JP2005015626A - One-pack aqueous polyurethane resin composition and aqueous resin composition containing the same - Google Patents
One-pack aqueous polyurethane resin composition and aqueous resin composition containing the same Download PDFInfo
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- JP2005015626A JP2005015626A JP2003182088A JP2003182088A JP2005015626A JP 2005015626 A JP2005015626 A JP 2005015626A JP 2003182088 A JP2003182088 A JP 2003182088A JP 2003182088 A JP2003182088 A JP 2003182088A JP 2005015626 A JP2005015626 A JP 2005015626A
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- Prior art keywords
- resin composition
- polyurethane resin
- component
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- aqueous polyurethane
- Prior art date
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 58
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- -1 hydrogen compound Chemical class 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 230000009257 reactivity Effects 0.000 claims description 8
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 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 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 66
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 230000008034 disappearance Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 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
- 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
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 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
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XRBXGZZMKCBTFP-UHFFFAOYSA-N 4-(2,2-dihydroxyethoxycarbonyl)benzoic acid Chemical compound OC(O)COC(=O)C1=CC=C(C(O)=O)C=C1 XRBXGZZMKCBTFP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- QPGQPZQYAMNOPE-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate;sodium Chemical compound [Na].COC(=O)C1=CC=CC(C(=O)OC)=C1 QPGQPZQYAMNOPE-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BNMCQIRVFUGISV-UHFFFAOYSA-N propan-2-one;prop-2-enamide Chemical compound CC(C)=O.NC(=O)C=C BNMCQIRVFUGISV-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
この発明は、一液性水系ポリウレタン樹脂組成物及び該組成物を含有する水性樹脂組成物に関し、更に詳しくは、常温硬化型で、耐水性、耐溶剤性、耐久性等に優れた皮膜を形成することができる、建物、車両、船舶、などの塗装に適した一液性水系ポリウレタン樹脂組成物及び該組成物を含有する水性樹脂組成物に関するものである。
【０００２】
【従来の技術】
耐水性や耐久性が要求される建築物などの外壁塗装用塗料として、従来より常温硬化性樹脂が使用されている。この常温硬化性樹脂には従来より有機溶剤を含有するポリウレタン樹脂が使用されているため、環境問題や消防法等の点から好ましくなく、有機溶剤を含まない水性樹脂への転換が要望されている。従って、有機溶剤を含有するポリウレタン樹脂と同等の性能を有する常温硬化性の水性ポリウレタン樹脂が必要とされるに至っている。
