JP2023096704A - Composition and method for producing artificial leather using the same - Google Patents
Composition and method for producing artificial leather using the same Download PDFInfo
- Publication number
- JP2023096704A JP2023096704A JP2021212633A JP2021212633A JP2023096704A JP 2023096704 A JP2023096704 A JP 2023096704A JP 2021212633 A JP2021212633 A JP 2021212633A JP 2021212633 A JP2021212633 A JP 2021212633A JP 2023096704 A JP2023096704 A JP 2023096704A
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- JP
- Japan
- Prior art keywords
- composition
- polyurethane resin
- group
- artificial leather
- inorganic acid
- 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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- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000002649 leather substitute Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- -1 inorganic acid salt Chemical class 0.000 claims abstract description 80
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 69
- 229920005862 polyol Polymers 0.000 claims abstract description 31
- 239000012736 aqueous medium Substances 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims abstract description 10
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 10
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 6
- 125000004185 ester group Chemical group 0.000 claims abstract description 6
- 125000001033 ether group Chemical group 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000004760 silicates Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 11
- 230000001112 coagulating effect Effects 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 33
- 229910052938 sodium sulfate Inorganic materials 0.000 description 33
- 235000011152 sodium sulphate Nutrition 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002585 base Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 150000003077 polyols Chemical class 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 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
- 239000002519 antifouling agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 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
- 239000002759 woven fabric Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RPNZHMGYRNKGQT-UHFFFAOYSA-M P.[K+].OP(O)([O-])=O Chemical compound P.[K+].OP(O)([O-])=O RPNZHMGYRNKGQT-UHFFFAOYSA-M 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- FAYYUXPSKDFLEC-UHFFFAOYSA-L calcium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ca+2].[O-]S([O-])(=O)=S FAYYUXPSKDFLEC-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940062135 magnesium thiosulfate Drugs 0.000 description 1
- TZKHCTCLSRVZEY-UHFFFAOYSA-L magnesium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Mg+2].[O-]S([O-])(=O)=S TZKHCTCLSRVZEY-UHFFFAOYSA-L 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、水性媒体中にポリウレタン樹脂を含有する組成物と、それを用いた人工皮革の製造方法に関する。 TECHNICAL FIELD The present invention relates to a composition containing a polyurethane resin in an aqueous medium and a method for producing artificial leather using the same.
従来、ポリウレタン樹脂などの柔軟で弾性を有する樹脂成分を不織布などの繊維基材に付着させることにより、天然皮革に近い風合を有する人工皮革が製造されており、近頃は、製造工程における作業環境面を配慮して有害な有機溶媒を使用せず、水性媒体中にポリウレタン樹脂を含有する組成物を用いて繊維基材に含浸させることにより、人工皮革が製造されている。 Conventionally, artificial leather having a feel close to that of natural leather has been produced by attaching a flexible and elastic resin component such as polyurethane resin to a fiber base material such as non-woven fabric. Artificial leather is produced by impregnating a fiber base material with a composition containing a polyurethane resin in an aqueous medium without using a harmful organic solvent in consideration of the surface.
しかしながら、単に水性媒体中にポリウレタン樹脂を含有する組成物を繊維基材に含浸させ乾燥させるだけでは、繊維基材中でのポリウレタン樹脂の分布が不均一になることなどにより、得られる人工皮革の柔軟性が不十分で触感が悪くなったり、耐摩耗性に劣ったりすることから、天然皮革に類似した高級感のある風合を有し耐久性のある人工皮革を得るために、種々の試みがなされている（特許文献１～６）。 However, simply impregnating a fiber base material with a composition containing a polyurethane resin in an aqueous medium and drying the resulting artificial leather may result in uneven distribution of the polyurethane resin in the fiber base material. Various attempts have been made to obtain a durable artificial leather that has a high-grade feel similar to natural leather and has poor tactile sensation due to insufficient flexibility and poor abrasion resistance. have been made (Patent Documents 1 to 6).
特許文献１、２には、繊維基材に含浸させ人工皮革を得るための、水性媒体中にポリウレタン樹脂を含有する組成物に硫酸ナトリウムなどの多価無機酸塩を添加することで、組成物の含有成分に加熱により凝固する性質（感熱凝固性）を持たせ、繊維基材に含浸した組成物が加熱により乾燥する際に凝固することで、繊維基材中でのポリウレタン樹脂の分布や、繊維へのポリウレタン樹脂の付着状態が改善され、風合いや耐久性等の諸特性に優れた人工皮革を得られることが開示されている。 In Patent Documents 1 and 2, a polyvalent inorganic acid salt such as sodium sulfate is added to a composition containing a polyurethane resin in an aqueous medium for impregnating a fiber base material to obtain an artificial leather. By imparting the property of coagulating by heating to the contained component (heat-sensitive coagulability), and by coagulating when the composition impregnated in the fiber base material dries by heating, the distribution of the polyurethane resin in the fiber base material, It is disclosed that the state of adhesion of polyurethane resin to fibers is improved, and artificial leather excellent in various properties such as texture and durability can be obtained.
特許文献３～６には、水性媒体中にポリウレタン樹脂を含有し、繊維基材に付与することにより人工皮革を得るために用いる組成物に、ポリウレタン樹脂としてポリマー構造中にカルボキシ基を有するアニオン性ポリウレタン樹脂を用いることにより、より風合いや耐久性等の諸特性に優れた人工皮革を得られることが開示されている。 Patent Documents 3 to 6 disclose an anionic polyurethane resin having a carboxyl group in the polymer structure as a polyurethane resin in a composition used for obtaining artificial leather by containing a polyurethane resin in an aqueous medium and applying it to a fiber base material. It is disclosed that the use of a polyurethane resin makes it possible to obtain an artificial leather having excellent properties such as texture and durability.
このようなポリマー構造中にカルボキシ基を有するアニオン性ポリウレタン樹脂を含有する組成物に多価無機酸塩を添加すると、組成物の含有成分が示す感熱凝固性はより大きくなることから、諸特性が更に優れた人工皮革が得られることが期待できる。しかしながら、アニオン性ポリウレタン樹脂と多価無機酸塩との間で感熱凝固性を発現する相互作用は非常に強いものであることから、繊維基材に付与する前の、液体状の組成物の状態において、加熱されない状況あってもアニオン性ポリウレタン樹脂と多価無機酸塩の相互作用は進行してしまい、組成物中で含有成分が凝集することで、繊維基材への付与時における組成物の使用に支障をきたすという問題があった。 When a polyvalent inorganic acid salt is added to a composition containing such an anionic polyurethane resin having a carboxyl group in the polymer structure, the heat-sensitive coagulability exhibited by the components contained in the composition is enhanced, and various properties are enhanced. It can be expected that a more excellent artificial leather will be obtained. However, since the interaction between the anionic polyurethane resin and the polyvalent inorganic acid salt that exhibits heat-sensitive coagulation is very strong, the state of the liquid composition before applying to the fiber substrate In , the interaction between the anionic polyurethane resin and the polyvalent inorganic acid salt progresses even if it is not heated, and the components contained in the composition aggregate. There was a problem that it interfered with use.
また、樹脂成分としてポリウレタン樹脂を含有する繊維処理剤組成物などに、ｐＨ調整剤やｐＨ緩衝剤や還元剤等として、炭酸ナトリウムやリン酸カリウムやチオ硫酸ナトリウム等を添加することや、バインダー成分としてポリウレタン樹脂を含有する塗料組成物に更に無機バインダー成分としてケイ酸ナトリウム等を添加することも行われており、これらの多価無機酸塩を含有する組成物において、ポリウレタン樹脂としてアニオン性ポリウレタン樹脂を用いる場合には、人工皮革の製造時と同様に、組成物中で含有成分が凝集し、組成物の使用に支障をきたすという問題があった。 In addition, sodium carbonate, potassium phosphate, sodium thiosulfate, etc. may be added as a pH adjuster, pH buffer, reducing agent, or the like to a fiber treatment composition containing a polyurethane resin as a resin component, or a binder component may be added. It has also been practiced to add sodium silicate or the like as an inorganic binder component to a coating composition containing a polyurethane resin as an anionic polyurethane resin as the polyurethane resin in a composition containing these polyvalent inorganic acid salts. When using, as in the case of the production of artificial leather, there is a problem that the components contained in the composition aggregate, hindering the use of the composition.
