CN116390856A - 层叠体和合成皮革 - Google Patents
层叠体和合成皮革 Download PDFInfo
- Publication number
- CN116390856A CN116390856A CN202180072701.4A CN202180072701A CN116390856A CN 116390856 A CN116390856 A CN 116390856A CN 202180072701 A CN202180072701 A CN 202180072701A CN 116390856 A CN116390856 A CN 116390856A
- Authority
- CN
- China
- Prior art keywords
- urethane resin
- mass
- resin composition
- polyol
- laminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 15
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 83
- 229920005862 polyol Polymers 0.000 claims abstract description 54
- 150000003077 polyols Chemical class 0.000 claims abstract description 52
- 239000011342 resin composition Substances 0.000 claims abstract description 39
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000004417 polycarbonate Substances 0.000 claims abstract description 23
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- -1 polytetramethylene Polymers 0.000 claims description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 239000010410 layer Substances 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002335 surface treatment layer Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 abstract description 9
- 230000001629 suppression Effects 0.000 abstract description 3
- 230000000740 bleeding effect Effects 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- 230000000052 comparative effect Effects 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 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
- 239000003795 chemical substances by application Substances 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-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
- 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
- 239000000463 material Substances 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-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
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 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
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 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
- 239000007795 chemical reaction product Substances 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
- 239000006185 dispersion Substances 0.000 description 2
- 239000006260 foam Substances 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
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002562 thickening agent Substances 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
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-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
- 229940035437 1,3-propanediol Drugs 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
- 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 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
- YUZJZPMLAIYVGM-UHFFFAOYSA-N 2-n-methylethane-1,1,2-triamine Chemical compound CNCC(N)N YUZJZPMLAIYVGM-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
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 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
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene 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
- 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
- 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
- 229930006000 Sucrose Natural products 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
- 229920006221 acetate fiber Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
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Classifications
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- 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
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- 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
