WO2022097331A1 - Urethane resin composition, film, laminate, and synthetic leather - Google Patents
Urethane resin composition, film, laminate, and synthetic leather Download PDFInfo
- Publication number
- WO2022097331A1 WO2022097331A1 PCT/JP2021/028037 JP2021028037W WO2022097331A1 WO 2022097331 A1 WO2022097331 A1 WO 2022097331A1 JP 2021028037 W JP2021028037 W JP 2021028037W WO 2022097331 A1 WO2022097331 A1 WO 2022097331A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urethane resin
- resin composition
- film
- mass
- synthetic leather
- Prior art date
Links
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 95
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 239000002649 leather substitute Substances 0.000 title claims abstract description 16
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 14
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims description 22
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 229920001228 polyisocyanate Polymers 0.000 claims description 20
- 125000003277 amino group Chemical group 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 230000008961 swelling Effects 0.000 abstract description 22
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 description 37
- -1 sheets Substances 0.000 description 32
- 229920005862 polyol Polymers 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 5
- 230000000740 bleeding effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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 compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000002335 surface treatment layer Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- HSZGXYFZPBCFSP-UHFFFAOYSA-N 2,6-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(N)=C1S(O)(=O)=O HSZGXYFZPBCFSP-UHFFFAOYSA-N 0.000 description 1
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- SPGHPHFQNQIZME-UHFFFAOYSA-N 2-n-ethylethane-1,1,2-triamine Chemical compound CCNCC(N)N SPGHPHFQNQIZME-UHFFFAOYSA-N 0.000 description 1
- JIRLWRUWVNHTQG-UHFFFAOYSA-N 3,4-diaminobutane-1-sulfonic acid Chemical compound NCC(N)CCS(O)(=O)=O JIRLWRUWVNHTQG-UHFFFAOYSA-N 0.000 description 1
- XJIIBKORMYCKON-UHFFFAOYSA-N 3,6-diamino-2-methylbenzenesulfonic acid Chemical compound CC1=C(N)C=CC(N)=C1S(O)(=O)=O XJIIBKORMYCKON-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 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
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 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
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 229960002887 deanol Drugs 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PJMICNUGBHGMKQ-UHFFFAOYSA-N ethane-1,1,2-triamine Chemical compound NCC(N)N PJMICNUGBHGMKQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229950001413 metamfepramone Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- GXMIHVHJTLPVKL-UHFFFAOYSA-N n,n,2-trimethylpropanamide Chemical compound CC(C)C(=O)N(C)C GXMIHVHJTLPVKL-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
-
- 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
-
- 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
- C08G18/08—Processes
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
-
- 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
- D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/06—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 by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
- D06N3/08—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 by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products with a finishing layer consisting of polyacrylates, polyamides or polyurethanes or polyester
-
- 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
Definitions
- the present invention is a urethane resin composition containing a urethane resin, and after immersing a film having a thickness of 30 ⁇ m, a length of 3 cm, and a width of 3 cm formed of the urethane resin composition in a plasticizer for 24 hours. It is an object of the present invention to provide a urethane resin composition characterized in that the swelling rate of the film is 10% or more.
- the present invention provides a film characterized by being formed of the urethane resin composition. Further, the present invention provides at least a polyvinyl chloride layer and a laminate characterized by having the film. Furthermore, the present invention provides synthetic leather characterized by having at least a polyvinyl chloride layer, the film, and a surface-treated layer in that order.
- urethane resin for example, a solvent-based urethane resin composition containing an organic solvent; an aqueous urethane resin composition containing water, or the like can be used.
- a water-based urethane resin composition is preferable from the viewpoint of reducing the environmental load.
- the content of the polyether polyol in the polyol (a1-1) is preferably 30% by mass or more, preferably 50% by mass or more.
- a polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
- the concentration of the hydrophilic group of the urethane resin is adjusted to further improve the water dispersion stability, hydrolysis resistance, and peel strength. From the viewpoint of immediate peeling property, bleeding resistance, and light resistance, the range of 0.01 to 10% by mass is preferable, and the range of 0.1 to 5% by mass is more preferable in the raw materials constituting the urethane resin. preferable.
- the same one as the polyol (a1-1) can be used, the swelling rate of the film can be easily adjusted to a specific range, and even better bleed resistance can be obtained.
- a polyether polyol is preferable, and a polytetramethylene glycol is more preferable.
- Examples of the synthetic leather include those having a base material, a thermoplastic resin layer, a film formed of the urethane resin composition, and a surface treatment layer in sequence.
- the surface treatment layer for example, a layer formed of a known solvent-based urethane resin, water-based urethane resin, solvent-based acrylic resin, water-based acrylic resin, or the like can be used.
- the bleed resistance was evaluated as follows. " ⁇ ”; 10% or more. "X”; less than 10%.
- Example 2 ⁇ Preparation of water-based urethane resin composition (2)> A water-based urethane resin composition (2) and a film were obtained in the same manner as in Example 1 except that 110 parts by mass of dicyclohexylmethane diisocyanate was changed to 95 parts by mass of isophorone diisocyanate, and bleed resistance was evaluated.
- Examples 1 to 4 which are the urethane resin compositions of the present invention, are excellent in bleed resistance.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The present invention addresses the problem of providing a urethane resin composition having excellent plasticizer-bleeding inhibition. The present invention provides a urethane resin composition containing a urethane resin, the urethane resin composition being characterized in that the swelling rate of a film, which is formed of said urethane resin composition and has a thickness of 30 μm, a length of 3 cm, and a width of 3 cm, after being immersed in a plasticizer for 24 hours is at least 10%. Moreover, the present invention provides a film characterized by being formed of said urethane resin composition. Further, the present invention provides a laminate characterized by having at least a polyvinyl chloride layer and said film. Furthermore, the present invention provides a synthetic leather characterized by having at least a polyvinyl chloride layer, said film, and a surface-treated layer in this order.
Description
本発明は、ウレタン樹脂組成物、皮膜、積層体、及び、合成皮革に関する。
The present invention relates to a urethane resin composition, a film, a laminate, and synthetic leather.
ウレタン樹脂を含有するウレタン樹脂組成物は、合成皮革、人口皮革、フィルム、シート、接着剤、シート状物の表面処理などに広く利用されている。この中でも、車輛用内装材用の合成皮革などの長期間使用される部材に利用される場合には、より高い耐久性が要求される。
Urethane resin compositions containing urethane resin are widely used for surface treatment of synthetic leather, artificial leather, films, sheets, adhesives, sheet-like materials, and the like. Among these, higher durability is required when used for long-term use members such as synthetic leather for interior materials for vehicles.
一方、コスト面からポリ塩化ビニル（ＰＶＣ）を基材にコーティング又は貼り合わせたＰＶＣ合皮の需要が伸長するも、低温屈曲性等の課題があり、これを解決するため、ウレタン樹脂をＰＶＣ層上にコーティングした、いわゆるセミ合皮が台頭しつつある状況にある。しかしながら、係るセミ合皮では、ＰＶＣ層に含有される可塑剤のブリードを抑制する必要がある。
On the other hand, from the viewpoint of cost, although the demand for PVC synthetic leather coated or bonded with polyvinyl chloride (PVC) as a base material grows, there are problems such as low temperature flexibility, and in order to solve this, urethane resin is used as a PVC layer. The so-called semi-synthetic leather coated on top is emerging. However, in such semi-synthetic leather, it is necessary to suppress the bleeding of the plasticizer contained in the PVC layer.
本発明が解決しようとする課題は、可塑剤のブリード抑制に優れた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 suppressing bleeding of a plasticizer.