そこで本発明は、水性媒体中にアニオン性のポリウレタン樹脂と多価無機酸塩を含有し、含有成分が凝集し難い組成物を提供することを目的とする。また、本発明は、繊維基材への付与時における組成物の使用に支障をきたすことなく、風合いなどの諸特性に優れた人工皮革が得られる人工皮革の製造方法を提供することを目的とする。 SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a composition containing an anionic polyurethane resin and a polyvalent inorganic acid salt in an aqueous medium in which the contained components are less likely to agglomerate. Another object of the present invention is to provide a method for producing an artificial leather that does not interfere with the use of the composition when it is applied to a fiber substrate, and that can provide an artificial leather that is excellent in various properties such as texture. do.
上記課題は、カーボネート基、エステル基及びエーテル基から選ばれる基を有するポリオール化合物に由来する構造と、カルボキシ基を有するポリオール化合物に由来する構造と、下記一般式（１）で表されるポリアルキレングリコールモノアルキルエーテルに由来する構造とを有するポリウレタン樹脂、多価無機酸塩、及び水性媒体を含有する組成物により基本的に解決される。
ＲＯ－（Ｃ2Ｈ4Ｏ）m（Ｃ3Ｈ6Ｏ）n－Ｈ （１）
一般式（１）において、Ｒは炭素数１～１０のアルキル基、ｍは１以上の整数、ｎは０以上の整数を表す。
The above-mentioned problems are a structure derived from a polyol compound having a group selected from a carbonate group, an ester group and an ether group, a structure derived from a polyol compound having a carboxy group, and a polyalkylene represented by the following general formula (1) The problem is basically solved by a composition containing a polyurethane resin having a structure derived from a glycol monoalkyl ether, a polyvalent inorganic acid salt, and an aqueous medium.
RO—(C 2 H 4 O) m (C 3 H 6 O) n —H (1)
In general formula (1), R represents an alkyl group having 1 to 10 carbon atoms, m represents an integer of 1 or more, and n represents an integer of 0 or more.
ここで、カルボキシ基を有するポリオール化合物は、ジメチロールプロピオン酸であることが好ましい。ポリアルキレングリコールモノアルキルエーテルのＲは、炭素数１～４のアルキル基であることが好ましく、ポリアルキレングリコールモノアルキルエーテルの数平均分子量は、５００～５０００であることが好ましい。多価無機酸塩はアルカリ金属の塩であり、硫酸塩、リン酸塩、炭酸塩、チオ硫酸塩及びケイ酸塩から選択される少なくとも１種であることが好ましい。組成物における多価無機酸塩の含有量はポリウレタン樹脂の含有量１００質量部に対し５０～２００質量部であることが好ましい。 Here, the polyol compound having a carboxyl group is preferably dimethylolpropionic acid. R in the polyalkylene glycol monoalkyl ether is preferably an alkyl group having 1 to 4 carbon atoms, and the polyalkylene glycol monoalkyl ether preferably has a number average molecular weight of 500 to 5,000. The polyvalent inorganic acid salt is an alkali metal salt, and is preferably at least one selected from sulfates, phosphates, carbonates, thiosulfates and silicates. The content of the polyvalent inorganic acid salt in the composition is preferably 50 to 200 parts by weight per 100 parts by weight of the polyurethane resin.
また、本発明の組成物は、人工皮革を製造する用途における繊維基材に付着処理する組成物として用いることが好ましく、上記課題は、本発明の組成物を繊維基材に付着させる工程を有する人工皮革の製造方法によっても基本的に解決される。 In addition, the composition of the present invention is preferably used as a composition for attachment treatment to a fiber substrate in the application of manufacturing artificial leather, and the above problem has a step of attaching the composition of the present invention to a fiber substrate. It can also be basically solved by the manufacturing method of artificial leather.
本発明により、水性媒体中にアニオン性のポリウレタン樹脂と多価無機酸塩を含有し、含有成分が凝集しにくい組成物を提供することができる。また、本発明により、繊維基材への付与時における組成物の使用に支障をきたすことなく、風合いなどの諸特性に優れた人工皮革が得られる人工皮革の製造方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composition containing an anionic polyurethane resin and a polyvalent inorganic acid salt in an aqueous medium, in which the contained components are unlikely to aggregate. In addition, the present invention can provide a method for producing artificial leather that does not interfere with the use of the composition when it is applied to a fiber substrate, and that produces artificial leather that is excellent in various properties such as texture.
本発明の組成物は、ポリウレタン樹脂と多価無機酸塩と水性媒体を含有する。 The composition of the present invention contains a polyurethane resin, a polyvalent inorganic acid salt and an aqueous medium.
水性媒体とは、水を５０質量％以上含有する液状媒体のことであり、使用する水としては、不純物を除いて精製した水を使用することが好ましいが、本発明の効果を生じる限りにおいて、工業用水や水道水等を用いてもよい。水を主体とする媒体には、水に加えて他の液状媒体を含有していてもよい。水以外の液状媒体としては、モノアルコール、多価アルコール、グリコールエーテル、グリコールエステル等の水溶性有機溶媒が挙げられ、有害性が低く、揮発蒸気などによる作業環境の悪化が起こり難いものから必要に応じて選ぶことができる。 An aqueous medium is a liquid medium containing 50% by mass or more of water, and as the water to be used, it is preferable to use purified water by removing impurities. Industrial water, tap water, or the like may be used. The water-based medium may contain other liquid media in addition to water. Examples of liquid media other than water include water-soluble organic solvents such as monoalcohols, polyhydric alcohols, glycol ethers, and glycol esters. You can choose accordingly.
本発明の組成物が含有するポリウレタン樹脂は、水酸基を２個以上有するポリオール化合物とイソシアネート基を２個以上有するポリイソシアネート化合物との重合反応で得られる高分子鎖を基本骨格とするポリマーであり、ポリマー分子構造中にはその合成に用いる原材料に由来する構造を有する。具体的には、カーボネート基、エステル基及びエーテル基から選ばれる基を有するポリオール化合物に由来する構造と、カルボキシ基を有するポリオール化合物に由来する構造と、下記一般式（１）で表されるポリアルキレングリコールモノアルキルエーテルに由来する構造とを少なくとも有するアニオン性のポリウレタン樹脂である。
ＲＯ－（Ｃ2Ｈ4Ｏ）m（Ｃ3Ｈ6Ｏ）n－Ｈ （１）
ここで、Ｒは炭素数１～１０のアルキル基、ｍは１以上の整数、ｎは０以上の整数を表す。
The polyurethane resin contained in the composition of the present invention is a polymer having a polymer chain as a basic skeleton obtained by a polymerization reaction of a polyol compound having two or more hydroxyl groups and a polyisocyanate compound having two or more isocyanate groups, The polymer molecular structure has a structure derived from the raw materials used for its synthesis. Specifically, a structure derived from a polyol compound having a group selected from a carbonate group, an ester group and an ether group, a structure derived from a polyol compound having a carboxy group, and a poly represented by the following general formula (1) It is an anionic polyurethane resin having at least a structure derived from an alkylene glycol monoalkyl ether.
RO—(C 2 H 4 O) m (C 3 H 6 O) n —H (1)
Here, R is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 or more, and n is an integer of 0 or more.
本発明の組成物が含有するポリウレタン樹脂の合成に用いる原材料である、カーボネート基、エステル基及びエーテル基から選ばれる基を有するポリオール化合物としては、ポリカーボネートポリオール、ポリエステルポリオール、ポリエステルポリカーボネートポリオール、ポリエーテルポリオールなどが挙げられる。 Polyol compounds having a group selected from a carbonate group, an ester group and an ether group, which are raw materials used for synthesizing the polyurethane resin contained in the composition of the present invention, include polycarbonate polyols, polyester polyols, polyester polycarbonate polyols and polyether polyols. etc.
ポリカーボネートポリオールとしては、１，３－プロパンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等の炭素数２～２０の多価アルコールの１種または２種以上と、ホスゲン、アルキル基の炭素数１～６のジアルキルカーボネート、炭素数２～６のアルキレン基を有するアルキレンカーボネート、炭素数６～９のアリール基を有するジアリールカーボネート、環式カーボネート等との反応生成物が挙げられ、例えば、ポリテトラメチレンカーボネートジオール、ポリペンタメチレンカーボネートジオール、ポリヘキサメチレンカーボネートジオール、ポリネオペンチルカーボネートジオール、３－メチル－５－ペンタン－カーボネートジオール、ポリ（１，４－シクロヘキサンジメチレンカーボネート）ジオール等や、これらのランダム／ブロック共重合体等を用いることができる。 Polycarbonate polyols include one of polyhydric alcohols having 2 to 20 carbon atoms such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polypropylene glycol, and polytetramethylene glycol, or Two or more kinds, phosgene, dialkyl carbonate having an alkyl group with 1 to 6 carbon atoms, alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, diaryl carbonate having an aryl group having 6 to 9 carbon atoms, cyclic carbonate, etc. Examples include polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyhexamethylene carbonate diol, polyneopentyl carbonate diol, 3-methyl-5-pentane-carbonate diol, poly(1,4 -cyclohexane dimethylene carbonate) diol, random/block copolymers thereof, and the like can be used.
