acids, sulfonic acid-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid, derivatives thereof, salts thereof, polyester polyols using these, polyamide polyols, polyamide polyester polyols, etc. be done.
- carboxy groups or sulfonic acid groups are preferable because they are excellent in water dispersibility of the final polyurethane obtained by neutralizing them into salts.
- the neutralizing agent include non-volatile bases such as sodium hydroxide and potassium hydroxide; tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanolamine; and volatile bases such as ammonia. is mentioned. Neutralization can be performed before, during, or after the urethanization reaction.
- the polyol having an anionic hydrophilic group is preferably a polyol having a carboxy group, more preferably 2,2-dimethylolpropionic acid, from the viewpoint of improving the storage stability of the aqueous polyurethane dispersion.
- Polyols other than the above-mentioned decanediol-derived polycarbonate polyols, the above-mentioned polyhydric alcohols, and the above-mentioned polyols having anionic hydrophilic groups can be used as polyols, since stable emulsions can be obtained. It is preferred to have a polyether polyol having structural units that Polyether polyols having structural units derived from ethylene glycol are not particularly limited, but examples thereof include polyoxyethylene polyoxypropylene random copolymer glycol and polyethylene glycol.
- polyoxyethylene-polyoxypropylene random copolymer glycols examples include ADEKA POLYETHER PR-3007 (manufactured by ADEKA, molecular weight: 3000, oxyethylene group content: 70%).
- polyethylene glycol examples include PEG-600S (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., molecular weight: 600).
- the ratio of the decanediol-derived polycarbonate polyol to the total polyol is not particularly limited, but from the viewpoint of excellent abrasion resistance and flexibility at low temperatures, it is preferably 50% by mass or more, and 60% by mass or more. and more preferably 70% by mass or more.
- the proportion of the decanediol-derived polycarbonate polyol in the total polyol is preferably 97% by mass or less, more preferably 93% by mass or less, and even more preferably 88% by mass or less.
- the blending ratio of the polyhydric alcohol in the total polyol is not particularly limited, but from the viewpoint of excellent wear resistance and flexibility at low temperatures, it is preferably 1% by mass or more, and 3% by mass or more. is more preferable, and 5% by mass or more is even more preferable.
- the proportion of the polyhydric alcohol in the total polyol is preferably 22% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less.
- the polyisocyanate used in the polyurethane resin composition of the present embodiment is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. From the viewpoint of excellent abrasion resistance and low-temperature flexibility, the polyisocyanate preferably contains an alicyclic polyisocyanate.
- aliphatic polyisocyanates include, but are not limited to, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. , 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and the like.
- the alicyclic polyisocyanate is not particularly limited, but examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate (hereinafter also referred to as “H 12 MDI”), and 1,4-cyclohexane diisocyanate. , methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and the like.
- aromatic polyisocyanates include, but are not limited to, tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, 4 ,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
- the araliphatic polyisocyanate is not particularly limited, but includes, for example, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate, and the like.
- polyisocyanate a modified form of the above-mentioned organic polyisocyanate may be used.
- Modified forms of organic polyisocyanates are not particularly limited, and examples thereof include carbodiimide forms, allophanate forms, biuret forms, isocyanurate forms, and adduct forms.
- polyisocyanate can also be used individually or in combination of 2 or more types.
- H 12 MDI 4,4′-dicyclohexylmethane diisocyanate
- the number average molecular weight of the polyisocyanate is not particularly limited, it is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and more preferably 150 or more and 280 or less.
- the polyamine used in the polyurethane resin composition of the present embodiment is not particularly limited, and for example, chain extenders commonly used in the technical field can be used.
- Polyamines include, for example, diamines, triamines, and tetraamines.
- Diamines include, for example, ethylenediamine, trimethylenediamine, piperazine, isophoronediamine, and the like.
- triamines include diethylenetriamine and dipropylenetriamine.
- triamines include triethylenetetramine and the like.