【０００３】
そのような背景から、カルボニル基含有アクリル系共重合体水分散体にヒドラジド基を有するウレタン共重合体水分散液を混合したものが提案されている（特許文献１及び特許文献２）。
【０００４】
また、カルボニル基を有するアクリル系共重合物に対してカルボニル基を含有する水性ポリウレタン樹脂を添加し、更に架橋剤としてヒドラジド基を有する化合物を添加した樹脂組成物が提案されている（特許文献３及び特許文献４）。
【０００５】
しかし、これらの樹脂組成物は、乾燥性、耐水性、塗膜弾性などに優れているとされているが、架橋度を十分に高くすることができず、得られる膜の諸物性、特に耐水性や耐溶剤について十分な結果を得ることがでない。
【０００６】
一方、水性ポリウレタンにアクリル樹脂を約５０〜７０％配合した場合、溶剤系ポリウレタン樹脂に比較して皮膜の弾性や強靭性が劣る傾向がある。また、従来のケトン性カルボニル基含有水性ウレタン樹脂では、分子末端にのみケトン性カルボニル基が導入されているため、十分な架橋密度を得ることができず、耐水性や耐溶剤を高めることができない。
【０００７】
【特許文献１】
特開平１−３０１７６１号公報（第２頁右上欄第１６行目〜左下欄第７行目）
【特許文献２】
特開平１−３０１７６２号公報（第２頁右上欄第１８行目〜左下欄第９行目）
【特許文献３】
特開平７−１１１９３号公報（段落番号０００５）
【特許文献４】
特開平７−１１３０６１号公報（段落番号０００５）
【０００８】
【発明が解決しようとする課題】
本発明は、上記従来技術の問題点を解決するために為されたもであり、本発明の目的は、耐水性、耐溶剤性、耐久性等に優れた皮膜を形成することができる、常温硬化型の一液性水系ポリウレタン樹脂組成物及び該組成物を含有する水性樹脂組成物を提供することである。
【０００９】
【課題を解決するための手段】
本発明の一液性水系ポリウレタン樹脂組成物は、（Ａ）１分子中に２個以上のケトン性カルボニル基を有する水系ポリウレタン樹脂と、（Ｃ）１分子中に２個以上のヒドラジド基を有するヒドラジド化合物とを含有してなることを特徴とする。
【００１０】
本発明に於いては、（Ａ）成分の分子中のケトン性カルボニルが（Ｃ）成分であるヒドラジド化合物のヒドラジド基と反応して＞Ｃ＝Ｎ−ＮＨ−結合を形成することにより、塗膜の耐水性、耐溶剤性、耐久性等が向上するものと考えられる。
【００１１】
また、本発明の一液性水系ポリウレタン樹脂組成物は、（Ｂ）１分子中に２個以上のケトン性カルボニル基及び２個以上のヒドラジド基を有する水系ポリウレタン樹脂を含有してなることを特徴とする。
【００１２】
本発明に於いては、（Ｂ）成分の分子中のヒドラジド基が他の分子のケトン性カルボニルと反応して＞Ｃ＝Ｎ−ＮＨ−結合を形成することにより、塗膜の耐水性、耐溶剤性、耐久性等が向上するものと考えられる。
【００１３】
【発明の実施の形態】
本発明の一液性水系ポリウレタン樹脂組成物は、上記のように、（Ａ）１分子中に２個以上のケトン性カルボニル基を有する水系ポリウレタン樹脂と、（Ｃ）１分子中に２個以上のヒドラジド基を有するヒドラジド化合物とを含有してなる。
【００１４】
ここで、（Ａ）の水系ポリウレタン樹脂に於いては、ケトン性カルボニル基は、ポリウレタン樹脂組成物中にカルボニル当量として５００〜１０，０００（ｇ／ｍｏｌ）となるように含まれていることが好ましく、１，０００〜５，０００ｇ／ｍｏｌ）となるように含まれていることがより好ましい。このカルボニル当量が上記範囲より小さいと、硬化収縮が大きくなり、また経済的にも不利となる。また、カルボニル当量が上記範囲より大きいと、架橋効果が不十分となる傾向が現れる。
【００１５】
本発明に於ける（Ａ）成分の水系ポリウレタン樹脂は、（ａ）有機ポリイソシアネートと、（ｂ）ＮＣＯ基との反応性を有する活性水素を２個以上含有する活性水素含有化合物と、（ｃ）ケトン性カルボニル基を含有し、かつ、ＮＣＯ基との反応性を有する活性水素を少なくとも１個以上含有するカルボニル基含有活性水素化合物との反応により得ることができる。
【００１６】
ここで、（ａ）成分の有機ポリイソシアネートとしては、従来から慣用されている芳香族、脂肪族または脂環族の有機ポリイソシアネートを使用することができ、具体例として、脂肪族ジイソシアネート（例えば、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、１，４−ブタンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２−メチルペンタン−１，５−ジイソシアネート、３−メチルペンタン−１，５−ジイソシアネートなどが例示できる）、脂環族ジイソシアネート（例えば、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’−シクロヘキシルメタンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサンなどが例示できる）、芳香族ジイソシアネート（例えば、トリレンジイソシアネート、２，２’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルジメチルメタンジイソシアネート、４，４’−ジベンジルジイソシアネート、１，５−ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネートなどが例示できる）、芳香脂肪族ジイソシアネート（例えば、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α−テトラメチルキシリレンジイソシアネートなどが例示できる）、トリレンジイソシアネ−ト等を挙げることができる。これらの有機ポリソシアネートは単独でも用いることができ、また２種以上の混合物にして用いることもできる。