ポリエステルポリオールとしては、例えば、酸成分とポリオール化合物との直接エステル化反応またはエステル交換反応による反応生成物を挙げることができる。酸成分としては、フタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、テトラヒドロフタル酸などの芳香族カルボン酸；これらの芳香族カルボン酸の水素添加物などの脂環族カルボン酸；マロン酸、コハク酸、酒石酸、シュウ酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、アルキルコハク酸、リノレイン酸、マレイン酸、フマル酸、メサコン酸、シトラコン酸、イタコン酸などの脂肪族カルボン酸などを挙げることができる。また、これらの無水物、塩、誘導体（アルキルエステル、酸ハライド）なども用いることができる。ポリオール化合物としては、ジオールやトリオール等の多価アルコールや、下記のポリエーテルポリオールとして例示した化合物などを挙げることができる。更にポリエステルポリオールとしては、ポリオール化合物と、カプロラクトン、バレロラクトン、ブチロラクトン等のラクトン類またはその加水分解開環反応によって得られるヒドロキシカルボン酸との、直接エステル化反応による反応生成物等も挙げられる。 Examples of polyester polyols include reaction products obtained by direct esterification reaction or transesterification reaction between an acid component and a polyol compound. Acid components include aromatic carboxylic acids such as phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetrahydrophthalic acid; alicyclic carboxylic acids such as hydrogenated products of these aromatic carboxylic acids; malonic acid, succinic acid, Aliphatic carboxylic acids such as tartaric acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkylsuccinic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid etc. can be mentioned. Anhydrides, salts and derivatives (alkyl esters and acid halides) thereof can also be used. Examples of polyol compounds include polyhydric alcohols such as diols and triols, and compounds exemplified as polyether polyols below. Further examples of polyester polyols include reaction products obtained by direct esterification reaction of polyol compounds with lactones such as caprolactone, valerolactone and butyrolactone, or hydroxycarboxylic acids obtained by hydrolytic ring-opening reaction thereof.
ポリエステルポリカーボネートポリオールとしては、例えば、ポリカプロラクトンポリオール等のポリエステルグリコールとアルキレンカーボネートとの反応生成物；アルキレンカーボネートと多価アルコールとの反応生成物に、カプロラクトン、バレロラクトン、ブチロラクトン等のラクトン類や有機ジカルボン酸を反応させて得られる反応生成物等が挙げられる。 Polyester polycarbonate polyols include, for example, reaction products of polyester glycols such as polycaprolactone polyols and alkylene carbonates; reaction products of alkylene carbonates and polyhydric alcohols; Examples thereof include reaction products obtained by reacting acids.
ポリエーテルポリオールとしては、分子構造中に炭素数２～１２のアルキレンオキサイドの繰り返し構造を有するポリアルキレンエーテルグリコール；１，２－プロパンジオール、１，３－プロパンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、トリメチロールプロパン、グリセリン、ポリグリセリン、ペンタエリスリトール等の炭素数２～２０の脂肪族多価アルコールへの、エチレンオキサイド、プロピレンオキサイド等の炭素数２～１２のアルキレンオキサイドの付加物；ビスフェノールＡ等の芳香族ポリオールへの、エチレンオキサイド、プロピレンオキサイド等の炭素数２～１２のアルキレンオキサイド付加物；エチレンジアミン等のアミン化合物等への、エチレンオキサイド、プロピレンオキサイド等の炭素数２～１２のアルキレンオキサイド付加物等が挙げられ、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール／ポリテトラメチレングリコールのブロックまたはランダム共重合体、ポリテトラメチレンエーテルグリコール、ポリヘキサメチレンエーテルグリコール等を用いることができる。 Polyether polyols include polyalkylene ether glycols having a repeating structure of alkylene oxides having 2 to 12 carbon atoms in the molecular structure; 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, polyglycerin, pentaerythritol and other aliphatic polyhydric alcohols with 2 to 20 carbon atoms, such as ethylene oxide and propylene oxide. adducts of alkylene oxides having 2 to 12 carbon atoms; alkylene oxide adducts having 2 to 12 carbon atoms such as ethylene oxide and propylene oxide to aromatic polyols such as bisphenol A; ethylene oxide to amine compounds such as ethylenediamine; alkylene oxide adducts having 2 to 12 carbon atoms such as propylene oxide; Methylene ether glycol and the like can be used.
これらのポリカーボネートポリオールやポリエステルポリオールやポリエステルポリカーボネートポリオールやポリエーテルポリオールの数平均分子量は、５００～５０００であることが好ましい。また、これらは１種のみを用いてもよいし、２種以上を併用してもよい。 The number average molecular weight of these polycarbonate polyols, polyester polyols, polyester polycarbonate polyols and polyether polyols is preferably 500-5000. Moreover, these may use only 1 type and may use 2 or more types together.
カルボキシ基を有するポリオール化合物としては、ジメチロールプロピオン酸やその塩、ジメチロールブタン酸やその塩、ジメチロール吉草酸やその塩等が挙げられ、ジメチロールプロピオン酸であることが好ましい。 Examples of the polyol compound having a carboxyl group include dimethylolpropionic acid and its salts, dimethylolbutanoic acid and its salts, dimethylolvaleric acid and its salts, and dimethylolpropionic acid is preferred.
上記一般式（１）で表されるポリアルキレングリコールモノアルキルエーテルは、炭素数１～１０のモノアルコールにエチレンオキサイドと、必要に応じプロピレンオキサイドが付加重合した化合物であり、モノアルコールに由来する炭素数１～１０のアルキル基Ｒを有する。アルキル基Ｒは直鎖構造であっても分岐構造であってもよい。アルキル基Ｒの炭素数は１～４であることが好ましい。ｍは１以上の整数であり、１００以下であることが好ましく、ｎは０以上の整数であり、１００以下であることが好ましい。エチレンオキサイドとプロピレンオキサイドが共に付加している場合には、モノアルコールへの付加はエチレンオキサイドが先であっても、プロピレンオキサイドが先であってもよく、それらの付加状態はブロック付加であってもランダム付加であってもよい。一般式（１）で表されるポリアルキレングリコールモノアルキルエーテルの数平均分子量は、５００～５０００であることが好ましい。一般式（１）で表されるポリアルキレングリコールモノアルキルエーテルは、１種のみを用いてもよいし、２種以上を併用してもよい。 The polyalkylene glycol monoalkyl ether represented by the above general formula (1) is a compound obtained by addition polymerization of ethylene oxide and optionally propylene oxide to a monoalcohol having 1 to 10 carbon atoms, and the carbon derived from the monoalcohol It has 1 to 10 alkyl groups R. The alkyl group R may have a linear structure or a branched structure. The number of carbon atoms in the alkyl group R is preferably 1-4. m is an integer of 1 or more and preferably 100 or less, and n is an integer of 0 or more and preferably 100 or less. When both ethylene oxide and propylene oxide are added, the addition to the monoalcohol may be ethylene oxide first or propylene oxide first, and their addition state is block addition. may also be random additions. The number average molecular weight of the polyalkylene glycol monoalkyl ether represented by general formula (1) is preferably 500-5000. The polyalkylene glycol monoalkyl ether represented by the general formula (1) may be used alone or in combination of two or more.
ポリイソシアネート化合物としては、本発明においてはポリウレタン樹脂を得るために用いられる公知の化合物を用いることができ、脂肪族ポリイソシアネート、脂環式ポリイソシアネート、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネート等が挙げられる。ポリイソシアネート化合物は１種のみを用いてもよいし、２種以上を併用してもよい。 As the polyisocyanate compound, a known compound used for obtaining a polyurethane resin can be used in the present invention, and aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, etc. mentioned. Only one kind of polyisocyanate compound may be used, or two or more kinds thereof may be used in combination.