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Abstract
本发明要解决的课题在于提供热塑性树脂层与由氨基甲酸酯树脂组合物形成的被膜的密合性、以及增塑剂的渗出抑制优异的氨基甲酸酯树脂组合物。本发明提供一种层叠体,其特征在于,具有热塑性树脂层和由含有氨基甲酸酯树脂的氨基甲酸酯树脂组合物形成的被膜,该氨基甲酸酯树脂具有来自于以碳原子数4~7的范围的二醇为原料的聚碳酸酯多元醇和聚醚多元醇的结构。另外,本发明提供一种合成皮革,其特征在于,在上述被膜的与热塑性树脂层相反的一侧具有表面处理层。作为上述热塑性树脂,优选使用聚氯乙烯。上述氨基甲酸酯树脂优选以具有氨基的扩链剂和脂肪族多异氰酸酯为原料。
Description
技术领域
本发明涉及层叠体和合成皮革。
背景技术
含有氨基甲酸酯树脂的氨基甲酸酯树脂组合物被广泛用于合成皮革、人造皮革、膜、片材、粘接剂、片状物的表面处理等。其中,在用于车辆用内饰材料用的合成皮革等长期使用的构件的情况下,要求更高的耐久性。
另一方面,从成本方面出发,就连将聚氯乙烯(PVC)涂覆或贴合于基材而成的PVC合成皮革的需求也扩大,存在低温弯曲性等课题,为了解决该问题,存在将氨基甲酸酯树脂涂覆在PVC层上而成的所谓的半合成皮革逐渐兴起的状况。然而,对于该半合成皮革而言,除了需要氨基甲酸酯树脂层与PVC层的良好的密合性以外,还需要抑制PVC层中所含有的增塑剂的渗出。
现有技术文献
专利文献
专利文献1:日本特开平11-293220号公报
发明内容
发明要解决的课题
本发明要解决的课题在于提供热塑性树脂层与由氨基甲酸酯树脂组合物形成的被膜的密合性、以及增塑剂的渗出抑制优异的氨基甲酸酯树脂组合物。
用于解决课题的手段
本发明提供一种层叠体,其特征在于,具有热塑性树脂层和由含有氨基甲酸酯树脂的氨基甲酸酯树脂组合物形成的被膜,该氨基甲酸酯树脂具有来自于以碳原子数4~7的范围的二醇为原料的聚碳酸酯多元醇和聚醚多元醇的结构。
另外,本发明提供一种合成皮革,其特征在于,还具有表面处理层。
发明效果
本发明的层叠体的热塑性树脂层与由氨基甲酸酯树脂组合物形成的被膜的密合性(以下,简记为“密合性”。)优异,并且增塑剂的渗出抑制(以下,简记为“耐渗出性”。)优异。
具体实施方式
本发明的层叠体具有热塑性树脂层和由含有使用了特定原料的氨基甲酸酯树脂的氨基甲酸酯树脂组合物形成的被膜。
作为上述热塑性树脂层,例如可以使用由公知的聚氯乙烯、聚乙酸乙烯酯、聚偏二氯乙烯、聚苯乙烯等形成的热塑性树脂层。在本发明中,即使在使用聚氯乙烯作为上述热塑性树脂的情况下,也具有优异的耐渗出性。
上述被膜由含有氨基甲酸酯树脂的氨基甲酸酯树脂组合物形成,该氨基甲酸酯树脂具有来自于以碳原子数4~7的范围的二醇为原料的聚碳酸酯多元醇和聚醚多元醇的结构。
在得到优异的密合性和耐渗出性的方面上,上述氨基甲酸酯树脂必须具有来自于以碳原子数4~7的范围的二醇为原料的聚碳酸酯多元醇和聚醚多元醇的结构。
作为上述氨基甲酸酯树脂,例如可以使用包含有机溶剂的溶剂系氨基甲酸酯树脂组合物;包含水的水系氨基甲酸酯树脂组合物等。其中,从降低环境负荷的方面出发,优选水系氨基甲酸酯树脂组合物。
作为上述溶剂系氨基甲酸酯树脂组合物,例如可举出包含氨基甲酸酯树脂和有机溶剂的物质。
作为上述氨基甲酸酯树脂,例如可以使用包含以碳原子数4~7的范围的二醇为原料的聚碳酸酯多元醇和聚醚多元醇的多元醇(a1-1)与多异氰酸酯(a2-1)的反应产物。
关于作为上述聚碳酸酯多元醇的原料的碳原子数为4~7的二醇,例如可以使用1,4-丁二醇、1,5-己二醇、1,6-己二醇、1,7-庚二醇等。这些二醇可以单独使用,也可以并用2种以上。
作为上述聚碳酸酯多元醇的原料,在上述之中,从可得到更加优异的密合性、耐渗出性、低温弯曲性和机械强度的方面出发,优选1,4-丁二醇和/或1,6-己二醇,更优选1,6-己二醇。
具体而言,上述聚碳酸酯二醇可以使用通过公知的方法使上述二醇与碳酸酯和/或光气进行反应而得的物质。
作为上述碳酸酯,例如可以使用碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸亚乙酯、碳酸亚丙酯等。这些化合物可以单独使用,也可以并用2种以上。