【００１７】
また、（ｂ）成分の活性水素含有化合物は、ＮＣＯ基との反応性を有する活性水素を２個以上含有するものである。即ち、ヒドロキシル基、アミノ基又はメルカプト基を有するもので、一般に公知のポリエーテル、ポリエステル、ポリエーテルエステル、ポリチオエーテル、ポリアセタール、ポリブタジエン、ポリシロキサン等であり、好ましくは、分子末端に２個以上のヒドロキシル基を有する化合物である。具体的には、２個以上の活性水素基を有するポリヒドロキシ化合物として、エチレングリコール、ジエチレングリコール、ブタンジオール、プロピレングリコール、ヘキサンジオール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、水素添加ビスフェノールＡ、ジブロモビスフェノールＡ、１，４−シクロヘキサンジメタノール、ジヒドロキシエチルテレフタレート、ハイドロキノンジヒドロキシエチルエーテル、トリメチロールプロパン、グリセリン、ジグリセリン，ペンタエリスリトール，ソルビトール等の多価アルコール、それらのオキシアルキレン誘導体又はそれらの多価アルコール若しくはオキシアルキレン誘導体と多価カルボン酸、多価カルボン酸無水物、若しくは多価カルボン酸エステルとにより得られるエステル化合物、ポリカーボネートポリオール、ポリカプロラクトンポリオール、ポリエステルポリオール、ポリチオエーテルポリオール、ポリアセタールポリオール、ポリテトラメチレングリコール、ポリブタジエンポリオール、ヒマシ油ポリオール、フッ素ポリオール、シリコンポリオール等のポリオール化合物やその変性体が挙げられる。
【００１８】
（ｃ）成分のカルボニル基含有活性水素化合物は、ケトン性カルボニル基を含有し、かつ、ＮＣＯ基との反応性を有する活性水素を少なくとも２個以上含有するものであり、具体的には、ダイアセトンアクリルアミドに対してジアルカノールアミンを付加反応させて得られる化合物を例示することができる。
【００１９】
本発明に於ける（Ｃ）成分のヒドラジド化合物は、１分子中に２個以上のヒドラジド基を有するものであり、具体例としては、シュウ酸ジヒドラジド，マロン酸ジヒドラジド，アジピン酸ジヒドラジド，アゼライン酸ジヒドラジド，コハク酸ジヒドラジド，セバシン酸ジヒドラジド，マレイン酸ジヒドラジド，フマル酸ジヒドラジド，イタコン酸ジヒドラジド等のジカルボン酸ジヒドラジド、１，３−ビス（ヒドラジノカルボエチル）−５−イソプロピルヒダントイン、カルボヒドラジド等が挙げられる。これらは単独で使用してもよく、２種以上を組み合わせて使用してもよい。これらのうちで、汎用性の点や水への溶解性が良好である点から、アジピン酸ジヒドラジドがより好ましい。また、（Ｃ）成分のヒドラジド化合物として、分子末端遊離イソシアネート基を有するポリウレタンプレポリマーに対して１分子中に２個以上のヒドラジド基を有する化合物を反応させて得られる分子末端に−ＮＨＮＨ２基を有するポリウレタンプレポリマーも例示することができ、この場合に於ける１分子中に２個以上のヒドラジド基を有する化合物として、アジピン酸ジヒドラジドを用いることが好ましい。
【００２０】
また、本発明の他の実施形態に係る一液性水系ポリウレタン樹脂組成物は、上記のように、（Ｂ）１分子中に２個以上のケトン性カルボニル基及び２個以上のヒドラジド基を有する水系ポリウレタン樹脂を含有してなるものである。
【００２１】
ここで、（Ｂ）の水系ポリウレタン樹脂に於いては、ケトン性カルボニル基は、ポリウレタン樹脂組成物中にカルボニル当量として５００〜１０，０００（ｇ／ｍｏｌ）となるように含まれていることが好ましく、１，０００〜５，０００ｇ／ｍｏｌ）となるように含まれていることがより好ましい。このカルボニル当量が上記範囲より小さいと、硬化収縮が大きくなり、また経済的にも不利となる。また、カルボニル当量が上記範囲より大きいと、架橋効果が不十分となる傾向が現れる。
【００２２】
本発明に於ける（Ｂ）成分である水系ポリウレタン樹脂としては、上記でそれぞれ例示した（ａ）成分の有機ポリイソシアネートと、（ｂ）成分の活性水素含有化合物と、（ｃ）成分のカルボニル基含有活性水素化合物との反応により分子末端にイソシアネート基を有するポリウレタンプレポリマーを得、その分子末端遊離イソシアネート基に対して、上記で例示した（Ｃ）成分のヒドラジド化合物を反応させることにより得られる、分子末端に−ＮＨＮＨ２基を有するポリウレタンプレポリマーを例示することができる。
【００２３】
【実施例】
（カルボニル基含有活性水素化合物Ｘ…（ｃ）成分の合成）
（ｃ）成分のカルボニル基含有活性水素化合物として、ダイアセトンアクリルアミドのジエタノールアミン付加物を以下のようにして合成した。
【００２４】
ダイアセトンアクリルアミド１６９重量部に対してジエタノールアミン９４．５重量部を添加し、１００℃×３時間加熱を行うことにより、（ｃ）成分であるダイアセトンアクリルアミドのジエタノールアミン付加物を得、これをカルボニル基含有活性水素化合物Ｘとした。このカルボニル基含有活性水素化合物Ｘの臭素価は６．１であった。臭素価はＪＩＳ−Ｋ−３３３１に準拠して測定した。
【００２５】