本発明の組成物において、ポリウレタン樹脂は水性媒体中で分散した水分散型ポリウレタン樹脂の性状を有する。このようなポリウレタン樹脂は、必要に応じ合成触媒を用いて、予め末端構造がイソシアネート基のプレポリマーを合成しておいて、水性媒体中で、必要により乳化剤、鎖伸長剤及び／または停止剤などの存在下に乳化させてエマルジョンの性状で得る方法や、必要に応じ合成触媒を用いて、末端構造が水酸基のポリウレタン樹脂を合成しておいて、水性媒体中で、必要により乳化剤の存在下に乳化させてエマルジョンの性状で得る方法などの公知の製造方法で得ることができる。本発明においては、合成触媒、乳化剤、鎖伸長剤、停止剤などは水分散型ポリウレタン樹脂を得るために用いられる公知の化合物を用いることができる。また、本発明の組成物が含有するポリウレタン樹脂の合成に用いる原材料としては、本発明の効果を生じる限りにおいて、カーボネート基、エステル基及びエーテル基から選ばれる基を有するポリオール化合物やカルボキシ基を有するポリオール化合物以外のポリオール化合物やポリアミン化合物などの、通常、ポリウレタン樹脂の合成に用いられている２個以上の活性水素を有する化合物などを用いてもよい。 In the composition of the present invention, the polyurethane resin has the properties of a water-dispersed polyurethane resin dispersed in an aqueous medium. Such a polyurethane resin is prepared by synthesizing a prepolymer having an isocyanate terminal structure in advance using a synthesis catalyst as necessary, and adding an emulsifier, a chain extender and/or a terminator, etc., in an aqueous medium as necessary. or by synthesizing a polyurethane resin having a terminal structure with a hydroxyl group, using a synthesis catalyst if necessary, and emulsifying it in an aqueous medium in the presence of an emulsifier if necessary. It can be obtained by a known production method such as a method of emulsifying to obtain an emulsion state. In the present invention, known compounds used for obtaining a water-dispersed polyurethane resin can be used as the synthesis catalyst, emulsifier, chain extender, terminator, and the like. In addition, as raw materials used for synthesizing the polyurethane resin contained in the composition of the present invention, as long as the effect of the present invention is produced, polyol compounds having groups selected from carbonate groups, ester groups and ether groups and carboxyl groups are used. A compound having two or more active hydrogens, such as a polyol compound other than a polyol compound, a polyamine compound, etc., which is usually used for synthesizing a polyurethane resin, may also be used.
ポリウレタン樹脂の酸価は、３～５０ｍｇＫＯＨ／ｇの範囲にあることが好ましく、５～３０ｍｇＫＯＨ／ｇの範囲にあることがより好ましい。酸価とは、適当な溶媒に溶解したカルボキシ基を有するポリウレタン樹脂を水酸化カリウム等のアルカリで滴定して得られる数値であり、カルボキシ基の含有量を示す指標となる値である。また、酸価は、ポリウレタン樹脂の合成に用いる原材料の使用量から算出することもできる。 The acid value of the polyurethane resin is preferably in the range of 3-50 mgKOH/g, more preferably in the range of 5-30 mgKOH/g. The acid value is a numerical value obtained by titrating a polyurethane resin having a carboxyl group dissolved in an appropriate solvent with an alkali such as potassium hydroxide, and serves as an indicator of the content of the carboxyl group. The acid value can also be calculated from the amounts of raw materials used for synthesizing the polyurethane resin.
本発明の組成物中のポリウレタン樹脂の含有率としては、本発明の効果を奏することを限度として、特に制限されず、例えば０．１～４０質量％、好ましくは０．５～２５質量％、より好ましくは１～１０質量％である。 The content of the polyurethane resin in the composition of the present invention is not particularly limited as long as the effects of the present invention can be achieved. More preferably, it is 1 to 10% by mass.
本発明の組成物が含有する多価無機酸塩は、硫酸やリン酸といった多価の無機酸の金属塩であり、例えば、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸マグネシウム、炭酸亜鉛、硫酸ナトリウム、硫酸カリウム、硫酸カルシウム、硫酸マグネシウム、硫酸亜鉛、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸カルシウム、亜硫酸マグネシウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、チオ硫酸カリウム、チオ硫酸カルシウム、チオ硫酸マグネシウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カルシウム、リン酸水素マグネシウム、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸リチウム、ケイ酸カルシウム等が挙げられ、これらの１種または２種以上を用いることができる。 The polyvalent inorganic acid salt contained in the composition of the present invention is a metal salt of a polyvalent inorganic acid such as sulfuric acid or phosphoric acid, such as sodium carbonate, potassium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, sodium sulfate. , potassium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, sodium sulfite, potassium sulfite, calcium sulfite, magnesium sulfite, sodium bisulfite, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, magnesium thiosulfate, sodium phosphate, phosphorus potassium phosphate, sodium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, sodium silicate, potassium silicate, lithium silicate, calcium silicate, etc., and one or more of these may be used. can.
本発明において、多価無機酸塩は、例えば、人工皮革用組成物用途においてポリウレタン樹脂との間で感熱凝固性を発現する硫酸ナトリウムであったり、繊維処理剤組成物用途においてｐＨ調整剤やｐＨ緩衝剤や還元剤等として機能する、炭酸ナトリウムやリン酸カリウムやチオ硫酸ナトリウムであったり、塗料組成物用途における無機バインダー成分として用いられるケイ酸ナトリウムなどといったように、使用する用途／目的に応じてそれらが発現する機能から適宜選択して用いることができるが、これらの中でも、本発明の効果をより有効に奏することができることから、アルカリ金属の塩であって、硫酸塩、リン酸塩、炭酸塩、チオ硫酸塩あるいはケイ酸塩であることが好ましい。また、多価無機酸塩は、本発明の組成物が含有する水性媒体に溶解するものであることが好ましい。 In the present invention, the polyvalent inorganic acid salt is, for example, sodium sulfate that expresses heat-sensitive coagulation with polyurethane resin in the use of artificial leather composition, or pH adjuster or pH in the use of fiber treatment composition. Sodium carbonate, potassium phosphate, sodium thiosulfate, etc., which function as buffering agents and reducing agents, and sodium silicate, which is used as an inorganic binder component in paint compositions, etc., depending on the application / purpose of use. However, among these, since the effects of the present invention can be more effectively exhibited, alkali metal salts such as sulfates, phosphates, Carbonates, thiosulfates or silicates are preferred. Moreover, the polyvalent inorganic acid salt is preferably one that dissolves in the aqueous medium contained in the composition of the present invention.
本発明の組成物は、水性媒体中で分散した水分散型ポリウレタン樹脂に多価無機酸塩を添加し、更に用途／目的に応じて下記の添加剤等を添加し、水性媒体を追加添加するなどして得ることができる。本発明の組成物においては含有成分の凝集が起こり難く、ポリウレタン樹脂の含有量に対する多価無機酸塩の含有量の比率を高めることが可能となることから、ポリウレタン樹脂含有組成物における多価無機酸塩の作用がより効果的に発現し、より諸特性が良好な人工皮革や繊維材料や塗装物などの目的物を得ることができる。また本発明においては、組成物における含有成分の濃度を高くすることができ、これは付与加工時の乾燥負荷の低減や物流コストの削減などに寄与することから、組成物の商品価値を高いものとすることができる。本発明の組成物における多価無機酸塩の含有量は、ポリウレタン樹脂の含有量１００質量部に対し５０～２００質量部であることが好ましく、８０～１６０質量部であることがより好ましい。本発明の組成物は、予め水分散型ポリウレタン樹脂及び多価無機酸塩や添加剤等を含有するものであってもよいが、その用途における使用の少し前に、多価無機酸塩を含有しない水分散型ポリウレタン樹脂に多価無機酸塩を添加し、添加剤添加や固形分濃度を調整するなどして調製することもできる。本発明の組成物に含まれる固形分（水性媒体以外の不揮発性成分）濃度としては、その用途／目的に応じて適宜調整することができ、例えば０．１～５０質量％の範囲が挙げられる。 The composition of the present invention is prepared by adding a polyvalent inorganic acid salt to a water-dispersed polyurethane resin dispersed in an aqueous medium, further adding the following additives according to the application/purpose, and then adding an aqueous medium. etc. can be obtained. Aggregation of the components contained in the composition of the present invention is unlikely to occur, and the ratio of the content of the polyvalent inorganic acid salt to the content of the polyurethane resin can be increased. The action of the acid salt is expressed more effectively, and it is possible to obtain the desired objects such as artificial leathers, fiber materials, and coated articles with better properties. In addition, in the present invention, the concentration of the ingredients contained in the composition can be increased, which contributes to the reduction of the drying load during the application process and the reduction of the distribution cost, so that the composition has a high commercial value. can be The content of the polyvalent inorganic acid salt in the composition of the present invention is preferably 50 to 200 parts by mass, more preferably 80 to 160 parts by mass, per 100 parts by mass of the polyurethane resin. The composition of the present invention may contain a water-dispersed polyurethane resin, a polyvalent inorganic acid salt, an additive, etc. in advance, but it may contain a polyvalent inorganic acid salt shortly before use in the application. It can also be prepared by adding a polyvalent inorganic acid salt to a water-dispersible polyurethane resin, adding additives, and adjusting the solid content concentration. The solid content (non-volatile components other than the aqueous medium) concentration contained in the composition of the present invention can be appropriately adjusted according to its use/purpose, and includes, for example, a range of 0.1 to 50% by mass. .