- the polyurethane resin composition of the present embodiment may contain other materials as long as the effects of the present invention are not impaired.
- other materials include, but are not particularly limited to, chain extenders other than the above polyamines, cross-linking agents, catalysts, and the like.
- Chain extenders other than the above polyamines are not particularly limited, but examples include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol and the like can be mentioned.
- the cross-linking agent include, but are not limited to, aminoplast compounds, epoxy compounds, carbodiimide compounds, glycerin, and the like.
- the catalyst is not particularly limited, but examples include metal catalysts and amine-based catalysts.
- metal catalysts include, but are not limited to, tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctate, lead catalysts such as lead octylate, lead octenoate, and lead naphthenate, bismuth octylate, and neodecane.
- Bismuth catalysts such as bismuth oxide and the like can be mentioned.
- the amine-based catalyst include, but are not particularly limited to, tertiary amine compounds such as triethylenediamine.
- the method for producing the polyurethane resin composition is not particularly limited, and it can be produced by a known method.
- the decanediol-derived polycarbonate polyol, the polyhydric alcohol, the polyol having an anionic hydrophilic group, other polyols, and polyisocyanate are reacted to form an isocyanate-terminated urethane prepolymer. Synthesize.
- the reaction is carried out without solvent or in an organic solvent without active hydrogen groups.
- dispersion emulsification is carried out in water.
- the equivalent ratio of the isocyanate groups of the polyisocyanate to the sum of the hydroxyl groups of the polyol and the amino groups of the chain extender is preferably 1:0.85 to 1.1.
- a surfactant When dispersing and emulsifying the isocyanate-terminated urethane prepolymer in water, a surfactant may be used as an emulsifier.
- surfactants include, but are not particularly limited to, nonionic surfactants, anionic surfactants, cationic surfactants, and the like. These surfactants may be used alone or in combination of two or more.
- nonionic surfactants include, but are not limited to, alcohols having 8 to 24 carbon atoms, alkenols having 8 to 24 carbon atoms, polycyclic phenols, amines having 8 to 44 carbon atoms, and 8 carbon atoms. 44 amides, fatty acids with 8 to 24 carbon atoms, polyhydric alcohol fatty acid esters, oils and fats, alkylene oxide adducts of polypropylene glycol, alkylene oxide adducts of polycyclic phenols, Pluronic (registered trademark) type non- Examples include ionic surfactants.
- Alkylene oxide adducts of polycyclic phenols are not particularly limited, but for example, polyoxyethylene distyrylphenyl ether type nonionic surfactants, polyoxyethylene polyoxypropylene distyrylphenyl ether type nonionic surfactants, Examples include polyoxyethylene tristyrylphenyl ether type nonionic surfactants, polyoxyethylene polyoxypropylene tristyrylphenyl ether type nonionic surfactants, and the like.
- polyoxyethylene distyrylphenyl ether type nonionic surfactants examples include polyoxyethylene tristyrylphenyl ether type nonionic surfactants, polyoxyethylene polyoxypropylene tristyrylphenyl ether type nonionic surfactants, and the like.
- two or more alkylene oxides are added to the nonionic surfactant, either block addition or random addition may be used.
- anionic surfactants include, but are not particularly limited to, alcohols, alkenols, anionic products of alkylene oxide adducts of the above nonionic surfactants, and the like.
- cationic surfactants include, but are not limited to, monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, carbon Examples thereof include dialkylamine acetates having 8 to 24 carbon atoms, alkylimidazoline quaternary salts having 8 to 24 carbon atoms, and the like.
- the surfactant is preferably a nonionic surfactant, more preferably an alkylene oxide adduct of a polycyclic phenol, or a Pluronic (registered trademark) type nonionic surfactant. .
- the amount of surfactant used is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the isocyanate-terminated urethane prepolymer solid content. Moreover, 10 mass parts or less are preferable and 8 mass parts or less are more preferable. When the amount of the surfactant used is within the above range, it is possible to obtain a polyurethane resin composition having excellent wear resistance and flexibility at low temperatures.