作为上述聚碳酸酯二醇的数均分子量,从可得到更加优异的机械强度、耐渗出性、密合性和低温弯曲性的方面出发,优选为1,500~3,500的范围。需要说明的是,上述聚碳酸酯多元醇的数均分子量表示通过凝胶渗透色谱(GPC)法测定的值。
作为上述聚醚多元醇,例如可以使用聚乙二醇、聚丙二醇、聚四亚甲基二醇、聚亚乙基聚丙二醇、聚亚乙基聚丙二醇、聚亚丙基聚四亚甲基二醇等。这些聚醚多元醇可以单独使用,也可以并用2种以上。这些之中,从可得到更加优异的机械强度、耐渗出性、密合性和低温弯曲性的方面出发,优选聚四亚甲基二醇。
作为上述聚四亚甲基二醇的数均分子量,从可得到更加优异的机械强度、耐渗出性、密合性和低温弯曲性的方面出发,优选为1,500~3,500的范围。需要说明的是,上述聚四亚甲基二醇的数均分子量表示通过凝胶渗透色谱(GPC)法测定的值。
作为上述聚碳酸酯多元醇(PC)与上述聚醚多元醇(PEt)的质量比[PC/PEt],从可得到更加优异的机械强度、耐渗出性、密合性和低温弯曲性的方面出发,优选为20/80~80/20的范围,更优选为40/60~60/40的范围。
作为上述聚碳酸酯多元醇和上述聚醚多元醇的合计量,从可得到更加优异的机械强度、耐渗出性、密合性和低温弯曲性的方面出发,在上述多元醇(a1-1)中优选为30质量%以上,优选为50质量%以上,更优选为70质量%以上。
作为上述多元醇(a1-1),可以使用其他多元醇。作为上述其他多元醇,例如可以使用聚酯多元醇、上述聚碳酸酯多元醇以外的聚碳酸酯多元醇等。这些多元醇可以单独使用,也可以并用2种以上。
作为上述其他多元醇的数均分子量,从膜的机械特性和耐渗出性的方面出发,优选为500~10,000的范围,更优选为700~8,000的范围。需要说明的是,上述其他多元醇的数均分子量表示通过凝胶渗透色谱(GPC)法测定的值。
上述多元醇(a1-1)中,可以根据需要并用分子量小于500(优选为50~450的范围)的扩链剂(a’1-1)。作为上述扩链剂(a’1-1),例如可以使用具有羟基的扩链剂、具有氨基的扩链剂等。这些扩链剂(a’1-1)可以单独使用,也可以并用2种以上。
作为上述具有羟基的扩链剂,例如可以使用乙二醇、二乙二醇、三乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、六亚甲基二醇、蔗糖、甲二醇、甘油、山梨糖醇等脂肪族多元醇化合物;双酚A、4,4’-二羟基联苯、4,4’-二羟基二苯基醚、4,4’-二羟基二苯基砜、氢化双酚A、氢醌等芳香族多元醇化合物;水等。这些扩链剂可以单独使用,也可以并用2种以上。
作为上述具有氨基的扩链剂,例如可以使用乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、哌嗪、2-甲基哌嗪、2,5-二甲基哌嗪、异佛尔酮二胺、4,4’-二环己基甲烷二胺、3,3’-二甲基-4,4’-二环己基甲烷二胺、4,4’-二苯基甲烷二胺、3,3’-二氯-4,4’-二苯基甲烷二胺、1,2-环己烷二胺、1,4-环己烷二胺、氨基乙基乙醇胺、肼、二亚乙基三胺、三亚乙基四胺等。这些扩链剂可以单独使用,也可以并用2种以上。
作为上述扩链剂(a’1-1),从可得到更加优异的密合性和耐渗出性的方面出发,优选具有氨基的扩链剂,更优选使用选自哌嗪、肼、异佛尔酮二胺和4,4’-二环己基甲烷二胺中的1种以上的化合物。
作为使用上述扩链剂(a’1-1)时的使用量,从可得到更加优异的密合性和耐渗出性的方面出发,在多元醇(a1-1)中优选为0.1~80质量%的范围,更优选为1~60质量%的范围。
作为上述多异氰酸酯(a2-1),例如可以使用4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、碳二亚胺改性二苯基甲烷二异氰酸酯、粗二苯基甲烷二异氰酸酯、苯二异氰酸酯、甲苯二异氰酸酯、萘二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯等芳香族多异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、环己烷二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯等脂肪族多异氰酸酯等。这些多异氰酸酯可以单独使用,也可以并用2种以上。这些之中,从可得到更加优异的密合性和耐渗出性的方面出发,优选脂肪族多异氰酸酯,优选选自六亚甲基二异氰酸酯、异佛尔酮二胺和二环己基甲烷二异氰酸酯中的1种以上的多异氰酸酯。