本発明の組成物には、その用途／目的に応じて、本発明の効果を生じる限りにおいて任意の添加剤を含んでもよい。添加剤としては例えば、本発明のポリウレタン樹脂以外の樹脂成分、架橋剤、界面活性剤、酸化防止剤、紫外線吸収剤、顔料、金属粉顔料、レオロジーコントロール剤、硬化促進剤、可塑剤、難燃剤、帯電防止剤、消臭剤、抗菌剤等や、本発明の組成物が繊維処理剤組成物である場合には、撥水剤、撥油剤、滑脱防止剤、柔軟剤、防汚剤、防しわ剤、耐熱剤等の繊維用薬剤が挙げられる。これらの添加剤は１種または２種以上を適宜組み合わせて用いることができる。 The composition of the present invention may contain any additive depending on its use/purpose as long as the effects of the present invention are produced. Examples of additives include resin components other than the polyurethane resin of the present invention, cross-linking agents, surfactants, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, plasticizers, flame retardants. , antistatic agents, deodorants, antibacterial agents, etc., and when the composition of the present invention is a fiber treatment composition, water repellents, oil repellents, anti-slip agents, softeners, antifouling agents, anti-fouling agents, etc. Textile agents such as wrinkling agents and heat-resistant agents are included. These additives can be used singly or in combination of two or more.
本発明の組成物は、人工皮革を製造する用途において、繊維基材に付着処理する組成物として用いることが好ましい。また、本発明の人工皮革の製造方法においては、本発明の組成物を繊維基材に付着させる工程を有する。繊維基材に本発明の組成物を付着処理して得られた人工皮革は風合いなどの諸特性に優れると共に、それを製造する工程において、繊維基材への付与時における組成物の使用に支障をきたすことが無い。 The composition of the present invention is preferably used as a composition for adhering to fiber substrates in applications for producing artificial leather. Moreover, the method for producing the artificial leather of the present invention has a step of adhering the composition of the present invention to the fiber base material. Artificial leather obtained by adhering the composition of the present invention to a fiber base material is excellent in various properties such as texture, and in the process of manufacturing it, there is no hindrance to the use of the composition when it is applied to the fiber base material. It does not cause
本発明における人工皮革を製造する用途において用いられる繊維基材としては、特に限定されるものではなく、人工皮革の基材として用いられる公知の不織布や編織布を使用することができる。不織布には補強等の目的で、編織布等が内部または表面に積層されていてもよい。繊維は、天然繊維であっても再生繊維であっても化学繊維であっても、これらが混紡された繊維であってもよい。これらの中でも、ポリアミド繊維またはポリエステル繊維を用い、フェルト状とした不織布や、超微細繊維を用いた不織布を用いた場合は、天然の皮革に近い風合い及び品位の人工皮革が得られる。 The fiber base material used in the application for manufacturing the artificial leather in the present invention is not particularly limited, and known nonwoven fabrics and knitted and woven fabrics used as base materials for artificial leather can be used. The nonwoven fabric may have a woven fabric or the like laminated inside or on the surface thereof for the purpose of reinforcement or the like. The fibers may be natural fibers, regenerated fibers, chemical fibers, or blended fibers thereof. Among these, when a felt-like nonwoven fabric using polyamide fibers or polyester fibers or a nonwoven fabric using ultrafine fibers is used, artificial leather having texture and quality close to those of natural leather can be obtained.
本発明の人工皮革の製造方法においては、本発明の組成物を繊維基材に付着させ、その後、組成物を加熱して凝固させ、乾燥機で乾燥することにより人工皮革を製造することができる。加熱による組成物の凝固により繊維基材中でのポリウレタン樹脂の分布が適正化した後は、基本的に多価無機酸塩は不要となることから、加熱凝固工程と乾燥工程との間に、多価無機酸塩を除去する水洗工程を導入してもよい。本発明の組成物を用いた繊維基材への付着処理は、公知の方法で行うことができる。処理方法としては限定されず、例えば、含浸装置や塗工装置等の付与装置を用いた処理が挙げられる。例えば、まず、組成物をそのまま、または水や任意の添加剤を加えるなどして加工液を調製する。次に、加工液で満たされた含浸装置に繊維基材を送り込み、繊維基材に加工液を含浸させた後、必要により余剰な加工液を除去する。付与装置としては特に限定されず、パッダ、キスロール式付与装置、グラビアコーター式付与装置、スプレー式付与装置、フォーム式付与装置、コーティング式付与装置等が好ましく採用できる。繊維基材への本発明の組成物の付着量としては、繊維基材の厚さや、得られる人工皮革の風合いや品位などに応じて適宜設定することができ、例えば、ポリウレタン樹脂の量で、繊維基材重量に対し１～１００質量％の範囲が挙げられる。 In the method for producing the artificial leather of the present invention, the artificial leather can be produced by attaching the composition of the present invention to a fiber base material, then heating the composition to solidify it, and drying it in a dryer. . After the distribution of the polyurethane resin in the fiber base material is optimized by coagulating the composition by heating, the polyvalent inorganic acid salt is basically unnecessary. A water washing step may be introduced to remove the polyvalent inorganic acid salt. Adhesion treatment to a fiber substrate using the composition of the present invention can be performed by a known method. The treatment method is not limited, and examples thereof include treatment using an application device such as an impregnation device or a coating device. For example, first, a working fluid is prepared by using the composition as it is or by adding water or optional additives. Next, the fibrous base material is fed into an impregnation device filled with the working liquid, and after the fibrous base material is impregnated with the working liquid, excess working liquid is removed if necessary. The applicator is not particularly limited, and a padder, kiss roll type applicator, gravure coater type applicator, spray type applicator, foam type applicator, coating type applicator and the like can be preferably employed. The amount of the composition of the present invention attached to the fiber base material can be appropriately set according to the thickness of the fiber base material and the texture and quality of the resulting artificial leather. A range of 1 to 100% by mass can be mentioned with respect to the weight of the fiber base material.
繊維基材に付着させた組成物の加熱による凝固及びその後の乾燥の方法としては、例えば、熱水浴中での加熱や、赤外線による加熱や、加熱水蒸気を吹き付けて加熱することにより凝固させた後、乾燥装置によって揮発性成分を除去、乾燥する方法や、乾燥装置中に導入して加熱し凝固させると共に乾燥する方法等を挙げることができる。繊維基材に付着させた組成物を加熱し凝固させる温度は、４０～１８０℃であることが好ましく、６０～１５０℃であることがより好ましい。加熱し凝固させる時間は、加熱温度によって異なるが、５秒～３０分であることが好ましく、１０秒～２０分であることがより好ましい。 The method for solidifying the composition adhered to the fiber base material by heating and subsequent drying includes, for example, heating in a hot water bath, heating by infrared rays, and heating by spraying heated steam to solidify. After that, a method of removing volatile components by a drying device and drying, and a method of introducing into a drying device, heating to solidify and drying, and the like can be mentioned. The temperature for heating and solidifying the composition adhered to the fiber substrate is preferably 40 to 180°C, more preferably 60 to 150°C. The time for heating and solidifying varies depending on the heating temperature, but is preferably 5 seconds to 30 minutes, more preferably 10 seconds to 20 minutes.
乾燥工程に用いる乾燥機としては、特に限定されず、ホットフルー、テンター等の拡布乾燥機、チーズ乾燥機、ビーム乾燥機、タンブルドライヤー等の温風乾燥機、高周波乾燥機等を用いることができる。乾燥温度は４０～１８０℃であることが好ましく、６０～１５０℃であることがより好ましい。乾燥時間は５秒～３０分であることが好ましく、１０秒～２０分であることがより好ましい。 The dryer used in the drying step is not particularly limited, and a spread dryer such as a hot flue or a tenter, a cheese dryer, a beam dryer, a warm air dryer such as a tumble dryer, a high frequency dryer, or the like can be used. . The drying temperature is preferably 40 to 180°C, more preferably 60 to 150°C. The drying time is preferably 5 seconds to 30 minutes, more preferably 10 seconds to 20 minutes.
以下、実施例により本発明をさらに具体的に説明するが、これらの実施例により本発明が限定されるものではない。なお実施例において、特に断りがない限り「部」は質量部を意味し、「％」は質量％を意味する。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, "parts" means parts by mass and "%" means % by mass unless otherwise specified.