- the molecular weight of the polyurethane resin composition is not particularly limited.
- the weight-average molecular weight is measured using a GPC apparatus using tetrahydrofuran (THF) as a solvent, and obtained as a polystyrene equivalent value.
- Specific measurement conditions are as follows. Column: Tosoh polystyrene gel column (TSK gel G4000HXL + TSK gel G3000HXL + TSK gel G2000HXL + TSK gel G1000HXL connected in series in this order) Column temperature: 40°C Detector: differential refractive index detector (RID-6A manufactured by Shimadzu Corporation) Flow rate: 1 ml/min.
- the acid value of the polyurethane resin composition is not particularly limited. For example, it is preferably 0.1 mgKOH/g to 20 mgKOH/g, more preferably 0.3 mgKOH/g to 15 mgKOH/g.
- the acid value indicates the acid value measured according to JIS K0070-1992.
- the polyurethane resin composition of the present embodiment is excellent in abrasion resistance and flexibility at low temperatures, so it can be effectively used as artificial leather or the like.
- the method for producing an artificial leather from the polyurethane resin composition of the present embodiment is not particularly limited, and conventional methods can be used. For example, after the polyurethane resin composition is applied to a release paper, water is evaporated to form a skin layer, an adhesive is applied to the skin layer, and then the fiber fabric layer is laminated to evaporate the water. Thus, artificial leather can be produced.
- This method is a method of producing a fiber laminate comprising a skin layer formed using the polyurethane resin composition of the present embodiment and a fiber fabric layer, and this fiber laminate corresponds to artificial leather.
- the obtained artificial leather can be used for, for example, vehicles, furniture, clothes, shoes, bags, bags, sandals, miscellaneous goods and the like.
- the artificial leather may further include a layer (for example, a metal layer, etc.) other than the skin layer and the fiber fabric layer.
- the adhesive used in this method is not particularly limited as long as it can bond the skin layer and the fiber base material together, and examples thereof include polyurethane adhesives.
- a cured product can be obtained by drying the polyurethane resin composition of the present embodiment. Further, the cured product and fiber laminate obtained in the present embodiment may be further subjected to post-processing such as surface treatment and kneading.
- Example 7 Polyurethane resin compositions of Examples and Comparative Examples were prepared according to the formulations (parts by mass) shown in the table below. In Example 8, instead of isophoronediamine used in Example 1, diethylenetriamine was used.
- Example 1 A polycarbonate diol having a structural unit derived from 1,10-decanediol, 4,4'-dicyclohexylmethane diisocyanate, a polyhydric alcohol having three or more hydroxy groups as functional groups, dimethylolpropionic acid, and methyl ethyl ketone. was added and allowed to react at 70-75°C for 120 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.8% by mass. The prepolymer was cooled to 35° C. and neutralized by adding triethylamine.
- this solution was emulsified using a homogenizer while gradually adding water.
- An aqueous solution of isophoronediamine dissolved in the resulting emulsified dispersion was added, and after confirming the disappearance of free isocyanate groups, methyl ethyl ketone was distilled off to obtain a polyurethane resin composition having a solid content of 40% by mass and an acid value of 4.2 mgKOH/g.
- An aqueous dispersion of the product was obtained.
- aqueous dispersion of the polyurethane resin composition was cast on release paper so that the dry film thickness was 200 ⁇ m, and then dried at 80° C. for 6 hours to prepare a film.
- Flexibility was evaluated as follows. ⁇ : 5.0 MPa or less ⁇ : More than 5.0 MPa and 8.0 MPa or less ⁇ : More than 8.0 MPa and 10.0 MPa or less ⁇ : More than 10.0 MPa
- Abrasion resistance was evaluated as follows. ⁇ : No damage or peeling at 2000 times of friction ⁇ : Damage or peeling occurred at 1000 or more and less than 2000 times of friction ⁇ : Damage or peeling occurred at less than 1000 times of friction
- the examples containing polyhydric alcohols having 3 or more hydroxy groups and a number average molecular weight of 420 or more and 2000 or less are comparative examples containing polyhydric alcohols having 3 or more hydroxy groups but a number average molecular weight of less than 420.