本発明は、ウレタン樹脂を含有するウレタン樹脂組成物であって、前記ウレタン樹脂組成物により形成された厚さ３０μｍ、縦３ｃｍ、及び、横３ｃｍのフィルムを、可塑剤に２４時間浸漬させた後のフィルムの膨潤率が、１０％以上であることを特徴とするウレタン樹脂組成物を提供することである。
The present invention is a urethane resin composition containing a urethane resin, and after immersing a film having a thickness of 30 μm, a length of 3 cm, and a width of 3 cm formed of the urethane resin composition in a plasticizer for 24 hours. It is an object of the present invention to provide a urethane resin composition characterized in that the swelling rate of the film is 10% or more.
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を提供するものである。また、本発明は、少なくとも、ポリ塩化ビニル層、及び、前記皮膜を有することを特徴とする積層体を提供するものである。更に、本発明は、少なくとも、ポリ塩化ビニル層、前記皮膜、及び、表面処理層を順次有することを特徴とする合成皮革を提供するものである。
Further, the present invention provides a film characterized by being formed of the urethane resin composition. Further, the present invention provides at least a polyvinyl chloride layer and a laminate characterized by having the film. Furthermore, the present invention provides synthetic leather characterized by having at least a polyvinyl chloride layer, the film, and a surface-treated layer in that order.
本発明のウレタン樹脂組成物は、可塑剤のブリード抑制（以下、「耐ブリード性」と略記する。）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、ポリ塩化ビニル層を有する合成皮革の製造に特に好適に使用することができる。
The urethane resin composition of the present invention is excellent in suppressing bleeding of a plasticizer (hereinafter, abbreviated as "bleed resistance"). Therefore, the urethane resin composition of the present invention can be particularly suitably used for producing synthetic leather having a polyvinyl chloride layer.
本発明のウレタン樹脂組成物は、ウレタン樹脂を含有するものであり、前記ウレタン樹脂組成物により形成された厚さ３０μｍ、縦３ｃｍ、及び、横３ｃｍのフィルムを、可塑剤に２４時間浸漬させた後のフィルムの膨潤率（以下、「フィルムの膨潤率」と略記する。）が、１０％以上であることが必須である。
The urethane resin composition of the present invention contains a urethane resin, and a film having a thickness of 30 μm, a length of 3 cm, and a width of 3 cm formed by the urethane resin composition is immersed in a plasticizer for 24 hours. It is essential that the swelling rate of the subsequent film (hereinafter, abbreviated as "film swelling rate") is 10% or more.
前記フィルムの膨潤率が、係る条件を満たす場合には、優れた耐ブリード性を得ることができる。この理由としては、前記フィルムの膨潤率が１０％以上である場合には、フィルム中のウレタン樹脂が可塑剤を内包しやすくなるため、優れた耐ブリード性が得られるものと推察される。前記フィルムの膨潤率としては、より一層優れた耐ブリード性が得られる点から、１０～４０％の範囲が好ましく、１０～２５％の範囲がより好ましい。なお、前記フィルムの膨潤率の測定方法は、後述する実施例に詳述する。
When the swelling rate of the film satisfies the condition, excellent bleed resistance can be obtained. It is presumed that the reason for this is that when the swelling rate of the film is 10% or more, the urethane resin in the film easily contains a plasticizer, so that excellent bleed resistance can be obtained. The swelling rate of the film is preferably in the range of 10 to 40%, more preferably in the range of 10 to 25%, from the viewpoint of obtaining even better bleed resistance. The method for measuring the swelling rate of the film will be described in detail in Examples described later.
前記可塑剤としては、フタル酸ジオクチル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジブチル等のフタル酸エステル；アジピン酸ジオクチル、アジピン酸ジイソノニル等のアジピン酸エステル；トリメルット酸トリオクチル等のトリメリット酸エステル；リン酸トリクレシル等のリン酸エステル；アセチルクエン酸トリブチル等のクエン酸エステル；エポキシ化大豆油、エポキシ化アマニ油等のエポキシ化植物油；セバシン酸エステル；アゼライン酸エステル；マレイン酸エステル；安息香酸エステル；その他ポリエステルなどを用いることができる。これらの可塑剤は単独で用いても２種以上を併用してもよい。本発明においては、ポリ塩化ビニルによく使用されるフタル酸エステルに対しても優れた耐ブリード性を有する。
Examples of the plasticizer include phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate and dibutyl phthalate; adiponic acid esters such as dioctyl adipate and diisononyl adipate; trimellitic acid esters such as trioctyl trimertate; Phosphoric acid esters such as tricresyl phosphate; citrate esters such as acetyltributyl citrate; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; sevacinic acid ester; azelaic acid ester; maleic acid ester; benzoic acid ester; In addition, polyester or the like can be used. These plasticizers may be used alone or in combination of two or more. In the present invention, it also has excellent bleed resistance against phthalates often used for polyvinyl chloride.
前記ウレタン樹脂としては、例えば、有機溶剤を含む溶剤系ウレタン樹脂組成物；水を含む水系ウレタン樹脂組成物等を用いることができる。この中でも、環境負荷低減の点から、水系ウレタン樹脂組成物が好ましい。
As the urethane resin, for example, a solvent-based urethane resin composition containing an organic solvent; an aqueous urethane resin composition containing water, or the like can be used. Among these, a water-based urethane resin composition is preferable from the viewpoint of reducing the environmental load.
前記溶剤系ウレタン樹脂組成物としては、例えば、ウレタン樹脂、及び、有機溶剤を含むものが挙げられる。
Examples of the solvent-based urethane resin composition include urethane resins and those containing an organic solvent.
前記ウレタン樹脂としては、例えば、ポリオール（ａ１－１）、及び、ポリイソシアネート（ａ２－１）の反応物を用いることができる。
As the urethane resin, for example, a reactant of polyol (a1-1) and polyisocyanate (a2-1) can be used.
前記ポリオール（ａ１－１）としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、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。前記ポリオール（ａ１－１）としては、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、ポリエーテルポリオールが好ましく、ポリテトラメチレングリコールがより好ましい。
As the polyol (a1-1), for example, a polyester polyol, a polyether polyol, a polycarbonate polyol, or the like can be used. These polyols may be used alone or in combination of two or more. As the polyol (a1-1), a polyether polyol is preferable, and a polytetramethylene glycol is more preferable, because the swelling rate of the film can be easily adjusted to a specific range and even more excellent bleed resistance can be obtained.
前記ポリオール（ａ１－１）中における前記ポリエーテルポリオールの含有量としては、同様の理由から、３０質量％以上が好ましく、５０質量％以上が好ましい。
For the same reason, the content of the polyether polyol in the polyol (a1-1) is preferably 30% by mass or more, preferably 50% by mass or more.
前記ポリオール（ａ１－１）の数平均分子量としては、フィルムの機械的特性、及び、耐ブリード性の点から、５００～１０，０００の範囲であることが好ましく、７００～８，０００の範囲がより好ましい。なお、前記ポリオール（ａ１－１）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 polyol (a1-1) is preferably in the range of 500 to 10,000, preferably in the range of 700 to 8,000, from the viewpoint of the mechanical properties of the film and the bleed resistance. More preferred. The number average molecular weight of the polyol (a1-1) indicates a value measured by a gel permeation chromatography (GPC) method.
前記ポリオール（ａ１－１）には、必要に応じて、分子量が５００未満（好ましくは５０～４５０の範囲）の鎖伸長剤（ａ’１－１）を併用してもよい。前記鎖伸長剤（ａ’１－１）としては、例えば、水酸基を有する鎖伸長剤、アミノ基を有する鎖伸長剤等を用いることができる。これらの鎖伸長剤（ａ’１－１）は単独で用いても２種以上を併用してもよい。
If necessary, a chain extender (a'1-1) having a molecular weight of less than 500 (preferably in the range of 50 to 450) may be used in combination with the polyol (a1-1). As the chain extender (a'1-1), for example, a chain extender having a hydroxyl group, a chain extender having an amino group, or the like can be used. These chain extenders (a'1-1) may be used alone or in combination of two or more.