（合成例１…（Ａ）成分の合成）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、イソホロンジイソシアネート１０７．２重量部、及びメチルエチルケトン１１４重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は５．１０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸１８．１重量部、先に合成したカルボニル基含有活性水素化合物Ｘを３９．５重量部、トリエチルアミン７．３重量部、及びメチルエチルケトン９４．５重量部を添加し、７０〜７５℃で１８０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．２０（％）であった。このプレポリマーを撹拌下において水で希釈した後、ジプロピレントリアミンを５．８重量部添加し、末端ＮＣＯ基をアミン伸長し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子側鎖にケトン性カルボニル基を有する（Ａ）成分のアニオン性ポリウレタンポリマー水溶液Ｉを得た（理論カルボニル当量は３４９０（ｇ／ｍｏｌ））。
【００２６】
（合成例２…（Ｂ）成分の合成）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、イソホロンジイソシアネート１０７．２重量部、及びメチルエチルケトン１３９重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は６．９０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸１８．１重量部、先に合成したカルボニル基含有活性水素化合物Ｘを３９．５重量部、トリエチルアミン７．３重量部、及びメチルエチルケトン９３．５重量部を添加し、７０〜７５℃で６０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．２０（％）であった。このプレポリマーを撹拌下において、アジピン酸ジヒドラジド２３．０重量部を溶解した希釈水で希釈し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子側鎖にケトン性カルボニル基を有し、かつ、末端ヒドラジド基を有する（Ｂ）成分のアニオン性ポリウレタンプレポリマー水溶液ＩＩを得た（理論カルボニル当量は３６４０（ｇ／ｍｏｌ））。
【００２７】
（合成例３…（Ａ）成分の合成）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０２、ミテックス株式会社製、水酸基価＝１１２．０）２００重量部、及びジメチルイソフタレートスルホン酸ソーダ２６．７重量部を添加し、更にパラトルエンスルホン酸ソーダを０．４５重量部添加し、減圧下で１６０℃×８時間加熱を行った。このときの水酸基価は５１．０であった。このポリエステルポリオールを１２７重量部採取し、更に１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）２４０．０重量部、先に合成したカルボニル基含有活性水素化合物Ｘを３５．１重量部、イソホロンジイソシアネート８３．３重量部、及びメチルエチルケトン３６２重量部を添加し、７０〜７５℃で２４０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．３０（％）であった。これに水を加えて乳化し、更に水で希釈した後、ジプロピレントリアミン６．５重量部を添加して末端ＮＣＯ基をアミン伸長し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子側鎖にケトン性カルボニル基を有する（Ａ）成分のアニオン性ポリウレタンポリマー水溶液ＩＩＩを得た（理論カルボニル当量は３４３０（ｇ／ｍｏｌ））。
【００２８】
（合成例４…（Ａ）成分の合成）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、トリメチロールプロパン１３．４重量部、イソホロンジイソシアネート１５３．２重量部、及びメチルエチルケトン１４０重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は７．１０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸２０．１重量部、先に合成したカルボニル基含有活性水素化合物Ｘを４４．２重量部、トリエチルアミン７．３重量部、及びメチルエチルケトン１２５．４重量部を添加し、７０〜７５℃で１８０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．５０（％）であった。このプレポリマーを撹拌下において水で希釈した後、ジプロピレントリアミンを７．７重量部添加して末端ＮＣＯ基をアミン伸長し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子側鎖にケトン性カルボニル基を有する（Ａ）成分のアニオン性ポリウレタンポリマー水溶液ＩＶを得た（理論カルボニル当量は３５９０（ｇ／ｍｏｌ））。