作为上述多异氰酸酯(a2-1)中的上述脂肪族多异氰酸酯的含量,从可得到更加优异的密合性和耐渗出性的方面出发,优选为30质量%以上,更优选为50质量%。
作为上述氨基甲酸酯树脂的制造方法,例如可举出通过投入上述多元醇(a1-1)、上述多异氰酸酯(a2-1)和根据需要的上述扩链剂(a’1-1)并使其反应来制造的方法。这些反应优选在50~100℃的温度下进行约3~10小时。另外,上述反应可以在后述的有机溶剂中进行。
作为上述多元醇(a1-1)所具有的羟基以及上述扩链剂(a’1-1)所具有的羟基和氨基的合计与上述多异氰酸酯(a2-1)所具有的异氰酸酯基的摩尔比[(异氰酸酯基)/(羟基和氨基)],优选为0.8~1.2的范围,更优选为0.9~1.1的范围。
作为上述氨基甲酸酯树脂的重均分子量,从膜的机械特性、密合性和耐渗出性的方面出发,优选为5,000~1,000,000的范围,更优选为10,000~500,000的范围。需要说明的是,上述氨基甲酸酯树脂的重均分子量表示与上述多元醇(a1-1)的数均分子量同样地测定而得到的值。
作为上述氨基甲酸酯树脂的含量,例如可举出溶剂系氨基甲酸酯树脂组合物中10~90质量份的范围。
作为上述有机溶剂,例如可以使用N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、N,N,2-三甲基丙酰胺、N,N-二甲基丙烯酰胺、N,N-二甲基丙酰胺、N,N-二乙基乙酰胺、N,N-二乙基丙烯酰胺、N-乙基吡咯烷酮、2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、二甲基亚砜等。这些有机溶剂可以单独使用,也可以并用2种以上。另外,可以根据需要并用乙酸乙酯、乙酸甲酯、乙酸丁酯、丙酮、甲乙酮、甲基异丁基酮、甲醇、乙醇、异丙醇、异丁醇、仲丁醇、叔丁醇等有机溶剂。
作为上述有机溶剂的含量,例如可举出溶剂系氨基甲酸酯树脂组合物中10~90质量%的范围。
作为上述水系氨基甲酸酯树脂组合物,例如可举出包含氨基甲酸酯树脂和水的物质。
上述氨基甲酸酯树脂是可以分散于水中的物质,例如可以使用具有阴离子性基团、阳离子性基团、非离子性基团等亲水性基团的氨基甲酸酯树脂;利用乳化剂强制性地分散于水中的氨基甲酸酯树脂等。这些氨基甲酸酯树脂可以单独使用,也可以并用2种以上。
作为得到上述具有阴离子性基团的氨基甲酸酯树脂的方法,例如可举出使用选自具有羧基的化合物和具有磺酰基的化合物中的1种以上的化合物作为原料的方法。
作为上述具有羧基的化合物,例如可以使用2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基酪酸、2,2-二羟甲基丙酸、2,2-戊酸等。这些化合物可以单独使用,也可以并用2种以上。
作为上述具有磺酰基的化合物,例如可以使用3,4-二氨基丁磺酸、3,6-二氨基-2-甲苯磺酸、2,6-二氨基苯磺酸、N-(2-氨基乙基)-2-氨基磺酸、N-(2-氨基乙基)-2-氨基乙基磺酸等。这些化合物可以单独使用,也可以并用2种以上。
上述羧基和磺酰基在氨基甲酸酯树脂组合物中可以部分或全部被碱性化合物中和。作为上述碱性化合物,例如可以使用氨、三乙胺、吡啶、吗啉等有机胺;单乙醇胺、二甲基乙醇胺等烷醇胺;包含钠、钾、锂、钙等的金属碱化合物等。
作为得到上述具有阳离子性基团的氨基甲酸酯树脂的方法,例如可举出使用具有氨基的化合物中的1种或2种以上作为原料的方法。
作为上述具有氨基的化合物,例如可以使用三亚乙基四胺、二亚乙基三胺等具有伯氨基和仲氨基的化合物;N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二氨基乙胺、N-乙基二氨基乙胺等N-烷基二氨基烷基胺等具有叔氨基的化合物等。这些化合物可以单独使用,也可以并用2种以上。
作为得到上述具有非离子性基团的氨基甲酸酯树脂的方法,例如可举出使用具有氧亚乙基结构的化合物中的1种或2种以上作为原料的方法。
作为上述具有氧亚乙基结构的化合物,例如可以使用聚氧亚乙基二醇、聚氧亚乙基聚氧亚丙基二醇、聚氧亚乙基聚氧四亚甲基二醇等具有氧亚乙基结构的聚醚多元醇。这些化合物可以单独使用,也可以并用2种以上。