- Example 1 and Comparative Example 2 containing a polyhydric alcohol having three or more hydroxy groups and a number average molecular weight exceeding 2000 it was found to have excellent wear resistance and excellent flexibility at low temperatures. .
- the present invention is not limited to the above-described embodiments, and can be implemented in various configurations without departing from the spirit of the present invention.
- the technical features in the embodiments and examples corresponding to the technical features in each form described in the Summary of the Invention are used to solve some or all of the above problems, or In order to achieve some or all of the effects, it is possible to appropriately replace or combine them.
- the technical features are not described as essential in this specification, they can be deleted as appropriate.
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Abstract
Description
本発明の実施形態であるポリウレタン樹脂組成物は、1,10-デカンジオールに由来する構造単位を有するポリカーボネートポリオールと、官能基としてヒドロキシ基のみを3つ以上有する数平均分子量420以上2000以下の多価アルコール(以下、単に「多価アルコール」とも呼ぶ)と、アニオン性親水性基を有するポリオールと、を含むポリオールと、ポリイソシアネートと、の反応物を、ポリアミンにより鎖伸長したものであることを特徴とする。本実施形態のポリウレタン樹脂組成物は、水分散体の形態として存在することができる。本実施形態のポリウレタン樹脂組成物は、耐久性に優れるとともに、低温での柔軟性に優れる。
本実施形態のポリウレタン樹脂組成物に用いられるポリオール成分(A)は、1,10-デカンジオールに由来する構造単位を有するポリカーボネートポリオール(以下、「デカンジオール由来ポリカーボネートポリオール」とも呼ぶ)と、官能基としてヒドロキシ基のみを3つ以上有する数平均分子量420以上2000以下の多価アルコールと、アニオン性親水性基を有するポリオールと、を含む。
デカンジオール由来ポリカーボネートポリオールの数平均分子量は、特に限定されないが、低温での柔軟性に優れる観点から、800以上が好ましく、900以上がより好ましく、950以上がさらに好ましい。一方、デカンジオール由来ポリカーボネートポリオールの数平均分子量は、取り扱いに優れる観点から、3400以下が好ましく、3200以下がより好ましく、3100以下がさらに好ましい。
官能基としてヒドロキシ基のみを3つ以上有する数平均分子量420以上2000以下の多価アルコールとしては、特に限定されないが、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等が挙げられる。本実施形態の多価アルコールとしては、耐久性と低温での柔軟性とに優れる観点から、ポリエーテルポリオールが好ましい。
本明細書において、アニオン性親水性基としては、カルボキシ基又はその塩、スルホン酸基又はその塩を示す。