前記水酸基を有する鎖伸長剤としては、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、サッカロース、メチレングリコール、グリセリン、ソルビトール等の脂肪族ポリオール化合物；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、水素添加ビスフェノールＡ、ハイドロキノン等の芳香族ポリオール化合物；水など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。
Examples of the chain extender having a hydroxyl group include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol. Aliphatic polyol compounds such as saccharose, methylene glycol, glycerin, and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compound; water and the like can be used. These chain extenders may be used alone or in combination of two or more.
前記アミノ基を有する鎖伸長剤としては、例えば、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、４，４’－ジフェニルメタンジアミン、３，３’－ジクロロ－４，４’－ジフェニルメタンジアミン、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。
Examples of the chain extender having an amino group include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 4,4'-diphenylmethanediamine, 3,3'-dichloro-4,4'-diphenylmethanediamine, 1,2-cyclohexane Diamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine and the like can be used. These chain extenders may be used alone or in combination of two or more.
前記鎖伸長剤（ａ’１－１）としては、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、アミノ基を有する鎖伸長剤が好ましく、ピペラジン、ヒドラジン、イソホロンジアミン、及び、４，４’－ジシクロヘキシルメタンジアミンからなる群より選ばれる１種以上の化合物を用いることがより好ましい。
As the chain extender (a'1-1), a chain extender having an amino group is preferable because it is easy to adjust the swelling rate of the film to a specific range and further excellent bleed resistance can be obtained. It is more preferable to use one or more compounds selected from the group consisting of piperazine, hydrazine, isophoronediamine, and 4,4'-dicyclohexylmethanediamine.
前記鎖伸長剤（ａ’１－１）を用いる場合の使用量としては、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、ポリオール（ａ１－１）中０．１～８０質量％の範囲が好ましく、１～６０質量％の範囲がより好ましい。
When the chain extender (a'1-1) is used, the amount used is such that the swelling rate of the film can be easily adjusted to a specific range and even better bleed resistance can be obtained, so that the polyol (a1-) can be used. 1) The range of 0.1 to 80% by mass is preferable, and the range of 1 to 60% by mass is more preferable.
前記ポリイソシアネート（ａ２－１）としては、例えば、４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、クルードジフェニルメタンジイソシアネート、フェニレンジイソシアネート、トルエンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ポリイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、水添キシリレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート等の脂肪族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、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、脂肪族ポリイソシアネートが好ましく、ヘキサメチレンジイソシアネート、イソホロンジアミン、及び、ジシクロヘキシルメタンジイソシアネートからなる群より選ばれる１種以上のポリイソシアネートが好ましい。
Examples of the polyisocyanate (a2-1) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylenediisocyanate, toluenediisocyanate, naphthalenediocyanate, and xylylene diisocyanate. , Aromatic polyisocyanate such as tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexanediisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, aliphatic polyisocyanate such as dicyclohexylmethane diisocyanate and the like can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aliphatic polyisocyanates are preferable because the swelling rate of the film can be easily adjusted to a specific range and even better bleed resistance can be obtained, from hexamethylene diisocyanate, isophorone diamine, and dicyclohexylmethane diisocyanate. One or more kinds of polyisocyanates selected from the above group are preferable.
前記ポリイソシアネート（ａ２－１）中の前記脂肪族ポリイソシアネートの含有量としては、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、３０質量％以上が好ましく、５０質量％がより好ましい。
The content of the aliphatic polyisocyanate in the polyisocyanate (a2-1) is 30% by mass because the swelling rate of the film can be easily adjusted to a specific range and even better bleed resistance can be obtained. The above is preferable, and 50% by mass is more preferable.
前記ウレタン樹脂の製造方法としては、例えば、前記ポリオール（ａ１－１）と前記ポリイソシアネート（ａ２－１）と必要に応じて前記鎖伸長剤（ａ’１－１）とを仕込み、反応させることによって製造する方法が挙げられる。これらの反応は、５０～１００℃の温度で概ね３～１０時間行うことが好ましい。また、前記反応は、後述する有機溶剤中で行ってもよい。
As a method for producing the urethane resin, for example, the polyol (a1-1), the polyisocyanate (a2-1) and, if necessary, the chain extender (a'1-1) are charged and reacted. There is a method of manufacturing by. These reactions are preferably carried out at a temperature of 50 to 100 ° C. for about 3 to 10 hours. Further, the reaction may be carried out in an organic solvent described later.
前記ポリオール（ａ１－１）が有する水酸基並びに前記鎖伸長剤（ａ’１－１）が有する水酸基及びアミノ基の合計と、前記ポリイソシアネート（ａ２－１）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、０．８～１．２の範囲であることが好ましく、０．９～１．１の範囲であることがより好ましい。
The molar ratio of the total of the hydroxyl groups of the polyol (a1-1) and the hydroxyl groups and amino groups of the chain extender (a'1-1) to the isocyanate groups of the polyisocyanate (a2-1) [(). The isocyanate group) / (hydroxyl group and amino group)] is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.1.
前記ウレタン樹脂の重量平均分子量としては、フィルムの機械的特性、及び、耐ブリード性の点から、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、前記ウレタン樹脂の重量平均分子量は、前記ポリオール（ａ１－１）の数平均分子量と同様に測定して得られた値を示す。
The weight average molecular weight of the urethane resin is preferably in the range of 5,000 to 1,000,000 from the viewpoint of mechanical properties of the film and bleed resistance, and is preferably 10,000 to 500,000. The range is more preferred. The weight average molecular weight of the urethane resin indicates a value obtained by measuring in the same manner as the number average molecular weight of the polyol (a1-1).
前記ウレタン樹脂の含有量としては、例えば、溶剤系ウレタン樹脂組成物中１０～９０質量部の範囲が挙げられる。
The content of the urethane resin may be, for example, in the range of 10 to 90 parts by mass in the solvent-based urethane resin composition.
前記有機溶剤としては、例えば、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－メチルピロリドン、Ｎ，Ｎ，２－トリメチルプロピオンアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルプロピオンアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－エチルピロリドン、２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン、ジメチルスルホキシド等を用いることができる。これらの有機溶媒は単独で用いても２種以上を併用してもよい。また、必要に応じて、酢酸エチル、酢酸メチル、酢酸ブチル、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、イソプロピルアルコール、イソブタノール、ｓｅｃ－ブタノール、ターシャリーブタノール等の有機溶剤を併用してもよい。
Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N, 2-trimethylpropionamide, N, N-dimethylacrylamide, N, N-dimethylpropion. Amides, N, N-diethylacetamide, N, N-diethylacrylamide, N-ethylpyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like can be used. These organic solvents may be used alone or in combination of two or more. If necessary, an organic solvent such as ethyl acetate, methyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, isobutanol, sec-butanol, and tertiary butanol may be used in combination. good.
前記有機溶剤の含有量としては、例えば、溶剤系ウレタン樹脂組成物中１０～９０質量％の範囲が挙げられる。
The content of the organic solvent may be, for example, in the range of 10 to 90% by mass in the solvent-based urethane resin composition.
前記水系ウレタン樹脂組成物としては、例えば、ウレタン樹脂、及び、水を含むものが挙げられる。
Examples of the water-based urethane resin composition include urethane resin and those containing water.
