JP5740221B2 - 人工皮革 - Google Patents
人工皮革 Download PDFInfo
- Publication number
- JP5740221B2 JP5740221B2 JP2011137648A JP2011137648A JP5740221B2 JP 5740221 B2 JP5740221 B2 JP 5740221B2 JP 2011137648 A JP2011137648 A JP 2011137648A JP 2011137648 A JP2011137648 A JP 2011137648A JP 5740221 B2 JP5740221 B2 JP 5740221B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- urethane
- acrylic
- artificial leather
- resin
- 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.)
- Active
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- 239000002649 leather substitute Substances 0.000 title claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 79
- 239000000178 monomer Substances 0.000 claims description 76
- 239000000805 composite resin Substances 0.000 claims description 53
- 239000000839 emulsion Substances 0.000 claims description 49
- 239000006185 dispersion Substances 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 39
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000012736 aqueous medium Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000005187 foaming Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 125000003172 aldehyde group Chemical group 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 125000000468 ketone group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- -1 acryl Chemical group 0.000 description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 45
- 239000010410 layer Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000003995 emulsifying agent Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 15
- 150000002009 diols Chemical class 0.000 description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229960003237 betaine Drugs 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 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 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007870 radical polymerization initiator Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- SNVRDQORMVVQBI-OWOJBTEDSA-N (e)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C\C(=O)NN SNVRDQORMVVQBI-OWOJBTEDSA-N 0.000 description 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BKUWWVKLLKXDJK-UHFFFAOYSA-N 2-(dimethylamino)icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(N(C)C)C(O)=O BKUWWVKLLKXDJK-UHFFFAOYSA-N 0.000 description 1