＜原材料の説明＞
・エタナコール（登録商標）ＵＨ－１００：ポリヘキサメチレンカーボネートジオール、数平均分子量１０００、宇部興産株式会社製
・エタナコールＵＨＣ５０－１００：ポリヘキサメチレンカーボネートジオールとカプロラクトンとの反応生成物、数平均分子量１０００、宇部興産株式会社製
・ＰＴＧ－１０００ＳＮ：ポリテトラメチレンエーテルグリコール、数平均分子量１０００、保土谷化学工業株式会社製
・ＰＥＧ－６００：ポリエチレングリコール、数平均分子量６００、三洋化成株式会社製
・ＰＥＧ－２０００：ポリエチレングリコール、数平均分子量２０００、三洋化成株式会社製
・ＰＥＳ：ポリエステルポリオール、水酸基価約３５０ｍｇＫＯＨ／ｇ、東ソー株式会社製
・ＢｉｓＭＰＡ：ジメチロールプロピオン酸、パーストープ社製
・ユニオックス（登録商標）Ｍ－２０００：ポリオキシエチレンモノメチルエーテル、数平均分子量２０００、日油株式会社製
・ユニルーブ（登録商標）５０ＭＢ－１１：ポリオキシエチレンポリオキシプロピレングリコールモノブチルエーテル、数平均分子量１０００、日油株式会社製
・エマルゲン（登録商標）１４７：ポリオキシエチレンモノラウリルエーテル、数平均分子量１０００、花王株式会社製
・タケネート（登録商標）５００：ｍ－キシリレンジイソシアネート、三井化学株式会社製
・デスモジュール（登録商標）Ｗ：メチレンビス（１，４－シクロヘキサンジイル）ビスイソシアナート、コベストロ社製
・ＶＥＳＴＡＮＡＴ（登録商標）ＩＰＤＩ：イソホロンジイソシアネート、エボニック社製
・デュラネート（登録商標）５０Ｍ：ヘキサメチレンジイソシアネート、旭化成株式会社製
・ネオスタン（登録商標）Ｕ－６００：ビスマス系触媒、日東化成株式会社製
<Description of raw materials>
Ethanol (registered trademark) UH-100: polyhexamethylene carbonate diol, number average molecular weight 1000, manufactured by Ube Industries, Ltd. Ethanol UHC50-100: reaction product of polyhexamethylene carbonate diol and caprolactone, number average molecular weight 1000 Ube Industries Co., Ltd. PTG-1000 SN: polytetramethylene ether glycol, number average molecular weight 1000, Hodogaya Chemical Industry Co., Ltd. PEG-600: polyethylene glycol, number average molecular weight 600, Sanyo Kasei Co., Ltd. PEG-2000 : Polyethylene glycol, number average molecular weight 2000, manufactured by Sanyo Chemical Co., Ltd. PES: Polyester polyol, hydroxyl value about 350 mgKOH / g, manufactured by Tosoh Corporation BisMPA: Dimethylolpropionic acid, manufactured by Perstorp Uniox (registered trademark) M -2000: Polyoxyethylene monomethyl ether, number average molecular weight 2000, manufactured by NOF Corporation Unilube (registered trademark) 50MB-11: Polyoxyethylene polyoxypropylene glycol monobutyl ether, number average molecular weight 1000, manufactured by NOF Corporation ・Emulgen (registered trademark) 147: Polyoxyethylene monolauryl ether, number average molecular weight 1000, manufactured by Kao Corporation Takenate (registered trademark) 500: m-xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc. Desmodur (registered trademark) W : Methylene bis (1,4-cyclohexanediyl) bisisocyanate, manufactured by Covestro VESTANAT (registered trademark) IPDI: Isophorone diisocyanate, manufactured by Evonik Duranate (registered trademark) 50M: Hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation Neostan ( Registered Trademark) U-600: Bismuth-based catalyst manufactured by Nitto Kasei Co., Ltd.
＜水分散型ポリウレタン樹脂の作製と評価＞
合成例１
攪拌機、冷却管及び温度計を備えたセパラブルフラスコに、エタナコールＵＨ－１００（６１．６部）、ＢｉｓＭＰＡ（３．６部）、ユニオックスＭ－２０００（５．０部）、トリメチロールプロパン（１．２部）、タケネート５００（１１．７部）、デスモジュールＷ（１６．３部）、ネオスタンＵ－６００（０．０３部）及びメチルエチルケトン（６６．７部）を加えて、攪拌下７０℃で４時間加熱した。この時のＪＩＳ Ｋ １６０３－１：２００７のＡ法に準拠して測定した反応液のＮＣＯ％は０．９９６％であり、原材料の仕込み量から計算した反応後の理論ＮＣＯ％である１．０４％以下になった。すなわち、十分にウレタン化反応が進行し、末端にイソシアネート基を有するウレタンプレポリマーが生じたと判断した。続いて、反応液温度を３０℃に冷却し、トリエチルアミン（２．２部）とメチルエチルケトン（１０．８部）を加え、強攪拌下にて水（２３０部）を１０分間かけて滴下することで乳化した。続いて、エチレンジアミン（０．６２部）を水（１２．４部）に溶かして反応液へ加えた。この時、反応液温度が約１℃上昇したため、ウレア化反応が進行したと判断した。さらに反応液を４５℃で１時間加熱攪拌したのち、メチルエチルケトンを減圧留去した。最後に固形分濃度が３０％になるように水を加えて、合成例１の水分散型ポリウレタン樹脂を得た。原材料の仕込み量から算出した酸価は、１５ｍｇＫＯＨ／ｇであった。
<Preparation and evaluation of water-dispersed polyurethane resin>
Synthesis example 1
Ethanol UH-100 (61.6 parts), BisMPA (3.6 parts), Uniox M-2000 (5.0 parts), trimethylolpropane ( 1.2 parts), Takenate 500 (11.7 parts), Desmodur W (16.3 parts), Neostan U-600 (0.03 parts) and methyl ethyl ketone (66.7 parts) were added and stirred for 70 minutes. C. for 4 hours. At this time, the NCO% of the reaction liquid measured according to JIS K 1603-1:2007 A method was 0.996%, and the theoretical NCO% after the reaction calculated from the amount of raw materials charged was 1.04. % or less. That is, it was determined that the urethanization reaction proceeded sufficiently to produce a urethane prepolymer having isocyanate groups at its terminals. Subsequently, the temperature of the reaction solution was cooled to 30° C., triethylamine (2.2 parts) and methyl ethyl ketone (10.8 parts) were added, and water (230 parts) was added dropwise over 10 minutes under strong stirring. emulsified. Subsequently, ethylenediamine (0.62 parts) was dissolved in water (12.4 parts) and added to the reaction solution. At this time, the temperature of the reaction solution rose by about 1° C., so it was determined that the urea-forming reaction had progressed. Further, the reaction solution was heated and stirred at 45° C. for 1 hour, and then methyl ethyl ketone was distilled off under reduced pressure. Finally, water was added so that the solid content concentration was 30%, and a water-dispersed polyurethane resin of Synthesis Example 1 was obtained. The acid value calculated from the charged amount of raw materials was 15 mgKOH/g.
合成例２～８、比較合成例１～４
使用する原材料を表１、表２に記載するもの及び量に変えた以外は合成例１と同様にして、合成例２～８、比較合成例１～４の各々の水分散型ポリウレタン樹脂を得た。ただし、合成例５ではトリエチルアミンをウレタン化反応時に添加することで、中和剤と反応触媒とを兼ねて使用した。原材料の仕込み量から算出したそれらの酸価も、表１及び表２に示す。
Synthesis Examples 2-8, Comparative Synthesis Examples 1-4
Water-dispersed polyurethane resins of Synthesis Examples 2 to 8 and Comparative Synthesis Examples 1 to 4 were obtained in the same manner as in Synthesis Example 1, except that the raw materials used were changed to those listed in Tables 1 and 2 and in the amounts. rice field. However, in Synthesis Example 5, by adding triethylamine during the urethanization reaction, triethylamine was used as both a neutralizing agent and a reaction catalyst. Tables 1 and 2 also show their acid values calculated from the charged amounts of the raw materials.