作为在得到上述强制性地分散于水中的氨基甲酸酯树脂时可以使用的乳化剂,例如可以使用聚氧亚乙基壬基苯基醚、聚氧亚乙基月桂基醚、聚氧亚乙基苯乙烯基苯基醚、聚氧亚乙基山梨糖醇四油酸酯、聚氧亚乙基-聚氧亚丙基共聚物等非离子性乳化剂;油酸钠等脂肪酸盐、烷基硫酸酯盐、烷基苯磺酸盐、烷基磺基琥珀酸盐、萘磺酸盐、聚氧亚乙基烷基硫酸盐、烷烃磺酸酯钠盐、烷基二苯基醚磺酸钠盐等阴离子性乳化剂;烷基胺盐、烷基三甲基铵盐、烷基二甲基苄基铵盐等阳离子性乳化剂等。这些乳化剂可以单独使用,也可以并用2种以上。
作为上述氨基甲酸酯树脂,从可得到更加优异的水分散稳定性、耐水解性、剥离强度、立即剥离性、耐渗出性和耐光性的方面出发,优选具有阴离子性基团的氨基甲酸酯树脂、和/或具有非离子性基团的氨基甲酸酯树脂。
作为为了制造上述具有亲水性基团的氨基甲酸酯树脂而使用的原料的使用量,从调整氨基甲酸酯树脂的亲水性基团的浓度而得到更加优异的水分散稳定性、耐水解性、剥离强度、立即剥离性、耐渗出性和耐光性的方面出发,在构成上述氨基甲酸酯树脂的原料中优选为0.01~10质量%的范围,更优选为0.1~5质量%的范围。
作为上述氨基甲酸酯树脂,具体而言,例如可举出包含以碳原子数8~12的范围的二醇为原料的聚碳酸酯多元醇的多元醇(a1-2)、多异氰酸酯(a2-2)以及为了制造上述具有亲水性基团的氨基甲酸酯树脂而使用的原料的反应产物。
作为上述包含聚碳酸酯多元醇的多元醇(a1-2),可以使用与上述多元醇(a1-1)同样的多元醇。
在上述多元醇(a1-2)中,可以根据需要并用分子量小于500(优选为50~450的范围)的扩链剂(a’1-2)。作为上述扩链剂(a’1-2),可以使用与上述扩链剂(a’1-1)同样的扩链剂,从可得到更加优异的密合性和耐渗出性的方面出发,优选具有氨基的扩链剂,更优选使用选自哌嗪、肼、异佛尔酮二胺和4,4’-二环己基甲烷二胺中的1种以上的化合物。
作为使用上述扩链剂(a’1-2)时的使用量,从可得到更加优异的密合性和耐渗出性的方面出发,在多元醇(a1-2)中优选为0.1~80质量%的范围,更优选为1~60质量%的范围。
作为上述多异氰酸酯(a2-2),可以使用与上述多异氰酸酯(a2-1)同样的多异氰酸酯,从可得到更加优异的密合性和耐渗出性的方面出发,优选脂环式多异氰酸酯,优选异佛尔酮二胺和/或二环己基甲烷二异氰酸酯。
作为上述多异氰酸酯(a2-2)中的上述脂环式多异氰酸酯的含量,从可得到更加优异的耐渗出性的方面出发,优选为30质量%以上,更优选为50质量%。
作为上述氨基甲酸酯树脂的制造方法,例如可举出将为了制造上述具有亲水性基团的氨基甲酸酯树脂而使用的原料、上述多异氰酸酯(a2-2)、多元醇(a1-2)、以及根据需要的上述扩链剂(a’1-2)一并投入并使其反应的方法等。关于这些反应,例如可举出在50~100℃的温度下进行3~10小时的方法。
作为在使用上述多元醇(a2-1)、为了制造上述具有亲水性基团的氨基甲酸酯树脂而使用的原料、以及上述扩链剂(a’1-2)的情况下其所具有的羟基和氨基的合计与上述芳香族多异氰酸酯(a2-2)所具有的异氰酸酯基的摩尔比[(异氰酸酯基)/(羟基和氨基的合计)],优选为0.8~1.2的范围,更优选为0.9~1.1的范围。
在制造上述氨基甲酸酯树脂时,优选使残留在上述氨基甲酸酯树脂中的异氰酸酯基失活。在使上述异氰酸酯基失活的情况下,优选使用甲醇等具有羟基的醇。作为使用上述醇时的使用量,相对于氨基甲酸酯树脂100质量份优选为0.001~10质量份的范围。
另外,在制造上述氨基甲酸酯树脂时,可以使用有机溶剂。作为上述有机溶剂,例如可以使用丙酮、甲乙酮等酮化合物;四氢呋喃、二噁烷等醚化合物;乙酸乙酯、乙酸丁酯等乙酸酯化合物;乙腈等腈化合物;二甲基甲酰胺、N-甲基吡咯烷酮等酰胺化合物等。这些有机溶剂可以单独使用,也可以并用2种以上。需要说明的是,上述有机溶剂优选在得到氨基甲酸酯树脂组合物时通过蒸馏法等而去除。
作为上述水,例如可以使用离子交换水、蒸馏水、自来水等。这些之中,优选使用杂质少的离子交换水。作为上述水(B)的含量,从作业性、涂敷性和保存稳定性的方面出发,在水系氨基甲酸酯树脂组合物中优选为20~90质量%的范围,更优选为40~80质量%的范围。
本发明的氨基甲酸酯树脂组合物在溶剂系氨基甲酸酯树脂组合物、水系氨基甲酸酯树脂组合物的任一情况下均可以根据需要含有其他添加剂。