前記ウレタン樹脂は、水に分散し得るものであり、例えば、アニオン性基、カチオン性基、ノニオン性基等の親水性基を有するウレタン樹脂；乳化剤で強制的に水中に分散したウレタン樹脂などを用いることができる。これらのウレタン樹脂は単独で用いても２種以上を併用してもよい。
The urethane resin can be dispersed in water, and for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; a urethane resin forcibly dispersed in water with an emulsifier, or the like. Can be used. These urethane resins may be used alone or in combination of two or more.
前記アニオン性基を有するウレタン樹脂を得る方法としては、例えば、カルボキシル基を有する化合物及びスルホニル基を有する化合物からなる群より選ばれる１種以上の化合物を原料として用いる方法が挙げられる。
Examples of the method for obtaining the urethane resin having an anionic group include a method using one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material.
前記カルボキシル基を有する化合物としては、例えば、２，２－ジメチロールプロピオン酸、２，２－ジメチロールブタン酸、２，２－ジメチロール酪酸、２，２－ジメチロールプロピオン酸、２，２－吉草酸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。
Examples of the compound having a carboxyl group include 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid, 2,2-dimethylol butyric acid, 2,2-dimethylol propionic acid, and 2,2-valeric acid. Valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.
前記スルホニル基を有する化合物としては、例えば、３，４－ジアミノブタンスルホン酸、３，６－ジアミノ－２－トルエンスルホン酸、２，６－ジアミノベンゼンスルホン酸、Ｎ－（２－アミノエチル）－２－アミノスルホン酸、Ｎ－（２－アミノエチル）－２－アミノエチルスルホン酸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。
Examples of the compound having a sulfonyl group include 3,4-diaminobutane sulfonic acid, 3,6-diamino-2-toluene sulfonic acid, 2,6-diaminobenzene sulfonic acid, and N- (2-aminoethyl)-. 2-Aminosulfonic acid, N- (2-aminoethyl) -2-aminoethylsulfonic acid and the like can be used. These compounds may be used alone or in combination of two or more.
前記カルボキシル基及びスルホニル基は、ウレタン樹脂組成物中で、一部又は全部が塩基性化合物に中和されていてもよい。前記塩基性化合物としては、例えば、アンモニア、トリエチルアミン、ピリジン、モルホリン等の有機アミン；モノエタノールアミン、ジメチルエタノールアミン等のアルカノールアミン；ナトリウム、カリウム、リチウム、カルシウム等を含む金属塩基化合物などを用いることができる。
The carboxyl group and the sulfonyl group may be partially or completely neutralized with a basic compound in the urethane resin composition. As the basic compound, for example, organic amines such as ammonia, triethylamine, pyridine, and morpholin; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds containing sodium, potassium, lithium, calcium and the like are used. Can be done.
前記カチオン性基を有するウレタン樹脂を得る方法としては、例えば、アミノ基を有する化合物の１種又は２種以上を原料として用いる方法が挙げられる。
Examples of the method for obtaining the urethane resin having a cationic group include a method using one or more compounds having an amino group as a raw material.
前記アミノ基を有する化合物としては、例えば、トリエチレンテトラミン、ジエチレントリアミン等の１級及び２級アミノ基を有する化合物；Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン等のＮ－アルキルジアルカノールアミン、Ｎ－メチルジアミノエチルアミン、Ｎ－エチルジアミノエチルアミン等のＮ－アルキルジアミノアルキルアミンなどの３級アミノ基を有する化合物など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。
Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl. Compounds having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
前記ノニオン性基を有するウレタン樹脂を得る方法としては、例えば、オキシエチレン構造を有する化合物の１種又は２種以上を原料として用いる方法が挙げられる。
Examples of the method for obtaining the urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.
前記オキシエチレン構造を有する化合物としては、例えば、ポリオキシエチレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシテトラメチレングリコール等のオキシエチレン構造を有するポリエーテルポリオール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 the compound having an oxyethylene structure, for example, a polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
前記強制的に水中に分散するウレタン樹脂を得る際に用いることができる乳化剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン性乳化剤；オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、ナフタレンスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、アルカンスルフォネートナトリウム塩、アルキルジフェニルエーテルスルフォン酸ナトリウム塩等のアニオン性乳化剤；アルキルアミン塩、アルキルトリメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩等のカチオン性乳化剤などを用いることができる。これらの乳化剤は単独で用いても２種以上を併用してもよい。
Examples of the emulsifier that can be used to obtain the urethane resin that is forcibly dispersed in water include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitol tetraole. Nonionic emulsifiers such as ate, polyoxyethylene / polyoxypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalensulphonate, polyoxyethylene alkyl Anionic emulsifiers such as sulfates, alkansulfonate sodium salts and alkyldiphenyl ether sulfonate sodium salts; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts can be used. These emulsifiers may be used alone or in combination of two or more.
前記ウレタン樹脂としては、より一層優れた水分散安定性、耐加水分解性、剥離強度、即剥離性、耐ブリード性、及び、耐光性が得られる点から、アニオン性基を有するウレタン樹脂、及び／又は、ノニオン性基を有するウレタン樹脂が好ましい。
As the urethane resin, a urethane resin having an anionic group and a urethane resin having an anionic group can be obtained from the viewpoints of further excellent water dispersion stability, hydrolysis resistance, peel strength, immediate peeling property, bleeding resistance, and light resistance. / Or, a urethane resin having a nonionic group is preferable.
前記親水性基を有するウレタン樹脂を製造するために用いる原料の使用量としては、ウレタン樹脂の親水性基の濃度を調整して、より一層優れた水分散安定性、耐加水分解性、剥離強度、即剥離性、耐ブリード性、及び、耐光性が得られる点から、前記ウレタン樹脂を構成する原料中０．０１～１０質量％の範囲が好ましく、０．１～５質量％の範囲がより好ましい。
As for the amount of the raw material used for producing the urethane resin having a hydrophilic group, the concentration of the hydrophilic group of the urethane resin is adjusted to further improve the water dispersion stability, hydrolysis resistance, and peel strength. From the viewpoint of immediate peeling property, bleeding resistance, and light resistance, the range of 0.01 to 10% by mass is preferable, and the range of 0.1 to 5% by mass is more preferable in the raw materials constituting the urethane resin. preferable.
前記ウレタン樹脂としては、具体的には、例えば、ポリオール（ａ１－２）、ポリイソシアネート（ａ２－２）、及び、前記親水性基を有するウレタン樹脂を製造するために用いる原料の反応物が挙げられる。
Specific examples of the urethane resin include a polyol (a1-2), a polyisocyanate (a2-2), and a reaction product of a raw material used for producing the urethane resin having a hydrophilic group. Be done.
前記ポリオール（ａ１－２）としては、前記ポリオール（ａ１－１）と同様のものを用いることができ、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、ポリエーテルポリオールが好ましく、ポリテトラメチレングリコールがより好ましい。
As the polyol (a1-2), the same one as the polyol (a1-1) can be used, the swelling rate of the film can be easily adjusted to a specific range, and even better bleed resistance can be obtained. From the point of view, a polyether polyol is preferable, and a polytetramethylene glycol is more preferable.
前記ポリオール（ａ１－２）中における前記ポリエーテルポリオールの含有量としては、同様の理由から、３０質量％以上が好ましく、５０質量％以上が好ましい。
For the same reason, the content of the polyether polyol in the polyol (a1-2) is preferably 30% by mass or more, preferably 50% by mass or more.