- XPALGXXLALUMLE-UHFFFAOYSA-N 2-(dimethylamino)tetradecanoic acid Chemical compound CCCCCCCCCCCCC(N(C)C)C(O)=O XPALGXXLALUMLE-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- VNUREHWOFQRPGE-UHFFFAOYSA-N 2-[2-dodecyl-1-(2-hydroxyethyl)-4,5-dihydroimidazol-1-ium-1-yl]acetate Chemical compound CCCCCCCCCCCCC1=NCC[N+]1(CCO)CC([O-])=O VNUREHWOFQRPGE-UHFFFAOYSA-N 0.000 description 1
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- NEWFQHAOPHWBPR-UHFFFAOYSA-N 2-methylidenebutanedihydrazide Chemical compound NNC(=O)CC(=C)C(=O)NN NEWFQHAOPHWBPR-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- HPSGLFKWHYAKSF-UHFFFAOYSA-N 2-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1=CC=CC=C1 HPSGLFKWHYAKSF-UHFFFAOYSA-N 0.000 description 1
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
- CUTWSDAQYCQTGD-UHFFFAOYSA-N 2-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)C(C)OC(=O)C=C CUTWSDAQYCQTGD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DDGPBVIAYDDWDH-UHFFFAOYSA-N 3-[dodecyl(dimethyl)azaniumyl]-2-hydroxypropane-1-sulfonate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC(O)CS([O-])(=O)=O DDGPBVIAYDDWDH-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N 3-phenylprop-2-enal Chemical compound O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CMXNFXBFNYHFAL-UHFFFAOYSA-N 5-methylhex-1-en-3-one Chemical compound CC(C)CC(=O)C=C CMXNFXBFNYHFAL-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
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- 239000004156 Azodicarbonamide Substances 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229920002545 silicone oil Polymers 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
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- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
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- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
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Images
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Graft Or Block Polymers (AREA)
Description
この発明にかかる人工皮革は、ウレタン−(メタ)アクリル系複合樹脂を含有する層を基材に積層することにより複合された積層体である。
上記のウレタン−(メタ)アクリル系複合樹脂は、1種又は複数種の(メタ)アクリル系単量体を予め分散した原料乳化液を、水系媒体の存在下、反応容器中に逐次的又は連続的に添加することにより、ウレタン樹脂の存在下で、上記1種又は複数種の(メタ)アクリル系単量体を乳化重合することにより得られるウレタン−(メタ)アクリル系複合樹脂水性分散液に含まれる樹脂である。なお、この発明において「(メタ)アクリル」とは、「アクリル又はメタクリル」を示す。