作为上述其他添加剂,例如可以使用氨基甲酸酯化催化剂、中和剂、交联剂、硅烷偶联剂、增稠剂、填充剂、触变赋予剂、增粘剂、蜡、热稳定剂、耐光稳定剂、荧光增白剂、发泡剂、颜料、染料、导电性赋予剂、抗静电剂、透湿性提高剂、疏水剂、疏油剂、中空发泡体、阻燃剂、吸水剂、吸湿剂、除臭剂、整泡剂、防粘连剂、防水解剂等。这些添加剂可以单独使用,也可以并用2种以上。
对于上述被膜,作为使裁切成厚度30μm、纵3cm和横3cm的被膜在增塑剂中浸渍24小时后的膜的溶胀率(以下,简记为“膜的溶胀率”。),在可以得到更加优异的耐渗出性的方面上,优选为10%以上,更优选为10~40%的范围,进一步优选为10~25%的范围。推测在上述膜的溶胀率满足上述条件的情况下,被膜中的氨基甲酸酯树脂容易内包增塑剂,因此可得到优异的耐渗出性。
作为上述增塑剂,可以使用邻苯二甲酸二辛酯、邻苯二甲酸二异壬酯、邻苯二甲酸二异癸酯、邻苯二甲酸二丁酯等邻苯二甲酸酯;己二酸二辛酯、己二酸二异壬酯等己二酸酯;偏苯三酸三辛酯等偏苯三酸酯;磷酸三甲苯酯等磷酸酯;乙酰柠檬酸三丁酯等柠檬酸酯;环氧化大豆油、环氧化亚麻籽油等环氧化植物油;癸二酸酯;壬二酸酯;马来酸酯;苯甲酸酯;其他聚酯等。这些增塑剂可以单独使用,也可以并用2种以上。在本发明中,对于聚氯乙烯中经常使用的邻苯二甲酸酯也具有优异的耐渗出性。
综上,本发明的层叠体的密合性和耐渗出性优异。
接下来,对本发明的合成皮革进行说明。
上述合成皮革例如可举出依次具有基材、热塑性树脂层、上述被膜和表面处理层的合成皮革。
作为上述基材,例如可以使用基于聚酯纤维、聚乙烯纤维、尼龙纤维、丙烯腈系纤维、聚氨酯纤维、乙酸酯纤维、人造丝纤维、聚乳酸纤维、棉、麻、丝、羊毛、玻璃纤维、碳纤维、它们的混纺纤维等的无纺布、织布、编织物等。
作为上述表面处理层,例如可以使用由公知的溶剂系氨基甲酸酯树脂、水系氨基甲酸酯树脂、溶剂系丙烯酸类树脂、水系丙烯酸类树脂等形成的表面处理层。
实施例
以下,使用实施例更详细地说明本发明。
[实施例1]
<水系氨基甲酸酯树脂组合物(1)的制备>
在氮气流下,向具备搅拌机、回流冷凝管、温度计和氮吹入管的四口烧瓶中加入聚碳酸酯多元醇(以1,6-己二醇为原料,数均分子量:2,000)170质量份、聚四亚甲基二醇(数均分子量:2,000)170质量份、甲乙酮300质量份、二羟甲基丙酸11质量份,均匀混合后,加入二环己基甲烷二异氰酸酯100质量份,接着加入羧酸铋0.15质量份,在75℃反应约4小时,得到具有异氰酸酯基的氨基甲酸酯预聚物的甲乙酮溶液。接下来,加入三乙胺10质量份,将上述氨基甲酸酯预聚物中的羧基中和后,加入离子交换水900质量份,接着加入哌嗪6.8质量份进行反应。反应结束后,在减压下蒸馏除去甲乙酮,由此得到水系氨基甲酸酯树脂组合物(1)。
<层叠体的制作>
在PVC基材(Engineering Test Service株式会社制)上,以干燥后的厚度成为10μm的方式涂敷上述水系氨基甲酸酯树脂组合物(1),在120℃干燥2分钟,得到层叠体。
[实施例2]
<水系氨基甲酸酯树脂组合物(2)的制备>
将二环己基甲烷二异氰酸酯100质量份变更为异佛尔酮二异氰酸酯85质量份,除此以外,与实施例1同样地操作,得到水系氨基甲酸酯树脂组合物(2)和层叠体。
[实施例3]
<水系氨基甲酸酯树脂组合物(3)的制备>
将哌嗪6.8质量份变更为肼4.9质量份,除此以外,与实施例1同样地操作,得到水系氨基甲酸酯树脂组合物(3)和层叠体。
[实施例4]
<水系氨基甲酸酯树脂组合物(4)的制备>
将哌嗪6.8质量份变更为异佛尔酮二胺13.4质量份,除此以外,与实施例1同样地操作,得到水系氨基甲酸酯树脂组合物(4)和层叠体。
[实施例5]
<水系氨基甲酸酯树脂组合物(5)的制备>
将聚碳酸酯多元醇的使用量从170质量份变更为210质量份,并将聚四亚甲基二醇的使用量从170质量份变更为130质量份,除此以外,与实施例1同样地操作,得到水系氨基甲酸酯树脂组合物(5)和层叠体。
[比较例1]
<水系氨基甲酸酯树脂组合物(R1)的制备>
将聚碳酸酯多元醇的使用量从170质量份变更为340质量份,并将聚四亚甲基二醇的使用量从170质量份变更为0质量份,除此以外,与实施例1同样地操作,得到水系氨基甲酸酯树脂组合物(R1)和层叠体。
[比较例2]
<水系氨基甲酸酯树脂组合物(R2)的制备>