（合成例５…（Ａ）成分の合成）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、先に合成したカルボニル基含有活性水素化合物Ｘを３９．５重量部、イソホロンジイソシアネート７５．９重量部、及びメチルエチルケトン２０６重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．２０（％）であった。次に、系の温度を５０℃まで冷却し、酢酸８．１重量部を添加し、十分撹拌した後、このプレポリマーを撹拌下において水で希釈し、更にジプロピレントリアミンを５．０重量部添加して末端ＮＣＯ基をアミン伸長し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子側鎖にケトン性カルボニル基を有する（Ａ）成分のカチオン性ポリウレタンポリマー水溶液Ｖを得た（理論カルボニル当量は３０６０（ｇ／ｍｏｌ））。
（合成例６…（Ｃ）成分の合成）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、イソホロンジイソシアネート８３．３重量部、及びメチルエチルケトン１１４重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は４．９０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸２０．１重量部、トリエチルアミン１．５重量部、及びメチルエチルケトン８５．２重量部を添加し、７０〜７５℃で６０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．６０（％）であった。このプレポリマーを３５℃まで冷却し、アジピン酸ジヒドラジドを２６．８重量部溶解させた希釈水を添加し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子末端にヒドラジド基を有する（Ｃ）成分のアニオン性ポリウレタンプレポリマー水溶液ＶＩを得た。
（比較合成例１）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、イソホロンジイソシアネート８３．３重量部、及びメチルエチルケトン１１４重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は４．９０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸２０．１重量部、トリエチルアミン１．５重量部、及びメチルエチルケトン８５．２重量部を添加し、７０〜７５℃で６０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．６０（％）であった。このプレポリマーを６０℃まで冷却し、ダイアセトンアルコール１９．６重量部を添加し、７５℃×３時間反応させた。このときの遊離イソシアネート基含有量は０．２％であった。このプレポリマーを３５℃まで冷却し、希釈水を添加し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにより、純分３５％の分子末端のみにケトン性カルボニル基を有するウレタンポリマー水溶液ｉを得た。
（比較合成例２）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、トリメチロールプロパン１３．４重量部、イソホロンジイソシアネート１１４．９重量部、及びメチルエチルケトン１４０重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は４．２０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸２０．１重量部、トリエチルアミン７．３重量部、及びメチルエチルケトン１２５．４重量部を添加し、７０〜７５℃で１８０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．３０（％）であった。このプレポリマーを６０℃まで冷却した後、ダイアセトンアルコール１７．７重量部を添加し、７５℃×３時間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は０．２０（％）であった。これを撹拌下において水で希釈し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにり、純分３５％の分子末端にケトン性カルボニル基を有するポリウレタンポリマー水溶液ｉｉを得た。
（比較合成例３）
１，６−ヘキサンジオールのカーボネート（ラベカーブ１０６、ミテックス株式会社製、水酸基価＝５６．１）３００重量部、イソホロンジイソシアネート８３．３重量部、及びメチルエチルケトン１１４重量部を添加し、７０〜７５℃で９０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は４．９０（％）であった。次に、系の温度を５０℃とし、ジメチロールプロピオン酸２０．１重量部、トリエチルアミン１．５重量部、及びメチルエチルケトン８５．２重量部を添加し、７０〜７５℃で６０分間反応させた。このときの遊離イソシアネート基含有量（固形分換算）は１．６０（％）であった。プレポリマーを３５℃まで冷却し、希釈水を添加し、更にジプロピレントリアミン６．７重量部を溶解した水溶液を添加し、遊離イソシアネート基（％）の消失を確認した後、メチルエチルケトンを留去することにり、純分３５％のウレタンポリマー水溶液ｉｉｉを得た。
【００２９】
＜常温硬化性の水性樹脂組成物の調製＞
（実施例１〜８）
合成例１〜６で得られたウレタンポリマー又はウレタンプレポリマーを表１に示す割合で配合し、常温硬化性の水性樹脂組成物を調製した。
【００３０】
【表１】
（比較例１〜３）
比較合成例１〜３で得られたウレタンポリマー又はウレタンプレポリマーを表２に示す割合で配合し、常温硬化性の水性樹脂組成物を調製した。