なお、主成分とは、その使用量が全単量体量の50%を超えるか、又は3種類以上の単量体を用いる場合、その中で最も使用量が多いものを言う。
上記ウレタン−(メタ)アクリル系複合樹脂水性分散液は、上記の通り、水系媒体の存在下で、反応容器中に原料乳化液を逐次的又は連続的に添加することにより、ウレタン樹脂の存在下で、上記1種又は複数種の(メタ)アクリル系単量体を乳化重合することにより得ることができる。
上記ウレタン−(メタ)アクリル系複合樹脂水性分散液中の複合樹脂の平均粒子径は、30nm以上がよく、50nm以上が好ましい。30nmより小さいと、エマルジョンが高粘度となって、作業性が悪化する傾向となる。一方、平均粒子径の上限は、1500nm(1.5μm)がよく、1000nmが好ましい。1500nmより大きいと、得られる複合樹脂水性分散液の安定性が低下したり、樹脂の沈降分離が発生することがある。
上記ウレタン−(メタ)アクリル系複合樹脂を含む水性樹脂分散液を、基材層に塗工して、この塗工層を発泡することにより、人工皮革を形成することができる。この人工皮革とは、織布や不織布等の基材層又はこれに樹脂を含浸させた繊維質基材に、上記ウレタン−(メタ)アクリル系複合樹脂を含む水性樹脂分散液を塗工し、乾燥させた後、発泡成形する場合や、予め発泡させた塗工液を塗工・乾燥して発泡塗膜を形成し、次いで、必要に応じて、得られた発泡層に、直接、エンボス加工等の表面処理を行ったり、エンボス加工等の表面処理をした表面層(スキン層)を積層させたり、又はスキン層の積層後にエンボス加工等の表面処理をしたりすることにより、表面処理したスキン層を有する繊維質基材積層体をいう。
[ガラス転移温度(Tg)の測定]
ビニル共重合体中の各構成単量体(重合性単量体)a,b,…の構成重量分率をWa,Wb,…とし、各構成単位a,b,…の単独重合体のガラス転移温度をTga,Tgb,…としたとき、下記に示すFOXの式で、共重合であるビニル重合体のTgの値を求めた。
1/Tg=Wa/Tga+Wb/Tgb+…
ウレタン−(メタ)アクリル系複合樹脂水性分散液を、フィルター(アドバンテック社製:DISMIC−25cs)でろ過したイオン交換水で10000倍に希釈する。それを測定用セルに充填し、動的光散乱法(大塚電子(株)製:ELS−8000を使用)にて、平均粒子径を測定した。
なお、ウレタンの水分散液についても、同様の方法で平均粒子径を測定した。
各種水分散性樹脂を固形分で100重量部になるように採取し、下記の配合で調整した塗工液を繊維質層のポリエステルフェルトに1mm厚に塗布して、140℃熱風乾燥機により、塗膜を乾燥させて、人工皮革としての評価用の試験片を作成した。
下記の各原材料をディスパーによりよく撹拌混合し、増粘剤を添加して、配合物粘度が13,000〜20,000mPa・sとなるように増粘させた。その後、ハンドミキサーにより、機械発泡させ、混合物密度を0.72〜0.75g/mlに調整したものを塗工液とした。
・共重合体(固形分)…100重量部
・ブロッキング防止剤…0.73重量部
・凝固剤…0.94重量部
・起泡剤…4.1重量部
・整泡剤…5.0重量部
・顔料…7.5重量部
・硬化剤…3.0重量部
上記で作製した試験片を2.5cm幅に切断し、発泡層面にシアノアクリレート接着剤を塗布し、アクリル板に圧着させ、24時間室温乾燥したものを剥離強度用試験片とした。
この剥離強度用試験片をオートコムC型万能機((株)キーエスイー製)を用いて、23℃、50%RHの測定雰囲気下、クロスヘッドスピード100mm/minで、180°剥離試験を行った。
上記で作製した試験片を屈曲させた後、自然に戻した際の屈曲部の折れ曲がり状態を目視観察により評価を行った。
○…屈曲前の状態に戻り、屈曲部にも屈曲による痕跡は見られない
×…屈曲前の状態に戻らないか、又は屈曲部に折れ目やひび割れが発生した
上記作製の試験片の表面を指触によりタックの有無を確認し、以下の評価によって判定した。
○…タックなし
△…ややタックあり
×…タックあり
上記作製の試験片の発泡層面を学振型試験器(大栄科学(株)製)を用いて、摩擦子にCC−280耐水研磨紙(理研コランダム株式会社製)を用い、荷重1kg、回数5000回で試験を実施した。
○…変化なし
△…僅かに摩耗変化あり
×…発泡層が削れる
上記作製の試験片を80℃、90%RHの雰囲気下に300時間処理し、その後、表面層の状態を処理前と処理後で目視観察し状態変化を確認した。
○…変化なし
×…変化あり
柔軟性、表面タック、折り曲げ時の反発等を鑑み、指触により、下記の基準で評価した。
○:良い
△:やや良い
×:悪い
[ウレタン樹脂]
・三洋化成(株)製:ケミチレンGA−500…平均粒子径850nm、固形分50.0重量%、ポリエーテル系無黄変タイプ、以下「GA−500」と称する。
・メタクリル酸メチル…三菱レイヨン(株)製、以下「MMA」と略する。
・アクリロニトリル…ダイヤニトリックス(株)製、以下「AN」と略する。
・アクリル酸エチル…三菱化学(株)製、以下「EA」と略する。
・アクリル酸ブチル…三菱化学(株)製、以下「BA」と略する。
・メタクリル酸…三菱レイヨン(株)製、以下「MAA」と略する。
・イタコン酸…磐田化学工業(株)製、以下「IA」と略する。