将聚碳酸酯多元醇的使用量从170质量份变更为0质量份,并将聚四亚甲基二醇的使用量从170质量份变更为340质量份,除此以外,与实施例1同样地操作,得到水系氨基甲酸酯树脂组合物(R2)和层叠体。
[数均分子量、重均分子量的测定方法]
实施例和比较例中使用的多元醇的数均分子量、氨基甲酸酯树脂的重均分子量表示通过凝胶渗透柱色谱(GPC)法在下述条件下测定而得到的值。
测定装置:高速GPC装置(东曹株式会社制“HLC-8220GPC”)
柱:将东曹株式会社制的下述柱串联连接而使用。
“TSKgel G5000”(7.8mmI.D.×30cm)×1根
“TSKgel G4000”(7.8mmI.D.×30cm)×1根
“TSKgel G3000”(7.8mmI.D.×30cm)×1根
“TSKgel G2000”(7.8mmI.D.×30cm)×1根
检测器:RI(差示折射计)
柱温:40℃
洗脱液:四氢呋喃(THF)
流速:1.0mL/分钟
注入量:100μL(试样浓度0.4质量%的四氢呋喃溶液)
标准试样:使用下述标准聚苯乙烯制作校准线。
(标准聚苯乙烯)
东曹株式会社制“TSKgel标准聚苯乙烯A-500”
东曹株式会社制“TSKgel标准聚苯乙烯A-1000”
东曹株式会社制“TSKgel标准聚苯乙烯A-2500”
东曹株式会社制“TSKgel标准聚苯乙烯A-5000”
东曹株式会社制“TSKgel标准聚苯乙烯F-1”
东曹株式会社制“TSKgel标准聚苯乙烯F-2”
东曹株式会社制“TSKgel标准聚苯乙烯F-4”
东曹株式会社制“TSKgel标准聚苯乙烯F-10”
东曹株式会社制“TSKgel标准聚苯乙烯F-20”
东曹株式会社制“TSKgel标准聚苯乙烯F-40”
东曹株式会社制“TSKgel标准聚苯乙烯F-80”
东曹株式会社制“TSKgel标准聚苯乙烯F-128”
东曹株式会社制“TSKgel标准聚苯乙烯F-288”
东曹株式会社制“TSKgel标准聚苯乙烯F-550”
[密合性的评价方法]
在实施例和比较例中得到的层叠体,以成为1cm的宽度的方式切出切口,实施棋盘格试验(5×5),根据剥离后的被膜残留数,如下进行评价。
“〇”:残留数为20以上且25以下
“△”:残留数为10以上且小于20
“×”:残留数小于10
<膜的制作>
将配合有实施例和比较例中得到的水系氨基甲酸酯树脂组合物各100质量份、DIC株式会社制缔合型增稠剂“ハイドランアシスターT10”1质量份、交联剂(NisshinboChemical株式会社制“CARBODILITE V-02-L2”)4质量份的配合液以固体成分厚膜成为30μm的方式涂布在平面脱模纸(LINTEC株式会社制“EK-100D”)上,在70℃干燥2分钟,进一步在120℃干燥2分钟,得到膜。
[耐渗出性的评价方法]
将所得到的膜裁切为纵3cm、横3cm,使其分别浸渍于3种增塑剂(邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二异壬酯(DINP),邻苯二甲酸二异癸酯(DIDP))中,测量24小时后的膜的长度,按照下述式(1)算出溶胀率(%)。
溶胀率(%)=(24小时试验后的膜的长度-试验前的膜的长度)/试验前的膜的长度×100(1)
根据所得到的溶胀率,如下评价耐渗出性。
“〇”:为10%以上。
“×”:小于10%。
[表1]
可知作为本发明的层叠体的实施例1~5的密合性和耐渗出性优异。
另一方面,比较例1是未使用聚醚多元醇的方式,耐渗出性不良。
另一方面,比较例2是未使用聚碳酸酯多元醇的方式,密合性不充分。
Claims (6)
1.一种层叠体,其特征在于,具有热塑性树脂层和由含有氨基甲酸酯树脂的氨基甲酸酯树脂组合物形成的被膜,该氨基甲酸酯树脂具有来自于以碳原子数4~7的范围的二醇为原料的聚碳酸酯多元醇和聚醚多元醇的结构。
2.根据权利要求1所述的层叠体,其中,所述氨基甲酸酯树脂以具有氨基的扩链剂为原料。
3.根据权利要求1或2所述的层叠体,其中,所述氨基甲酸酯树脂以脂肪族多异氰酸酯为原料。
4.根据权利要求1~3中任一项所述的层叠体,其中,所述聚醚多元醇为聚四亚甲基二醇。
5.一种合成皮革,其特征在于,在所述被膜的与热塑性树脂层相反的一侧具有表面处理层。
6.根据权利要求5所述的合成皮革,其中,所述热塑性树脂为聚氯乙烯。
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