ポリオールとしては、上記のデカンジオール由来ポリカーボネートポリオールと、上記の多価アルコールと、上記のアニオン性親水性基を有するポリオール以外のポリオールとして、安定な乳化体を得ることができるため、エチレングリコールに由来する構造単位を有するポリエーテルポリオールを有することが好ましい。エチレングリコールに由来する構造単位を有するポリエーテルポリオールとしては、特に限定されないが、例えば、ポリオキシエチレンポリオキシプロピレンランダム共重合体グリコール、ポリエチレングリコールなどが挙げられる。ポリオキシエチレンポリオキシプロピレンランダム共重合体グリコールとしては、例えば、アデカポリエーテルPR-3007(ADEKA社製、分子量:3000、オキシエチレン基含有量:70%)等が挙げられる。ポリエチレングリコールとしては、例えば、PEG-600S(第一工業製薬社製、分子量:600)等が挙げられる。
本実施形態のポリウレタン樹脂組成物に用いられるポリイソシアネートは、特に限定されないが、例えば、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネート等を挙げることができる。耐摩耗性と低温での柔軟性とに優れる観点から、ポリイソシアネートとしては、脂環族ポリイソシアネートを含むことが好ましい。
本実施形態のポリウレタン樹脂組成物に用いられるポリアミンは、特に限定されないが、例えば、当該技術分野で一般的に使用される鎖伸長剤を用いることができる。ポリアミンとしては、例えば、ジアミン、トリアミン、テトラアミンが挙げられる。ジアミンとしては、例えば、エチレンジアミン、トリメチレンジアミン、ピペラジン、イソホロンジアミン等が挙げられる。トリアミンとしては、例えば、ジエチレントリアミン、ジプロピレントリアミン等が挙げられる。トリアミンとしては、例えば、トリエチレンテトラミン等が挙げられる。
本実施形態のポリウレタン樹脂組成物は、本発明の効果を阻害しない範囲で他の材料を含んでいてもよい。他の材料としては、特に限定されないが、例えば、上記ポリアミン以外の鎖伸長剤、架橋剤、触媒等が挙げられる。
ポリウレタン樹脂組成物の製造方法は、特に限定されず、公知の方法により製造することができる。例えば、まず、上記デカンジオール由来ポリカーボネートポリオールと、上記多価アルコールと、上記アニオン性親水性基を有するポリオールと、その他のポリオールと、ポリイソシアネートとを、反応させることによりイソシアネート末端のウレタンプレポリマーを合成する。この反応は、溶剤なしで行うか、または活性水素基を有しない有機溶媒中で行う。その後、必要に応じてアニオン性親水基の中和を行った後、水中において分散乳化を行う。その後、上記ウレタンプレポリマーに残存するイソシアネート基より少ない当量の鎖伸長剤(例えば、イソシアネート基と鎖伸長剤中のアミノ基との当量比1:0.5~0.95)を加えた後、乳化ミセル中のイソシアネート基と鎖伸長剤とを界面重合反応させることにより、ウレア結合を生成させる。この反応によって、乳化ミセル内の高分子量化が進み、ポリウレタン樹脂水分散体が得られる。その後、必要に応じて使用した溶剤を除去することにより、ポリウレタン樹脂組成物の水分散体を得ることができる。この方法では、ポリイソシアネートのイソシアネート基と、上記ポリオールの水酸基および鎖伸長剤のアミノ基の合計と、の当量比は、1:0.85~1.1であることが好ましい。
カラム:東ソー社製のポリスチレンゲルカラム(TSK gel G4000HXL+TSK gel G3000HXL+TSK gel G2000HXL+TSK gel G1000HXL2本をこの順で直列に接続)
カラム温度:40℃
検出器:示差屈折率検出器(島津製作所社製のRID-6A)
流速:1ml/分。
(1,10-デカンジオールに由来する構造単位を有するポリカーボネートジオール)
・BENEBiOL(登録商標)NL1010DB(三菱化学社製)(官能基数:2、数平均分子量:1000)
・BENEBiOL(登録商標)NL2010DB(三菱化学社製)(官能基数:2、数平均分子量:2000)
・BENEBiOL(登録商標)NL2030DB(三菱化学社製)(官能基数:2、数平均分子量:2000)
・BENEBiOL(登録商標)NL3010DB(三菱化学社製)(官能基数:2、数平均分子量:3000)
(ポリイソシアネート)
・4,4´-ジシクロヘキシルメタンジイソシアネート(官能基数:2、数平均分子量:262)
(官能基としてヒドロキシ基を3つ以上有する多価アルコール)
・サンニックスGP-600(三洋化成社製)(官能基数:3、数平均分子量:600)
・エクセノール430(旭硝子社製)(官能基数:3、数平均分子量:420)
・エクセノール1030(旭硝子社製)(官能基数:3、数平均分子量:1000)
・エクセノール410NE(旭硝子社製)(官能基数:4、数平均分子量:547)
・エクセノール3030(旭硝子社製)(官能基数:3、数平均分子量:3000)(比較例)