水分散型ポリウレタン樹脂の多価無機酸塩最大許容量の評価
得られた各水分散型ポリウレタン樹脂の水希釈液に硫酸ナトリウム（Ｎａ2ＳＯ4）を加えてよく混合し、ウレタン樹脂の固形分濃度が５％で、硫酸ナトリウムの固形分濃度が１、２、３、４、５、６、７及び８％の各混合液を調製した。これらの混合液を５分間静置した後、含有成分の凝集（ゲル化や沈殿の発生）の有無を目視観察して、含有成分の凝集が発生していない混合液を確認し、それらの中で最大の硫酸ナトリウム固形分濃度を「硫酸ナトリウムの最大許容量」とした。ただし、硫酸ナトリウムの固形分濃度が１％でも含有成分の凝集が起こる場合は「＜１％」、硫酸ナトリウムの固形分濃度が８％でも含有成分の凝集が起こらない場合は「≧８％」とした。結果を表１及び表２に示す。
Evaluation of maximum permissible amount of polyvalent inorganic acid salt in water-dispersed polyurethane resin Sodium sulfate (Na 2 SO 4 ) was added to the obtained water-diluted solution of each water-dispersed polyurethane resin and mixed well to determine the solid content of the urethane resin. Mixtures were prepared with a concentration of 5% and solids concentrations of sodium sulfate of 1, 2, 3, 4, 5, 6, 7 and 8%. After these mixed solutions were left to stand for 5 minutes, the presence or absence of aggregation of the ingredients (occurrence of gelation or precipitation) was visually observed to confirm the mixtures in which aggregation of the ingredients did not occur. The maximum sodium sulfate solid content concentration was defined as the "maximum permissible amount of sodium sulfate". However, "<1%" if the contained ingredients aggregate even if the solid concentration of sodium sulfate is 1%, and "≧8%" if the contained ingredients do not aggregate even if the solid concentration of sodium sulfate is 8%. and The results are shown in Tables 1 and 2.
硫酸ナトリウムの代わりにリン酸カリウム（Ｋ3ＰＯ4）を用いた以外は「硫酸ナトリウムの最大許容量」と同様にして「リン酸カリウムの最大許容量」を評価した。また、硫酸ナトリウムの代わりに炭酸ナトリウム（Ｎａ2ＣＯ3）を用いた以外は「硫酸ナトリウムの最大許容量」と同様にして「炭酸ナトリウムの最大許容量」を評価した。更に、硫酸ナトリウムの代わりにチオ硫酸ナトリウム（Ｎａ2Ｓ2Ｏ3）を用いた以外は「硫酸ナトリウムの最大許容量」と同様にして「チオ硫酸ナトリウムの最大許容量」を評価した。加えて、硫酸ナトリウムの代わりにケイ酸ナトリウム（Ｎａ2ＳｉＯ3）を用いた以外は「硫酸ナトリウムの最大許容量」と同様にして「ケイ酸ナトリウムの最大許容量」を評価した。これらの結果も表１及び表２に示す。 The "maximum permissible amount of potassium phosphate" was evaluated in the same manner as the "maximum permissible amount of sodium sulfate" except that potassium phosphate ( K3PO4 ) was used instead of sodium sulfate. Also, the "maximum permissible amount of sodium carbonate" was evaluated in the same manner as the "maximum permissible amount of sodium sulfate" except that sodium carbonate (Na 2 CO 3 ) was used instead of sodium sulfate. Further, the "maximum permissible amount of sodium thiosulfate" was evaluated in the same manner as the "maximum permissible amount of sodium sulfate" except that sodium thiosulfate (Na 2 S 2 O 3 ) was used instead of sodium sulfate. In addition, the "maximum permissible amount of sodium silicate" was evaluated in the same manner as the "maximum permissible amount of sodium sulfate" except that sodium silicate (Na 2 SiO 3 ) was used instead of sodium sulfate. These results are also shown in Tables 1 and 2.
表１及び表２の結果より、合成例と比較合成例を対比すると、本発明の組成物に用いる水分散型ポリウレタン樹脂は多価無機酸塩の最大許容量が高く、多価無機酸塩の存在下で凝集し難いことが分かる。 From the results in Tables 1 and 2, comparing Synthesis Examples and Comparative Synthesis Examples, the water-dispersible polyurethane resin used in the composition of the present invention has a high maximum allowable amount of polyvalent inorganic acid salt, and the maximum allowable amount of polyvalent inorganic acid salt is It can be seen that it is difficult to aggregate in the presence.
＜組成物、人工皮革の作製と評価＞
実施例１の組成物及び人工皮革の作製
水に、合成例１の水分散型ポリウレタン樹脂を固形分濃度で５％、硫酸ナトリウムを固形分濃度で５％添加して実施例１の組成物を作製し加工液とした。この加工液を繊維基材「ＫフェルトＫＴ１００１」（フェルト状不織布、ポリエステル１００％、大きさ１８０ｍｍ×１８０ｍｍ、厚さ約１ｍｍ、清原株式会社製）に含浸してマングルで絞り、ピンテンターを用いて１３０℃で９０秒乾燥した。続いて、これを約９０℃の熱水で洗って硫酸ナトリウムを水洗して除去し、その後、ピンテンターを用いて９０℃で５分間乾燥して、実施例１の人工皮革を得た。
<Production and evaluation of composition and artificial leather>
Preparation of composition and artificial leather of Example 1 To water, the water-dispersible polyurethane resin of Synthesis Example 1 was added at a solid content concentration of 5% and sodium sulfate at a solid content concentration of 5% to prepare the composition of Example 1. It was prepared and used as a working fluid. This working liquid is impregnated into a fiber base material “K Felt KT1001” (felt-like nonwoven fabric, 100% polyester, size 180 mm × 180 mm, thickness about 1 mm, manufactured by Kiyohara Co., Ltd.), squeezed with a mangle, and 130 using a pin tenter. C. for 90 seconds. Subsequently, this was washed with hot water at about 90°C to remove sodium sulfate, and then dried at 90°C for 5 minutes using a pin tenter to obtain the artificial leather of Example 1.
比較例１－１の組成物及び人工皮革の作製
実施例１の組成物の作製において、硫酸ナトリウムを用いないこと以外は同様にして、比較例１－１の組成物を作製して加工液とし、実施例１の人工皮革の作製において、この加工液を用いた以外は同様にして比較例１－１の人工皮革を得た。
Preparation of the composition of Comparative Example 1-1 and artificial leather The composition of Comparative Example 1-1 was prepared in the same manner as in the preparation of the composition of Example 1, except that sodium sulfate was not used, and used as a working liquid. An artificial leather of Comparative Example 1-1 was obtained in the same manner as in the preparation of the artificial leather of Example 1, except that this working liquid was used.
実施例２～８、比較例１－２～１－８の組成物及び人工皮革の作製
実施例１の組成物の作製において、合成例１の水分散型ポリウレタン樹脂の代わりに合成例２～８の各水分散型ポリウレタン樹脂を用いた以外は同様にして、実施例２～８の各組成物を作製して加工液とし、実施例１の人工皮革の作製において、これらの加工液を用いた以外は同様にして実施例２～８の各人工皮革を得た。また、実施例２～８の各組成物の作製において、硫酸ナトリウムを用いないこと以外は同様にして、比較例１－２～１－８の各組成物を作製して加工液とし、実施例２～８の各人工皮革の作製において、これらの加工液を用いた以外は同様にして比較例１－２～１－８の各人工皮革を得た。
Preparation of compositions and artificial leathers of Examples 2 to 8 and Comparative Examples 1-2 to 1-8 In the preparation of the composition of Example 1, instead of the water-dispersible polyurethane resin of Synthesis Example 1, Synthesis Examples 2 to 8 Each composition of Examples 2 to 8 was prepared in the same manner as the working liquid except that each water-dispersed polyurethane resin was used, and these working liquids were used in the preparation of the artificial leather of Example 1. Artificial leathers of Examples 2 to 8 were obtained in the same manner as above. Further, each composition of Comparative Examples 1-2 to 1-8 was prepared as a working liquid in the same manner as in the preparation of each composition of Examples 2 to 8 except that sodium sulfate was not used. Artificial leathers of Comparative Examples 1-2 to 1-8 were obtained in the same manner as in the production of artificial leathers of 2 to 8, except that these working liquids were used.
