JP6937951B1 - 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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- JP6937951B1 JP6937951B1 JP2021023107A JP2021023107A JP6937951B1 JP 6937951 B1 JP6937951 B1 JP 6937951B1 JP 2021023107 A JP2021023107 A JP 2021023107A JP 2021023107 A JP2021023107 A JP 2021023107A JP 6937951 B1 JP6937951 B1 JP 6937951B1
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- Prior art keywords
- polyurethane resin
- resin composition
- polyol
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- Prior art date
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 52
- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 239000000835 fiber Substances 0.000 title claims description 15
- 239000002649 leather substitute Substances 0.000 title claims description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 60
- 150000003077 polyols Chemical class 0.000 claims abstract description 60
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 28
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 28
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 24
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
- 229920000768 polyamine Polymers 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 27
- 229920000570 polyether Polymers 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 5
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000010586 diagram Methods 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 description 14
- -1 polymethylene Polymers 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 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
- 239000004970 Chain extender Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 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
- 239000004094 surface-active agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 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
- 230000000052 comparative effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 210000003491 skin Anatomy 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 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
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920005906 polyester polyol 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
- 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 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000013329 compounding Methods 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
- 210000002615 epidermis Anatomy 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 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
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 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
- 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
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 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
- 159000000021 acetate salts 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
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 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
- 125000005265 dialkylamine group Chemical group 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
- 150000002009 diols Chemical class 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-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
- 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
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method 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
- 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
- AVWRKZWQTYIKIY-UHFFFAOYSA-M urea-1-carboxylate Chemical group NC(=O)NC([O-])=O AVWRKZWQTYIKIY-UHFFFAOYSA-M 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
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Abstract
Description
(1)本発明の一形態によれば、ポリウレタン樹脂組成物が提供される。このポリウレタン樹脂組成物は、ポリテトラメチレンエーテルグリコールとポリプロピレングリコールとの少なくとも一方のポリエーテルポリオールと、1,10−デカンジオールと、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り、前記ポリエーテル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90質量%以下であり、前記1,10−デカンジオールの前記ポリオール中に占める配合割合が1質量%以上30質量%以下であることを特徴とする。
その他、本発明は、以下の形態として実現することができる。
本発明の実施形態であるポリウレタン樹脂組成物は、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。本実施形態のポリオールは、ポリテトラメチレンエーテルグリコール(以下、「PTMG」とも呼ぶ)とポリプロピレングリコール(以下、「PPG」とも呼ぶ)との少なくとも一方のポリエーテルポリオールと、1,10−デカンジオールと、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。
(ポリテトラメチレンエーテルグリコール)
本実施形態のポリテトラメチレンエーテルグリコール(PTMG)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、PTMGの数平均分子量は、例えば、500以上が好ましく、800以上がより好ましく、1500以上がさらに好ましく、1800以上が特に好ましい。一方、耐摩耗性に優れる観点から、PTMGの数平均分子量は、例えば、3400以下が好ましく、3000以下がより好ましく、2500以下がさらに好ましく、2300以下が特に好ましい。
本実施形態のポリプロピレングリコール(PPG)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、PPGの数平均分子量は、例えば、500以上が好ましく、800以上がより好ましく、1500以上がさらに好ましく、1800以上が特に好ましい。一方、耐摩耗性に優れる観点から、PPGの数平均分子量は、例えば、3400以下が好ましく、3000以下がより好ましく、2500以下がさらに好ましく、2300以下が特に好ましい。ポリエーテルポリオールとしては、耐久性に優れるとともに、低温での柔軟性に優れる観点から、PTMGを含むことが好ましい。
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。
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、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、ポリテトラメチレンエーテルグリコールとポリプロピレングリコールとの少なくとも一方のポリエーテルポリオールと、1,10−デカンジオールと、上記アニオン性親水性基を有するポリオールと、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張剤(例えば、イソシアネート基と鎖伸張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張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張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。
人工皮革等として有効に用いることができる。本実施形態のポリウレタン樹脂組成物で人工皮革を作製する方法としては、特に限定されず、従来の方法を用いることができる。例えば、ポリウレタン樹脂組成物を離型紙に塗布した後、水分を蒸発させることにより表皮層を形成し、この表皮層のうえに接着剤を塗布した後、繊維布帛層と貼り合わせて水分を蒸発させることにより、人工皮革を作製することができる。この方法は、本実施形態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繊維積層体を作製する方法であり、この繊維積層体が人工皮革に相当する。得られた人工皮革は、例えば、車両、家具、衣料、靴、鞄、袋物、サンダル、雑貨等に使用することができる。人工皮革としては、さらに表皮層や繊維布帛層以外の層(例えば、金属層等)を備えていてもよい。この方法に使用する接着剤は表皮層と繊維基材を貼り合わせることのできるものであれば特に限定されないが、例えば、ポリウレタン接着剤が挙げられる。また、本実施形態のポリウレタン樹脂組成物を乾燥させることにより硬化物を得ることができる。また、本実施形態で得られた硬化物や繊維積層体は、更に、表面処理、揉み加工等の後加工を施してもよい。
(i)ポリオール
(PTMG)
・PolyTHF(登録商標)2000(三菱ケミカル社製)(官能基数:2、数平均分子量:2000)
・PolyTHF(登録商標)1000(三菱ケミカル社製)(官能基数:2、数平均分子量:1000)
・PolyTHF(登録商標)3000(三菱ケミカル社製)(官能基数:2、数平均分子量:3000)
(PPG)
・エクセノール2020(旭硝子社製)(官能基数:2、数平均分子量:2000)
(デカンジオール)
・1,10−デカンジオール(豊国製油社製)(官能基数:2、数平均分子量:174.28)
(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)
(その他のポリオール)
・デュラノール(登録商標)T4672(旭化成社製)(官能基数:2、数平均分子量:2000)
・ニッポラン4010(東ソー社製)(官能基数:2、数平均分子量:2000)
・テスラックTA22−781(日立化成社製)(官能基数:2、数平均分子量:1780)
・ポリエチレングリコール(第一工業製薬社製PEG−2000)(官能基数:2、数平均分子量:2000)
・トリメチロールプロパン(三菱ガス化学社製)(官能基数:3、数平均分子量:134.17)
・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)
(ポリイソシアネート)
・IPDI(VESTANAT(登録商標)IPDI(Evonik社製))(官能基数:2、数平均分子量:222.29)
(その他)
・トリエチルアミン(ダイセル社製)(数平均分子量:101.19)
・イソホロンジアミン(VESTAMIN(登録商標)IPD(Evonik社製))
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。
[実施例1]
PTMGと、1,10−デカンジオールと、トリメチロールプロパンと、IPDIと、ジメチロールプロピオン酸と、ポリエチレングリコール(第一工業製薬社製PEG−600S)と、メチルエチルケトンとを混合し、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6.3mgKOH/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回未満で傷または剥がれ発生
△:摩擦回数1000回未満で傷または剥がれが発生
Claims (7)
- ポリテトラメチレンエーテルグリコールとポリプロピレングリコールとの少なくとも一方のポリエーテルポリオールと、1,10−デカンジオールと、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り、
前記ポリエーテル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90質量%以下であり、
前記1,10−デカンジオールの前記ポリオール中に占める配合割合が1質量%以上30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に記載のポリウレタン樹脂組成物であって、
前記ポリエーテルポリオールとして、ポリテトラメチレンエーテルグリコ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、
前記ポリエーテルポリオールの前記ポリオール中に占める配合割合が60質量%以上90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3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、
前記ポリエーテルポリオールの数平均分子量が500以上2500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の硬化物。
- 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6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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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 |
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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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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 |
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