【００３２】
【表２】
上記で調製した実施例１〜８及び比較例１〜３の水性樹脂組成物を用いて塗膜を形成し、以下に示す方法で、その耐水性、アセトン不溶解分、並びに強度及び伸度を評価した。その評価結果を表１及び表２にそれぞれ示した。
【００３４】
その結果、実施例１〜８の塗膜は耐水性に優れていたが、比較例１〜３の塗膜は何れも白化が見られた。また、アセトン不溶解分については、実施例１〜８の塗膜は何れも高い数値を示したが、比較例１及び比較例３の塗膜は低い数値となった。更に、塗膜の強度及び伸度につていも、実施例１〜８の塗膜は高い数値を示したが、比較例１及び比較例２の塗膜は低い数値となった。これらの結果を総合すれば、実施例１〜８の水性樹脂組成物は、有機溶剤を含有するポリウレタン樹脂に代替が可能であると判断することができる。これに対して、比較例１〜３は、耐水性、耐溶剤性又は耐久性の何れかの点において有機溶剤系のポリウレタン樹脂に劣っていることが分かる。
【００３５】
＜耐水性＞
６ＭＩＬドクターブレードを用いて各実施例及び各比較例の常温硬化性の水性樹脂組成物をガラス板に塗布し、３日間常温乾燥することにより、塗膜を形成した。この塗膜を４０℃の温水に１日間浸漬し、塗膜の外観の変化を目視で評価した。評価基準は下記の通りである。
【００３６】
◎：異常なし
○：やや白化
△：白化
×：膨潤または溶解。
【００３７】
＜アセトン不溶解分＞
＃４０のバーコータを用いて各実施例及び各比較例の常温硬化性の水性樹脂組成物をアルミニウム板に塗布し、３日間常温乾燥することにより、塗膜を形成した。この塗膜をアセトンで３時間煮沸したときの塗膜の重量残存率（％）を求めた。
【００３８】
＜塗膜の強度及び伸度＞
塗膜の膜厚が乾燥時で約７０μｍになるように各実施例及び各比較例の常温硬化性の水性樹脂組成物を用いてフィルムを作成した。これをＪＩＳ−Ａ−６９１０の伸び試験法に従って養生し、２号ダンベルにより打ち抜いたものを試験片とし、２０℃で強度及び伸度を測定した。
【００３９】
【発明の効果】
本発明の一液性水系ポリウレタン樹脂組成物及び該組成物を含有する水性樹脂組成物は、水性ウレタン樹脂の側鎖にケトン性カルボニル基を導入するためのカルボニル基含有活性水素化合物を工業的に容易に製造し得る技術を確立することにより、工業生産が可能となった。
【００４０】
これにより、分子側鎖にケトン性カルボニル基を導入した水性ウレタン樹脂を得ることができるため、アジピン酸ジヒドラジド等の架橋剤との架橋点の数を任意にコントロールでき、架橋密度が高い皮膜を得ることが可能となる。これにより、ウレタン樹脂単独で耐水性及び耐溶剤に優れた皮膜を得ることができ、かつ、溶剤系ウレタン樹脂のような皮膜弾性や強靭性を得ることが可能となり、常温硬化性樹脂として、十分な皮膜弾性、強靭性、耐水性、耐溶剤性等を得ることが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a one-part aqueous polyurethane resin composition and an aqueous resin composition containing the composition. More specifically, the present invention is a room temperature curing type film that is excellent in water resistance, solvent resistance, durability, and the like. The present invention relates to a one-part water-based polyurethane resin composition suitable for painting buildings, vehicles, ships, etc., and an aqueous resin composition containing the composition.
[0002]
[Prior art]
Conventionally, room temperature curable resins have been used as paints for exterior wall coatings such as buildings that require water resistance and durability. Since this room temperature curable resin has conventionally used a polyurethane resin containing an organic solvent, it is not preferable from the viewpoint of environmental problems and the Fire Service Act, and there is a demand for conversion to an aqueous resin containing no organic solvent. . Therefore, a room temperature curable aqueous polyurethane resin having performance equivalent to that of a polyurethane resin containing an organic solvent has been required.