・トリメチロールプロパン(官能基数:3、数平均分子量:134.17)(比較例)
(エチレングリコールに由来する構造単位を有するポリエーテルポリオール)
・アデカポリエーテルPR-3007(ADEKA社製)(官能基数:2、数平均分子量:3000)
・ポリエチレングリコール(第一工業製薬社製PEG-600S)(官能基数:2、数平均分子量:600)
(アニオン性親水基を有するポリオール)
・ジメチロールプロピオン酸(Perstorp社製Bis-MPA(登録商標))(官能基数:2、数平均分子量:134.13)
(その他)
・トリエチルアミン(数平均分子量:101.19)
・イソホロンジアミン(鎖伸長剤)
・ジエチレントリアミン(鎖伸長剤)
以下の表に示す配合(質量部)に従って、実施例及び比較例のポリウレタン樹脂組成物を作製した。なお、実施例8では、実施例1で用いたイソホロンジアミンの代わりにジエチレントリアミンを用いた。
[実施例1]
1,10-デカンジオールに由来する構造単位を有するポリカーボネートジオールと、4,4´-ジシクロヘキシルメタンジイソシアネートと、官能基としてヒドロキシ基を3つ以上有する多価アルコールと、ジメチロールプロピオン酸と、メチルエチルケトンとを添加し、70~75℃で120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1.8質量%であった。このプレポリマーを35℃まで冷却し、トリエチルアミンを添加し中和を行った。その後、この溶液に水を徐々に加えながらホモジナイザーを使用して乳化させた。得られた乳化分散体に、イソホロンジアミンを溶解した水溶液を添加し、遊離イソシアネート基の消失を確認した後、メチルエチルケトンを留去し固形分40質量%、酸価4.2mgKOH/gのポリウレタン樹脂組成物の水分散体を得た。
得られたポリウレタン樹脂組成物の水分散体を、乾燥膜厚が200μmとなるように離型紙にキャストした後、80℃で6時間乾燥させることにより、皮膜を作製した。
得られた皮膜をあらかじめ定められた大きさに裁断した試料を、JIS K 6301に準じて、引張速度200mm/分で引っ張り、規定の伸びを与えたときの応力(100%モジュラス)を測定した。柔軟性の評価は、試料を作成した直後と、5℃で2週間保持した後と、5℃で4週間保持した後との3度行った。応力が小さいほど、柔軟性に優れる。
◎:5.0MPa以下
○:5.0MPa超8.0MPa以下
△:8.0MPa超10.0MPa以下
×:10.0MPa超
平面摩耗試験機(大栄科学精器製作所社製PA-300A)を用いて、荷重500g/cm2、60回/分にて、得られた皮膜の表面を2000回摩擦し、傷の発生の有無を目視により観察した。傷や剥がれが起こらないほど、耐摩耗性に優れる。
◎:摩擦回数2000回で傷、剥がれ無し
○:摩擦回数1000回以上2000回未満で傷又は剥がれ発生
△:摩擦回数1000回未満で傷又は剥がれが発生
Claims (8)
- 1,10-デカンジオールに由来する構造単位を有するポリカーボネートポリオールと、官能基としてヒドロキシ基のみを3つ以上有する数平均分子量420以上2000以下の多価アルコールと、アニオン性親水性基を有するポリオールと、を含むポリオールと、
ポリイソシアネートと、
の反応物を、ポリアミンにより鎖伸長したものであることを特徴とする、ポリウレタン樹脂組成物。 - 請求項1に記載のポリウレタン樹脂組成物であって、
前記ポリオールとして、さらに、エチレングリコールに由来する構造単位を有するポリエーテルポリオールを含むことを特徴とする、ポリウレタン樹脂組成物。 - 請求項1又は請求項2に記載のポリウレタン樹脂組成物であって、
前記1,10-デカンジオールに由来する構造単位を有するポリカーボネートポリオールの前記ポリオール中に占める配合割合が50質量%以上97質量%以下であることを特徴とする、ポリウレタン樹脂組成物。 - 請求項1又は請求項2に記載のポリウレタン樹脂組成物であって、
前記多価アルコールの全ポリオール中に占める配合割合が3質量%以上20質量%以下であることを特徴とする、ポリウレタン樹脂組成物。 - 請求項1から請求項4までのいずれか1項に記載のポリウレタン樹脂組成物であって、
前記多価アルコールの数平均分子量が500以上1000以下であることを特徴とする、ポリウレタン樹脂組成物。 - 請求項1から請求項5までのいずれか1項に記載のポリウレタン樹脂組成物の硬化物。