・N−(1,1−ジメチル−3−オキソブチル)アクリルアミド…日本化成(株)製:ジアセトンアクリルアミド、以下、「DAAm」と略する。
・アジピン酸ジヒドラジド…大塚化学(株)製:以下、「ADH」と略する。
[ラジカル重合開始剤]
・過硫酸カリウム…(株)ADEKA製、以下「KPS」と略する。
・無水重亜硫酸ナトリウム…(有)戸川化学工業所、以下「SBS」と略する。
[乳化剤]
・エマルゲン1135S−70…花王(株)製、以下「E1135S−70」と略する。
・TSF451−100…ジメチルシリコーンオイル(MOMENTIVE社製:TSF451−100)
[凝固剤]
・TPA4380…ポリエーテル変性シリコーンオイル(MOMENTIVE社製:TPA4380)
・ペレックスTA…スルホコハク酸N−アルキルモノアミドジナトリウム(花王(株)製:ペレックスTA)
・DC−100A…ステアリン酸アンモニウム水分散液(サンノプコ(株)製:DC−100A)
・T−60…60%酸化チタン分散液(中央理化工業(株)製:T−60)
[硬化剤]
・EX−8…脂肪酸ポリグリシジルエーテル(中央理化工業(株)製:リカボンドEX−8)
[増粘剤]
・FK−600S…アルカリ増粘性アクリル共重合体(中央理化工業(株)製:リカボンドFK−600S)
[基材層]
・ポリエステルフェルト…ダイソー(株)製:ポリエステルフェルト
下記表1に記載の種類及び量のウレタン樹脂に、表1に記載の種類及び量の(メタ)アクリル系単量体を添加・混合し、第1段目の樹脂混合物、及び第2段目の樹脂混合物を調整した。次いで、それらに乳化剤として、E1135S−70を第1段目に3重量部、第2段目に2重量部を加え、さらに、液全体の固形分が60重量%となるようにイオン交換水を添加し、第1段目の原料乳化液及び第2段目の原料乳化液を得た。
また、撹拌翼を有する容積2リットルの反応容器に、乳化重合後のエマルジョンの固形分が47重量%となるように水を加え、次いで、この反応容器の撹拌翼を60rpmで回転させて撹拌しつつ、60℃に昇温した。
そして、まず、上記第1段目の原料乳化液を3時間かけて連続的に滴下した。次いで、第1段目の原料乳化液の滴下終了後、続いて、第2段目の原料乳化液を1時間半かけて滴下し、その後、2時間温度を保持して、重合を完結させた。その後、多価ヒドラジド化合物としてADHを1.08重量部(DAAmに対して25.7重量%)添加・混合した。
得られたウレタン−(メタ)アクリル系複合樹脂水性分散液について、上記の各種測定を行った。その結果を表1に示す。
合成例1で得られた複合樹脂水性分散液を用いて前述の配合で塗工液を作成し、上記の方法で人工皮革用積層体を作成して各種測定・評価を行った。その結果を表2及び3に示す。
Claims (8)
- ウレタン樹脂含有量が5重量%以上90重量%以下のウレタン−(メタ)アクリル系複合樹脂を含有する層を基材に積層することにより複合された人工皮革であって、
上記ウレタン−(メタ)アクリル系複合樹脂が、
1種又は複数種の(メタ)アクリル系単量体を予め分散した原料乳化液を、水系媒体の存在下、反応容器中に逐次的又は連続的に添加することにより、
ウレタン樹脂の存在下で、上記1種又は複数種の(メタ)アクリル系単量体を乳化重合して得られるウレタン−(メタ)アクリル系複合樹脂水性分散液に含まれる樹脂であって、
添加される上記原料乳化液として、互いに異なる組成を有する少なくとも2種類の原料乳化液を用い、
一つの原料乳化液の添加が終了した後、次の原料乳化液の添加を開始し、
かつ、先に添加される原料乳化液は、ケト基又はアルデヒド基に基づくカルボニル基を分子中に少なくとも1個有する重合性単量体を含有し、
上記原料乳化液のうち、最初に上記反応容器中に添加する原料乳化液にウレタン樹脂が含有されたものであり、
上記ウレタン−(メタ)アクリル系複合樹脂を構成する(メタ)アクリル系重合体のガラス転移温度が−80℃以上、80℃以下であり、
上記のウレタン−(メタ)アクリル系複合樹脂を含有する層は発泡層であることを特徴とする人工皮革。 - 上記ウレタン−(メタ)アクリル系複合樹脂を含有する層は、基材に0.1〜1.0mm厚(乾燥分)となるように塗布することにより形成されたことを特徴とする請求項1に記載の人工皮革。
- 上記ウレタン−(メタ)アクリル系複合樹脂を含有する層は、機械発泡又は化学発泡によって発泡した発泡層であることを特徴とする請求項1又は2に記載の人工皮革。
- 上記発泡層と基材との剥離強度が、0.6kgf/cm以上であることを特徴とする請求項1乃至3のいずれか1項に記載の人工皮革。
- 請求項1乃至4のいずれか1項に記載の人工皮革の製造方法であり、
上記基材に、上記ウレタン−(メタ)アクリル系複合樹脂を含む、粘度5000〜30000mPa・sの塗布液を塗布した後、乾燥及び発泡を行う人工皮革の製造方法。 - 上記塗布は、複数回行う請求項5に記載の人工皮革の製造方法。
- 上記乾燥を、温度50〜180℃の条件下で行う請求項5又は6に記載の人工皮革の製造方法。
- 上記の乾燥は、温度の異なる複数の工程で行い、かつ、最初の乾燥工程での温度を50〜100℃の範囲内とし、最後の乾燥工程での温度を、最初の乾燥工程との温度差が、10℃以上とする請求項7に記載の人工皮革の製造方法。
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