前記ポリオール（ａ１－２）には、必要に応じて、分子量が５００未満（好ましくは５０～４５０の範囲）の鎖伸長剤（ａ’１－２）を併用してもよい。前記鎖伸長剤（ａ’１－２）としては、前記鎖伸長剤（ａ’１－１）と同様のものを用いることができ、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、アミノ基を有する鎖伸長剤が好ましく、ピペラジン、ヒドラジン、イソホロンジアミン、及び、４，４’－ジシクロヘキシルメタンジアミンからなる群より選ばれる１種以上の化合物を用いることがより好ましい。
If necessary, a chain extender (a'1-2) having a molecular weight of less than 500 (preferably in the range of 50 to 450) may be used in combination with the polyol (a1-2). As the chain extender (a'1-2), the same one as the chain extender (a'1-1) can be used, and the swelling rate of the film can be easily adjusted to a specific range, further. A chain extender having an amino group is preferable from the viewpoint of obtaining excellent bleed resistance, and one or more compounds selected from the group consisting of piperazine, hydrazine, isophoronediamine, and 4,4'-dicyclohexylmethanediamine. It is more preferable to use it.
前記鎖伸長剤（ａ’１－２）を用いる場合の使用量としては、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、ポリオール（ａ１－２）中０．１～８０質量％の範囲が好ましく、１～６０質量％の範囲がより好ましい。
When the chain extender (a'1-2) is used, the amount used is such that the swelling rate of the film can be easily adjusted to a specific range and even better bleed resistance can be obtained, so that the polyol (a1-) can be used. 2) The range of 0.1 to 80% by mass is preferable, and the range of 1 to 60% by mass is more preferable.
前記ポリイソシアネート（ａ２－２）としては、前記ポリイソシアネート（ａ２－１）と同様のものを用いることができ、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、脂環式ポリイソシアネートが好ましく、イソホロンジアミン、及び／又は、ジシクロヘキシルメタンジイソシアネートが好ましい。
As the polyisocyanate (a2-2), the same one as the polyisocyanate (a2-1) can be used, the swelling rate of the film can be easily adjusted to a specific range, and even more excellent bleed resistance can be obtained. From the viewpoint obtained, alicyclic polyisocyanate is preferable, and isophorone diamine and / or dicyclohexylmethane diisocyanate is preferable.
前記ポリイソシアネート（ａ２－２）中の前記脂環式ポリイソシアネートの含有量としては、フィルムの膨潤率を特定の範囲に調整しやすく、より一層優れた耐ブリード性が得られる点から、３０質量％以上が好ましく、５０質量％がより好ましい。
The content of the alicyclic polyisocyanate in the polyisocyanate (a2-2) is 30 mass because it is easy to adjust the swelling rate of the film to a specific range and even better bleed resistance can be obtained. % Or more is preferable, and 50% by mass is more preferable.
前記ウレタン樹脂の製造方法としては、例えば、前記親水性基を有するウレタン樹脂を製造するために用いる原料、前記ポリイソシアネート（ａ２－２）、ポリオール（ａ１－２）、及び、必要に応じて前記鎖伸長剤（ａ’１－２）を一括に仕込み反応させる方法等が挙げられる。これらの反応は、例えば、５０～１００℃の温度で３～１０時間行う方法が挙げられる。
As a method for producing the urethane resin, for example, the raw material used for producing the urethane resin having a hydrophilic group, the polyisocyanate (a2-2), the polyol (a1-2), and if necessary, the above. Examples thereof include a method in which a chain extender (a'1-2) is charged in a batch and reacted. Examples thereof include a method in which these reactions are carried out at a temperature of 50 to 100 ° C. for 3 to 10 hours.
前記ポリオール（ａ２－１）と前記親水性基を有するウレタン樹脂を製造するために用いる原料、並びに、前記鎖伸長剤（ａ’１－２）を用いる場合にはそれが有する水酸基及びアミノ基の合計と、前記芳香族ポリイソシアネート（ａ２－２）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の合計）］としては、０．８～１．２の範囲であることが好ましく、０．９～１．１の範囲がより好ましい。
The raw material used to produce the polyol (a2-1) and the urethane resin having the hydrophilic group, and the hydroxyl group and amino group contained therein when the chain extender (a'1-2) is used. The molar ratio [(isocyanate group) / (total of hydroxyl groups and amino groups)] of the total to the isocyanate group of the aromatic polyisocyanate (a2-2) is in the range of 0.8 to 1.2. It is preferable, and the range of 0.9 to 1.1 is more preferable.
前記前記ウレタン樹脂を製造する際には、前記ウレタン樹脂に残存するイソシアネート基を失活させることが好ましい。前記イソシアネート基を失活させる場合には、メタノール等の水酸基を有するアルコールを用いることが好ましい。前記アルコールを用いる場合の使用量としては、ウレタン樹脂１００質量部に対し、０．００１～１０質量部の範囲であることが好ましい。
When producing the urethane resin, it is preferable to inactivate the isocyanate groups remaining in the urethane resin. When deactivating the isocyanate group, it is preferable to use an alcohol having a hydroxyl group such as methanol. When the alcohol is used, the amount used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the urethane resin.
また、前記ウレタン樹脂を製造する際には、有機溶剤を用いてもよい。前記有機溶剤としては、例えば、アセトン、メチルエチルケトン等のケトン化合物；テトラヒドロフラン、ジオキサン等のエーテル化合物；酢酸エチル、酢酸ブチル等の酢酸エステル化合物；アセトニトリル等のニトリル化合物；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド化合物などを用いることができる。これらの有機溶媒は単独で用いても２種以上を併用してもよい。なお、前記有機溶剤は、ウレタン樹脂組成物を得る際には蒸留法等によって除去されることが好ましい。
Further, when producing the urethane resin, an organic solvent may be used. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone. An amide compound or the like can be used. These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably removed by a distillation method or the like when the urethane resin composition is obtained.
前記水としては、例えば、例えば、イオン交換水、蒸留水、水道水等を用いることができる。これらの中でも、不純物の少ないイオン交換水を用いることが好ましい。前記水（Ｂ）の含有量としては、作業性、塗工性、及び保存安定性の点から、水系ウレタン樹脂組成物中２０～９０質量％の範囲が好ましく、４０～８０質量％の範囲がより好ましい。
As the water, for example, ion-exchanged water, distilled water, tap water, or the like can be used. Among these, it is preferable to use ion-exchanged water having few impurities. The content of the water (B) is preferably in the range of 20 to 90% by mass, preferably in the range of 40 to 80% by mass in the water-based urethane resin composition from the viewpoint of workability, coatability, and storage stability. More preferred.
本発明のウレタン樹脂組成物は、溶剤系ウレタン樹脂組成物、水系ウレタン樹脂組成物のいずれの場合においても、必要に応じてその他の添加剤を含有してもよい。
The urethane resin composition of the present invention may contain other additives, if necessary, in either the solvent-based urethane resin composition or the water-based urethane resin composition.
前記その他の添加剤としては、例えば、ウレタン化触媒、中和剤、架橋剤、シランカップリング剤、増粘剤、充填剤、チキソ付与剤、粘着付与剤、ワックス、熱安定剤、耐光安定剤、蛍光増白剤、発泡剤、顔料、染料、導電性付与剤、帯電防止剤、透湿性向上剤、撥水剤、撥油剤、中空発泡体、難燃剤、吸水剤、吸湿剤、消臭剤、整泡剤、ブロッキング防止剤、加水分解防止剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。
Examples of the other additives include a urethanization catalyst, a neutralizing agent, a cross-linking agent, a silane coupling agent, a thickener, a filler, a thixo-imparting agent, a tackifier, a wax, a heat stabilizer, and a light-resistant stabilizer. , Fluorescent whitening agent, foaming agent, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, flame retardant, water absorbing agent, moisture absorbing agent, deodorant , Anti-foaming agent, anti-blocking agent, anti-hydrolysis agent and the like can be used. These additives may be used alone or in combination of two or more.