比較例２－１～２－３、３－１～３－３の組成物及び人工皮革の作製
実施例１の組成物の作製において、合成例１の水分散型ポリウレタン樹脂の代わりに比較合成例１～３の各水分散型ポリウレタン樹脂を用いた以外は同様にして、比較例２－１～２－３の各組成物を作製して加工液とし、実施例１の人工皮革の作製において、これらの加工液を用いた以外は同様にして比較例２－１～２－３の各人工皮革を得た。ただし、比較合成例１～３の各水分散型ポリウレタン樹脂の「硫酸ナトリウムの最大許容量」は各々２％であって、実施例と同様に硫酸ナトリウムの固形分濃度を５％とすると組成物が凝集して使用できないため、比較例２－１～２－３の各組成物の硫酸ナトリウムの固形分濃度は２％とした。比較合成例４の水分散型ポリウレタン樹脂に関しては、「硫酸ナトリウムの最大許容量」は１％未満であって、組成物への有効な量の硫酸ナトリウムの添加が行えないことから、組成物及び人工皮革の作製は行わなかった。また、比較例２－１～２－３の各組成物の作製において、硫酸ナトリウムを用いないこと以外は同様にして、比較例３－１～３－３の各組成物を作製して加工液とし、比較例２－１～２－３の各人工皮革の作製において、これらの加工液を用いた以外は同様にして比較例３－１～３－３の各人工皮革を得た。
Preparation of compositions and artificial leathers of Comparative Examples 2-1 to 2-3 and 3-1 to 3-3 Each composition of Comparative Examples 2-1 to 2-3 was prepared in the same manner as above except that each of the water-dispersed polyurethane resins of 1 to 3 was used as a working liquid, and in the preparation of the artificial leather of Example 1, Artificial leathers of Comparative Examples 2-1 to 2-3 were obtained in the same manner except that these working liquids were used. However, the "maximum permissible amount of sodium sulfate" of each of the water-dispersed polyurethane resins of Comparative Synthesis Examples 1 to 3 was 2%, and the solid content concentration of sodium sulfate was 5% as in Examples. Since it cannot be used due to aggregation, the solid content concentration of sodium sulfate in each composition of Comparative Examples 2-1 to 2-3 was set to 2%. Regarding the water-dispersible polyurethane resin of Comparative Synthesis Example 4, the "maximum allowable amount of sodium sulfate" was less than 1%, and an effective amount of sodium sulfate could not be added to the composition. No artificial leather was produced. Further, each composition of Comparative Examples 3-1 to 3-3 was prepared in the same manner as in the preparation of each composition of Comparative Examples 2-1 to 2-3 except that sodium sulfate was not used, and the working liquid Then, the artificial leathers of Comparative Examples 3-1 to 3-3 were obtained in the same manner as in the preparation of the artificial leathers of Comparative Examples 2-1 to 2-3, except that these working fluids were used.
実施例６－１～６－７の組成物及び人工皮革の作製
実施例６の組成物の作製において、表５に示す硫酸ナトリウムの添加量とした以外は同様にして実施例６－１～６－７の各組成物を作製して加工液とし、実施例６の人工皮革の作製において、これらの加工液を用いた以外は同様にして実施例６－１～６－７の各人工皮革を得た。
Preparation of compositions and artificial leather of Examples 6-1 to 6-7 In the preparation of the composition of Example 6, except that the amount of sodium sulfate added shown in Table 5 was used in the same manner as in Examples 6-1 to 6 -7 each composition was prepared as a working liquid, and in the preparation of the artificial leather of Example 6, each artificial leather of Examples 6-1 to 6-7 was similarly prepared except that these working liquids were used. Obtained.
ポリウレタン樹脂付着量の測定
上記で用いた各繊維基材と得られた各人工皮革の質量を最小目盛０．１ｇの電子天秤で測定し、その差をポリウレタン樹脂付着量として算出した。また、硫酸ナトリウムを用いた人工皮革と硫酸ナトリウムを用いなかった人工皮革との間で、ポリウレタン樹脂付着量の差異は小さいことを示すために、実施例１と比較例１－１、・・・、実施例８と比較例１－８、比較例２－１と比較例３－１、・・・、比較例２－３と比較例３－３の組み合わせで、ポリウレタン樹脂付着量の差（「実施例の樹脂付着量」－「比較例の樹脂付着量」）を算出した。これらの結果を表３及び表４に示す。表５においては、実施例６及び実施例６－１～６－７の各人工皮革と比較例１－６の人工皮革との間のポリウレタン樹脂付着量の差を示す。
Measurement of Amount of Polyurethane Resin Attached The mass of each fiber base material used above and each artificial leather obtained was measured with an electronic balance with a minimum scale of 0.1 g, and the difference was calculated as the amount of polyurethane resin attached. In addition, in order to show that the difference in polyurethane resin adhesion amount between the artificial leather using sodium sulfate and the artificial leather not using sodium sulfate is small, Example 1 and Comparative Example 1-1, . . . , Example 8 and Comparative Example 1-8, Comparative Example 2-1 and Comparative Example 3-1, . The resin adhesion amount of the example"−"the resin adhesion amount of the comparative example") was calculated. These results are shown in Tables 3 and 4. Table 5 shows the difference in polyurethane resin adhesion amount between the artificial leathers of Example 6 and Examples 6-1 to 6-7 and the artificial leathers of Comparative Example 1-6.
剛軟度の評価
得られた人工皮革の剛軟度について、ハンドロメーターＨＯＭ－２（大栄科学精器製作所製）を用い、ＪＩＳ Ｌ １０９６：２０１０ ８．２１．５ Ｅ法（ハンドルオメータ法）に準拠して測定した。（試験片サイズ：１８０ｍｍ×１８０ｍｍ、スロット幅：１０ｍｍ）また、硫酸ナトリウムを用いた人工皮革と硫酸ナトリウムを用いなかった人工皮革との剛軟度の差を示すために、実施例１と比較例１－１、・・・、実施例８と比較例１－８、比較例２－１と比較例３－１、・・・、比較例２－３と比較例３－３の組み合わせで、剛軟度の差（「実施例の剛軟度」－「比較例の剛軟度」）を算出した。この剛軟度の差（低下量）が大きいほど、硫酸ナトリウムを用いることによる風合いの改善効果がより大きいことを表す。これらの結果を表３及び表４に示す。表５においては、実施例６及び実施例６－１～６－７の各人工皮革と比較例１－６の人工皮革との間の剛軟度の差を示す。
Evaluation of bending resistance Regarding the bending resistance of the obtained artificial leather, using a handrometer HOM-2 (manufactured by Daiei Kagaku Seiki Seisakusho), JIS L 1096: 2010 8.21.5 E method (Handle Ometer method ) was measured according to (Test piece size: 180 mm × 180 mm, slot width: 10 mm) In addition, in order to show the difference in bending resistance between the artificial leather using sodium sulfate and the artificial leather not using sodium sulfate, Example 1 and Comparative Example 1-1, . . . , Example 8 and Comparative Example 1-8, Comparative Example 2-1 and Comparative Example 3-1, . The difference in softness (“bending resistance of example”−“bending resistance of comparative example”) was calculated. The greater the difference in bending resistance (decreased amount), the greater the effect of improving the feel due to the use of sodium sulfate. These results are shown in Tables 3 and 4. Table 5 shows the difference in bending resistance between each artificial leather of Example 6 and Examples 6-1 to 6-7 and the artificial leather of Comparative Example 1-6.
表３～表５の結果より、上記一般式（１）で表されるポリアルキレングリコールモノアルキルエーテルに由来する構造を有するアニオン性の水分散型ポリウレタン樹脂を用いた本発明の組成物は、ポリアルキレングリコールモノアルキルエーテル部位を有さないアニオン性の水分散型ポリウレタン樹脂を用いた場合よりも多価無機酸塩を高濃度で用いても含有成分が凝集し難いため、繊維基材への付与時における組成物の使用に支障をきたすことがなく、また、それを用いることにより、良好な風合いを有する人工皮革を製造できることがわかる。 From the results of Tables 3 to 5, the composition of the present invention using an anionic water-dispersible polyurethane resin having a structure derived from the polyalkylene glycol monoalkyl ether represented by the general formula (1) is poly Even if the polyvalent inorganic acid salt is used at a high concentration, the contained components are less likely to aggregate than when an anionic water-dispersible polyurethane resin that does not have an alkylene glycol monoalkyl ether moiety is used. It can be seen that there is no hindrance to the use of the composition at times, and by using it, an artificial leather having a good texture can be produced.
Claims (8)
ＲＯ－（Ｃ2Ｈ4Ｏ）m（Ｃ3Ｈ6Ｏ）n－Ｈ （１）
（Ｒは炭素数１～１０のアルキル基、ｍは１以上の整数、ｎは０以上の整数を表す。） A structure derived from a polyol compound having a group selected from a carbonate group, an ester group and an ether group, a structure derived from a polyol compound having a carboxy group, and a polyalkylene glycol monoalkyl ether represented by the following general formula (1) A composition containing a polyurethane resin having a structure derived from, a polyvalent inorganic acid salt, and an aqueous medium.
RO—(C 2 H 4 O) m (C 3 H 6 O) n —H (1)
(R is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 or more, and n is an integer of 0 or more.)
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