- 請求項1から請求項5までのいずれか1項に記載のポリウレタン樹脂組成物を用いて形成された表皮層と、繊維布帛層とを備えることを特徴とする、繊維積層体。
- 請求項7に記載の繊維積層体を備えることを特徴とする、人工皮革。
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Citations (5)
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JP2016027114A (ja) * | 2014-06-23 | 2016-02-18 | 三菱化学株式会社 | 合成皮革用ポリウレタン |
JP2017119755A (ja) | 2015-12-28 | 2017-07-06 | 日華化学株式会社 | 水分散型ポリカーボネート系ポリウレタン樹脂組成物、それを用いて処理した繊維製品、及び水分散型ポリカーボネート系ポリウレタン樹脂組成物の製造方法 |
WO2018159359A1 (ja) * | 2017-02-28 | 2018-09-07 | 三洋化成工業株式会社 | 合成皮革用ポリウレタン樹脂 |
JP2019044292A (ja) * | 2017-08-31 | 2019-03-22 | 東レ株式会社 | シート状物 |
WO2020129605A1 (ja) * | 2018-12-18 | 2020-06-25 | Dic株式会社 | ウレタン樹脂組成物、皮膜、及び、合成皮革 |
-
2021
- 2021-02-17 JP JP2021023106A patent/JP6937950B1/ja active Active
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2022
- 2022-01-31 EP EP22755904.4A patent/EP4296054A1/en active Pending
- 2022-01-31 KR KR1020237023180A patent/KR20230145048A/ko unknown
- 2022-01-31 CN CN202280013362.7A patent/CN116848165A/zh active Pending
- 2022-01-31 US US18/273,308 patent/US20240117099A1/en active Pending
- 2022-01-31 WO PCT/JP2022/003481 patent/WO2022176582A1/ja active Application Filing
- 2022-02-08 TW TW111104455A patent/TW202233712A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016027114A (ja) * | 2014-06-23 | 2016-02-18 | 三菱化学株式会社 | 合成皮革用ポリウレタン |
JP2017119755A (ja) | 2015-12-28 | 2017-07-06 | 日華化学株式会社 | 水分散型ポリカーボネート系ポリウレタン樹脂組成物、それを用いて処理した繊維製品、及び水分散型ポリカーボネート系ポリウレタン樹脂組成物の製造方法 |
WO2018159359A1 (ja) * | 2017-02-28 | 2018-09-07 | 三洋化成工業株式会社 | 合成皮革用ポリウレタン樹脂 |
JP2019044292A (ja) * | 2017-08-31 | 2019-03-22 | 東レ株式会社 | シート状物 |
WO2020129605A1 (ja) * | 2018-12-18 | 2020-06-25 | Dic株式会社 | ウレタン樹脂組成物、皮膜、及び、合成皮革 |
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TW202233712A (zh) | 2022-09-01 |
JP2022125494A (ja) | 2022-08-29 |
JP6937950B1 (ja) | 2021-09-22 |
KR20230145048A (ko) | 2023-10-17 |
US20240117099A1 (en) | 2024-04-11 |
EP4296054A1 (en) | 2023-12-27 |
CN116848165A (zh) | 2023-10-03 |
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