以上、本発明のウレタン樹脂組成物は、可塑剤の耐ブリード性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、ポリ塩化ビニル層を有する合成皮革の製造に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 has excellent bleed resistance of the plasticizer. Therefore, the urethane resin composition of the present invention can be particularly suitably used for producing synthetic leather having a polyvinyl chloride layer.
次に、本発明の合成皮革について説明する。
Next, the synthetic leather of the present invention will be described.
前記合成皮革は、例えば、基材、熱可塑性樹脂層、前記ウレタン樹脂組成物により形成された皮膜、及び、表面処理層を順次有するものが挙げられる。
Examples of the synthetic leather include those having a base material, a thermoplastic resin layer, a film formed of the urethane resin composition, and a surface treatment layer in sequence.
前記基材としては、例えば、ポリエステル繊維、ポリエチレン繊維、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、綿、麻、絹、羊毛、グラスファイバー、炭素繊維、それらの混紡繊維等による不織布、織布、編み物などを用いることができる。
Examples of the base material include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, linen, silk, wool, glass fiber, carbon fiber, and a blend thereof. Non-woven fabrics made of fibers, woven fabrics, knitting and the like can be used.
前記熱可塑性樹脂層としては、例えば、公知のポリ塩化ビニル、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリスチレン等により形成されたものを用いることができる。本発明に於いては、前記熱可塑性樹脂として、ポリ塩化ビニルを用いた場合であっても優れた耐ブリード性を有する。
As the thermoplastic resin layer, for example, one formed of known polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene or the like can be used. In the present invention, even when polyvinyl chloride is used as the thermoplastic resin, it has excellent bleed resistance.
前記表面処理層としては、例えば、公知の溶剤系ウレタン樹脂、水系ウレタン樹脂、溶剤系アクリル樹脂、水系アクリル樹脂等により形成されたものを用いることができる。
As the surface treatment layer, for example, a layer formed of a known solvent-based urethane resin, water-based urethane resin, solvent-based acrylic resin, water-based acrylic resin, or the like can be used.
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 with reference to examples.
［実施例１］
＜水系ウレタン樹脂組成物（１）の調製＞
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４ツ口フラスコに、窒素気流下、ポリテトラメチレングリコール（数平均分子量：２，０００）２２０質量部、メチルエチルケトン１５０質量部、ジメチロールプロピオン酸１７質量部を加え、均一に混合した後、ジシクロヘキシルメタンジイソシアネート１１０質量部を加え、次いでカルボン酸ビスマス０．０２質量部を加え、７５℃で約４時間反応させ、イソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。次いで、トリエチルアミン１６質量部を加え、前記ウレタンプレポリマー中のカルボキシ基を中和した後、イオン交換水７８０質量部を加え、次いでヒドラジン５．９質量部を加え反応させた。反応終了後、メチルエチルケトンを減圧下留去することによって、水系ウレタン樹脂組成物（１）を得た。 [Example 1]
<Preparation of water-based urethane resin composition (1)>
In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube, 220 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000), 150 parts by mass of methyl ethyl ketone, dimethylol under a nitrogen stream. After adding 17 parts by mass of propionic acid and mixing uniformly, 110 parts by mass of dicyclohexylmethane diisocyanate is added, then 0.02 part by mass of bismuth carboxylate is added, and the mixture is reacted at 75 ° C. for about 4 hours to make a urethane pre having an isocyanate group. A methyl ethyl ketone solution of the polymer was obtained. Next, 16 parts by mass of triethylamine was added to neutralize the carboxy group in the urethane prepolymer, then 780 parts by mass of ion-exchanged water was added, and then 5.9 parts by mass of hydrazine was added for the reaction. After completion of the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous urethane resin composition (1).
＜水系ウレタン樹脂組成物（１）の調製＞
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４ツ口フラスコに、窒素気流下、ポリテトラメチレングリコール（数平均分子量：２，０００）２２０質量部、メチルエチルケトン１５０質量部、ジメチロールプロピオン酸１７質量部を加え、均一に混合した後、ジシクロヘキシルメタンジイソシアネート１１０質量部を加え、次いでカルボン酸ビスマス０．０２質量部を加え、７５℃で約４時間反応させ、イソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。次いで、トリエチルアミン１６質量部を加え、前記ウレタンプレポリマー中のカルボキシ基を中和した後、イオン交換水７８０質量部を加え、次いでヒドラジン５．９質量部を加え反応させた。反応終了後、メチルエチルケトンを減圧下留去することによって、水系ウレタン樹脂組成物（１）を得た。 [Example 1]
<Preparation of water-based urethane resin composition (1)>
In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube, 220 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000), 150 parts by mass of methyl ethyl ketone, dimethylol under a nitrogen stream. After adding 17 parts by mass of propionic acid and mixing uniformly, 110 parts by mass of dicyclohexylmethane diisocyanate is added, then 0.02 part by mass of bismuth carboxylate is added, and the mixture is reacted at 75 ° C. for about 4 hours to make a urethane pre having an isocyanate group. A methyl ethyl ketone solution of the polymer was obtained. Next, 16 parts by mass of triethylamine was added to neutralize the carboxy group in the urethane prepolymer, then 780 parts by mass of ion-exchanged water was added, and then 5.9 parts by mass of hydrazine was added for the reaction. After completion of the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous urethane resin composition (1).
＜フィルムの作製＞
前記水系ウレタン樹脂組成物（１）を１００質量部、ＤＩＣ株式会社製会合型増粘剤「ハイドラン アシスターＴ１０」１質量部、架橋剤（日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）４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」）上に固形分厚膜が３０μｍとなるように塗布し、７０℃で２分間、更に１２０℃で２分間乾燥させ、フィルムを得た。 <Making a film>
100 parts by mass of the aqueous urethane resin composition (1), 1 part by mass of the association type thickener "Hydran Assistor T10" manufactured by DIC Corporation, and a cross-linking agent ("Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd.) 4 A compounding solution containing parts by mass is applied on a flat release paper (“EK-100D” manufactured by Lintec Corporation) so that the solid content thick film is 30 μm, and dried at 70 ° C. for 2 minutes and then at 120 ° C. for 2 minutes. , Obtained a film.
前記水系ウレタン樹脂組成物（１）を１００質量部、ＤＩＣ株式会社製会合型増粘剤「ハイドラン アシスターＴ１０」１質量部、架橋剤（日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）４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」）上に固形分厚膜が３０μｍとなるように塗布し、７０℃で２分間、更に１２０℃で２分間乾燥させ、フィルムを得た。 <Making a film>
100 parts by mass of the aqueous urethane resin composition (1), 1 part by mass of the association type thickener "Hydran Assistor T10" manufactured by DIC Corporation, and a cross-linking agent ("Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd.) 4 A compounding solution containing parts by mass is applied on a flat release paper (“EK-100D” manufactured by Lintec Corporation) so that the solid content thick film is 30 μm, and dried at 70 ° C. for 2 minutes and then at 120 ° C. for 2 minutes. , Obtained a film.
＜耐ブリード性の評価方法＞
得られたフィルムを縦３ｃｍ、横３ｃｍに裁断し、これを３種の可塑剤（フタル酸ジオクチル（ＤＯＰ）、フタル酸ジイソノニル（ＤＩＮＰ）、フタル酸ジイソデシル（ＤＩＤＰ））にそれぞれ浸漬させ、２４時間後のフィルムの長さを計測し、膨潤率（％）を下記式（１）に従って算出した。
膨潤率（％）＝（２４時間試験後のフィルムの長さ－試験前のフィルムの長さ）／試験前のフィルムの長さ×１００ （１） <Evaluation method of bleed resistance>
The obtained film was cut into 3 cm in length and 3 cm in width, and this was immersed in three kinds of plasticizers (dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP)) for 24 hours. The length of the film after that was measured, and the swelling rate (%) was calculated according to the following formula (1).
Swelling rate (%) = (film length after 24-hour test-film length before test) / film length before test x 100 (1)
得られたフィルムを縦３ｃｍ、横３ｃｍに裁断し、これを３種の可塑剤（フタル酸ジオクチル（ＤＯＰ）、フタル酸ジイソノニル（ＤＩＮＰ）、フタル酸ジイソデシル（ＤＩＤＰ））にそれぞれ浸漬させ、２４時間後のフィルムの長さを計測し、膨潤率（％）を下記式（１）に従って算出した。
膨潤率（％）＝（２４時間試験後のフィルムの長さ－試験前のフィルムの長さ）／試験前のフィルムの長さ×１００ （１） <Evaluation method of bleed resistance>
The obtained film was cut into 3 cm in length and 3 cm in width, and this was immersed in three kinds of plasticizers (dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP)) for 24 hours. The length of the film after that was measured, and the swelling rate (%) was calculated according to the following formula (1).
Swelling rate (%) = (film length after 24-hour test-film length before test) / film length before test x 100 (1)
得られた膨潤率により、耐ブリード性を以下のように評価した。
「〇」；１０％以上である。
「×」；１０％未満である。 Based on the obtained swelling rate, the bleed resistance was evaluated as follows.
"○"; 10% or more.
"X"; less than 10%.
「〇」；１０％以上である。
「×」；１０％未満である。 Based on the obtained swelling rate, the bleed resistance was evaluated as follows.
"○"; 10% or more.
"X"; less than 10%.
［実施例２］
＜水系ウレタン樹脂組成物（２）の調製＞
ジシクロヘキシルメタンジイソシアネート１１０質量部をイソホロンジイソシアネート９５質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（２）、フィルムを得、耐ブリード性の評価を行った。 [Example 2]
<Preparation of water-based urethane resin composition (2)>
A water-based urethane resin composition (2) and a film were obtained in the same manner as in Example 1 except that 110 parts by mass of dicyclohexylmethane diisocyanate was changed to 95 parts by mass of isophorone diisocyanate, and bleed resistance was evaluated.
＜水系ウレタン樹脂組成物（２）の調製＞
ジシクロヘキシルメタンジイソシアネート１１０質量部をイソホロンジイソシアネート９５質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（２）、フィルムを得、耐ブリード性の評価を行った。 [Example 2]
<Preparation of water-based urethane resin composition (2)>
A water-based urethane resin composition (2) and a film were obtained in the same manner as in Example 1 except that 110 parts by mass of dicyclohexylmethane diisocyanate was changed to 95 parts by mass of isophorone diisocyanate, and bleed resistance was evaluated.
［実施例３］
＜水系ウレタン樹脂組成物（３）の調製＞
ヒドラジン５．９質量部をピペラジン８．１質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（３）、フィルムを得、耐ブリード性の評価を行った。 [Example 3]
<Preparation of water-based urethane resin composition (3)>
A water-based urethane resin composition (3) and a film were obtained in the same manner as in Example 1 except that 5.9 parts by mass of hydrazine was changed to 8.1 parts by mass of piperazine, and bleed resistance was evaluated.
＜水系ウレタン樹脂組成物（３）の調製＞
ヒドラジン５．９質量部をピペラジン８．１質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（３）、フィルムを得、耐ブリード性の評価を行った。 [Example 3]
<Preparation of water-based urethane resin composition (3)>
A water-based urethane resin composition (3) and a film were obtained in the same manner as in Example 1 except that 5.9 parts by mass of hydrazine was changed to 8.1 parts by mass of piperazine, and bleed resistance was evaluated.
［実施例４］
＜水系ウレタン樹脂組成物（４）の調製＞
ヒドラジン５．９質量部をイソホロンジアミン１６質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（４）、フィルムを得、耐ブリード性の評価を行った。 [Example 4]
<Preparation of water-based urethane resin composition (4)>
An aqueous urethane resin composition (4) and a film were obtained in the same manner as in Example 1 except that 5.9 parts by mass of hydrazine was changed to 16 parts by mass of isophorone diamine, and bleed resistance was evaluated.
＜水系ウレタン樹脂組成物（４）の調製＞
ヒドラジン５．９質量部をイソホロンジアミン１６質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（４）、フィルムを得、耐ブリード性の評価を行った。 [Example 4]
<Preparation of water-based urethane resin composition (4)>
An aqueous urethane resin composition (4) and a film were obtained in the same manner as in Example 1 except that 5.9 parts by mass of hydrazine was changed to 16 parts by mass of isophorone diamine, and bleed resistance was evaluated.
［比較例１］
＜水系ウレタン樹脂組成物（Ｒ１）の調製＞
ポリテトラメチレングリコール（数平均分子量：２，０００）２２０質量部をポリカーボネートポリオール（数平均分子量：２，０００）２２０質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（Ｒ１）、フィルムを得、耐ブリード性の評価を行った。 [Comparative Example 1]
<Preparation of water-based urethane resin composition (R1)>
A water-based urethane resin composition (R1) in the same manner as in Example 1 except that 220 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000) was changed to 220 parts by mass of polycarbonate polyol (number average molecular weight: 2,000). ), A film was obtained and the bleed resistance was evaluated.
＜水系ウレタン樹脂組成物（Ｒ１）の調製＞
ポリテトラメチレングリコール（数平均分子量：２，０００）２２０質量部をポリカーボネートポリオール（数平均分子量：２，０００）２２０質量部に変更した以外は実施例１と同様にして水系ウレタン樹脂組成物（Ｒ１）、フィルムを得、耐ブリード性の評価を行った。 [Comparative Example 1]
<Preparation of water-based urethane resin composition (R1)>
A water-based urethane resin composition (R1) in the same manner as in Example 1 except that 220 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000) was changed to 220 parts by mass of polycarbonate polyol (number average molecular weight: 2,000). ), A film was obtained and the bleed resistance was evaluated.
［数平均分子量、重量平均分子量の測定方法］
実施例および比較例で用いたポリオールの数平均分子量、ウレタン樹脂の重量平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により、下記の条件で測定し得られた値を示す。 [Measurement method of number average molecular weight and weight average molecular weight]
The number average molecular weight of the polyol and the weight average molecular weight of the urethane resin used in Examples and Comparative Examples show the values obtained by measuring under the following conditions by the gel permeation column chromatography (GPC) method.
実施例および比較例で用いたポリオールの数平均分子量、ウレタン樹脂の重量平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により、下記の条件で測定し得られた値を示す。 [Measurement method of number average molecular weight and weight average molecular weight]
The number average molecular weight of the polyol and the weight average molecular weight of the urethane resin used in Examples and Comparative Examples show the values obtained by measuring under the following conditions by the gel permeation column chromatography (GPC) method.
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 connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 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.
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 connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 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)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
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)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
本発明のウレタン樹脂組成物である実施例１～４は、耐ブリード性に優れることが分かった。
It was found that Examples 1 to 4, which are the urethane resin compositions of the present invention, are excellent in bleed resistance.
一方、比較例１は、フィルムの膨潤率が本発明で規定する範囲を下回る態様であるが、耐ブリード性が不良であった。
On the other hand, in Comparative Example 1, the swelling rate of the film was below the range specified in the present invention, but the bleed resistance was poor.
Claims (7)
- ウレタン樹脂を含有するウレタン樹脂組成物であって、前記ウレタン樹脂組成物により形成された厚さ３０μｍ、縦３ｃｍ、及び、横３ｃｍのフィルムを、可塑剤に２４時間浸漬させた後のフィルムの膨潤率が、１０％以上であることを特徴とするウレタン樹脂組成物。 A urethane resin composition containing a urethane resin, wherein a film having a thickness of 30 μm, a length of 3 cm, and a width of 3 cm formed by the urethane resin composition is immersed in a plasticizer for 24 hours, and then the film swells. A urethane resin composition having a ratio of 10% or more.
- 前記ウレタン樹脂が、アミノ基を有する鎖伸長剤を原料とするものである、請求項１記載のウレタン樹脂組成物。 The urethane resin composition according to claim 1, wherein the urethane resin is made from a chain extender having an amino group.
- 前記ウレタン樹脂が、脂肪族ポリイソシアネートを原料とするものである、請求項１又は２記載のウレタン樹脂組成物。 The urethane resin composition according to claim 1 or 2, wherein the urethane resin is made from an aliphatic polyisocyanate.
- 請求項１～３のいずれか１項記載の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。 A film characterized by being formed by the urethane resin composition according to any one of claims 1 to 3.
- 少なくとも、熱可塑性樹脂層、及び、請求項４記載の皮膜を有することを特徴とする積層体。 A laminate characterized by having at least a thermoplastic resin layer and the film according to claim 4.
- 少なくとも、熱可塑性樹脂層、請求項４記載の皮膜、及び、表面処理層を順次有することを特徴とする合成皮革。 A synthetic leather having at least a thermoplastic resin layer, the film according to claim 4, and a surface-treated layer in that order.
- 前記熱可塑性樹脂が、ポリ塩化ビニルである請求項６記載の合成皮革。 The synthetic leather according to claim 6, wherein the thermoplastic resin is polyvinyl chloride.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002012812A (en) * | 2000-06-29 | 2002-01-15 | Mitsui Chemicals Inc | Water-based coating material |
| JP2002235027A (en) * | 2001-02-13 | 2002-08-23 | Mitsui Chemicals Inc | Aqueous coating material, coating film formed from the coating material, method for coating film formation and coated material having the coating film |
| JP2005089650A (en) * | 2003-09-18 | 2005-04-07 | Mitsui Chemicals Inc | Water-based coating material containing self-emulsifying aqueous polyurethane resin and film-formed product obtained therefrom |
| JP2005206970A (en) * | 2004-01-23 | 2005-08-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing fiber laminate, fiber laminate and synthetic leather |
| JP2005273083A (en) * | 2004-03-25 | 2005-10-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing fiber laminate, fiber laminate and synthetic leather |
| JP2006036960A (en) * | 2004-07-28 | 2006-02-09 | Nicca Chemical Co Ltd | Method for producing leather material and leather material therefrom |
| JP2006523756A (en) * | 2003-04-16 | 2006-10-19 | ジェントロール | Aqueous polyurethane composition and synthetic leather having novel structure |
| WO2012017724A1 (en) * | 2010-08-06 | 2012-02-09 | Dic株式会社 | Urethane resin composition, coating agent, urethane resin composition for forming surface layer of leather-like sheet, laminate, and leather-like sheet |
| CN104629609A (en) * | 2015-02-06 | 2015-05-20 | 安庆昊业树脂材料科技有限公司 | Waterborne polyurethane suede coating and preparation method thereof |
| CN106750149A (en) * | 2016-11-28 | 2017-05-31 | 陕西科技大学 | A kind of preparation method and application method of expansion type aqueous polyurethane |
| CN107419540A (en) * | 2017-08-15 | 2017-12-01 | 福建鸣鸿树脂有限公司 | Water-based gorgeous black resistance to bright face PU inorganic agents of colour migration of use for synthetic leather and preparation method thereof |
| WO2019054104A1 (en) * | 2017-09-14 | 2019-03-21 | Dic株式会社 | Method for manufacturing synthetic leather |
| WO2019098039A1 (en) * | 2017-11-15 | 2019-05-23 | Dic株式会社 | Foamed urethane sheet and synthetic leather |
| WO2019202938A1 (en) * | 2018-04-20 | 2019-10-24 | Dic株式会社 | Resin composition and synthetic leather |
| JP2019199498A (en) * | 2018-05-14 | 2019-11-21 | 三井化学株式会社 | Polyurethane resin composition, coating agent, adhesive, coating and synthetic artificial leather |
| WO2020129604A1 (en) * | 2018-12-18 | 2020-06-25 | Dic株式会社 | Urethane resin composition, film and synthetic leather |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3384315B2 (en) * | 1998-02-02 | 2003-03-10 | 東洋インキ製造株式会社 | Recording material |
| JP5726168B2 (en) * | 2009-04-14 | 2015-05-27 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Use of polyurethane adhesives from polyester diols, polyether diols and silane compounds for the manufacture of film-coated furniture |
-
2021
- 2021-07-29 WO PCT/JP2021/028037 patent/WO2022097331A1/en active Application Filing
- 2021-07-29 JP JP2022519726A patent/JPWO2022097331A1/ja active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002012812A (en) * | 2000-06-29 | 2002-01-15 | Mitsui Chemicals Inc | Water-based coating material |
| JP2002235027A (en) * | 2001-02-13 | 2002-08-23 | Mitsui Chemicals Inc | Aqueous coating material, coating film formed from the coating material, method for coating film formation and coated material having the coating film |
| JP2006523756A (en) * | 2003-04-16 | 2006-10-19 | ジェントロール | Aqueous polyurethane composition and synthetic leather having novel structure |
| JP2005089650A (en) * | 2003-09-18 | 2005-04-07 | Mitsui Chemicals Inc | Water-based coating material containing self-emulsifying aqueous polyurethane resin and film-formed product obtained therefrom |
| JP2005206970A (en) * | 2004-01-23 | 2005-08-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing fiber laminate, fiber laminate and synthetic leather |
| JP2005273083A (en) * | 2004-03-25 | 2005-10-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing fiber laminate, fiber laminate and synthetic leather |
| JP2006036960A (en) * | 2004-07-28 | 2006-02-09 | Nicca Chemical Co Ltd | Method for producing leather material and leather material therefrom |
| WO2012017724A1 (en) * | 2010-08-06 | 2012-02-09 | Dic株式会社 | Urethane resin composition, coating agent, urethane resin composition for forming surface layer of leather-like sheet, laminate, and leather-like sheet |
| CN104629609A (en) * | 2015-02-06 | 2015-05-20 | 安庆昊业树脂材料科技有限公司 | Waterborne polyurethane suede coating and preparation method thereof |
| CN106750149A (en) * | 2016-11-28 | 2017-05-31 | 陕西科技大学 | A kind of preparation method and application method of expansion type aqueous polyurethane |
| CN107419540A (en) * | 2017-08-15 | 2017-12-01 | 福建鸣鸿树脂有限公司 | Water-based gorgeous black resistance to bright face PU inorganic agents of colour migration of use for synthetic leather and preparation method thereof |
| WO2019054104A1 (en) * | 2017-09-14 | 2019-03-21 | Dic株式会社 | Method for manufacturing synthetic leather |
| WO2019098039A1 (en) * | 2017-11-15 | 2019-05-23 | Dic株式会社 | Foamed urethane sheet and synthetic leather |
| WO2019202938A1 (en) * | 2018-04-20 | 2019-10-24 | Dic株式会社 | Resin composition and synthetic leather |
| JP2019199498A (en) * | 2018-05-14 | 2019-11-21 | 三井化学株式会社 | Polyurethane resin composition, coating agent, adhesive, coating and synthetic artificial leather |
| WO2020129604A1 (en) * | 2018-12-18 | 2020-06-25 | Dic株式会社 | Urethane resin composition, film and synthetic leather |
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