[0003]
From such a background, a mixture of a carbonyl group-containing acrylic copolymer aqueous dispersion and a urethane copolymer aqueous dispersion having a hydrazide group has been proposed (Patent Document 1 and Patent Document 2).
[0004]
Further, a resin composition is proposed in which an aqueous polyurethane resin containing a carbonyl group is added to an acrylic copolymer having a carbonyl group, and a compound having a hydrazide group is added as a crosslinking agent (Patent Document 3). And Patent Document 4).
[0005]
However, although these resin compositions are said to be excellent in drying properties, water resistance, coating film elasticity, etc., the degree of crosslinking cannot be sufficiently increased, and various physical properties of the resulting film, particularly water resistance. It is not possible to obtain sufficient results with respect to properties and solvent resistance.
[0006]
On the other hand, when about 50 to 70% of an acrylic resin is blended with the aqueous polyurethane, the elasticity and toughness of the film tends to be inferior compared to the solvent-based polyurethane resin. Further, in the conventional ketonic carbonyl group-containing aqueous urethane resin, a ketonic carbonyl group is introduced only at the molecular end, so that a sufficient crosslinking density cannot be obtained, and water resistance and solvent resistance cannot be improved. .
[0007]
[Patent Document 1]
JP-A-1-3011761 (page 2, upper right column, line 16 to lower left column, line 7)
[Patent Document 2]
JP-A-1-301762 (page 2, upper right column, line 18 to lower left column, line 9)
[Patent Document 3]
JP 7-11193 A (paragraph number 0005)
[Patent Document 4]
JP-A-7-113061 (paragraph number 0005)
[0008]
[Problems to be solved by the invention]
The present invention was made in order to solve the above-mentioned problems of the prior art, and the object of the present invention is to form a film excellent in water resistance, solvent resistance, durability, etc. It is to provide a curable one-component aqueous polyurethane resin composition and an aqueous resin composition containing the composition.
[0009]
[Means for Solving the Problems]
The one-component aqueous polyurethane resin composition of the present invention has (A) an aqueous polyurethane resin having two or more ketonic carbonyl groups in one molecule, and (C) two or more hydrazide groups in one molecule. And a hydrazide compound.
[0010]
In the present invention, the ketonic carbonyl in the molecule of the component (A) reacts with the hydrazide group of the hydrazide compound which is the component (C) to form a> C = N—NH— bond, thereby forming a coating film. It is considered that the water resistance, solvent resistance, durability and the like of the resin are improved.
[0011]
Moreover, the one-component aqueous polyurethane resin composition of the present invention comprises (B) an aqueous polyurethane resin having two or more ketonic carbonyl groups and two or more hydrazide groups in one molecule. And
[0012]
In the present invention, the hydrazide group in the molecule of component (B) reacts with the ketonic carbonyl of another molecule to form a> C = N-NH- bond, whereby the water resistance, Solvent property, durability, etc. are considered to be improved.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the one-component aqueous polyurethane resin composition of the present invention comprises (A) an aqueous polyurethane resin having two or more ketonic carbonyl groups in one molecule, and (C) two or more in one molecule. And a hydrazide compound having a hydrazide group.
[0014]
Here, in the water-based polyurethane resin (A), the ketonic carbonyl group is included in the polyurethane resin composition so as to have a carbonyl equivalent of 500 to 10,000 (g / mol). Preferably, it is contained so that it may become 1,000-5,000 g / mol). When this carbonyl equivalent is smaller than the above range, curing shrinkage becomes large, and it becomes economically disadvantageous. If the carbonyl equivalent is larger than the above range, the crosslinking effect tends to be insufficient.
[0015]
The aqueous polyurethane resin of component (A) in the present invention comprises (a) an organic polyisocyanate and (b) an active hydrogen-containing compound containing two or more active hydrogens having reactivity with NCO groups, and (c) ) It can be obtained by reaction with a carbonyl group-containing active hydrogen compound containing a ketonic carbonyl group and containing at least one active hydrogen having reactivity with an NCO group.
[0016]
Here, as the organic polyisocyanate of the component (a), conventionally used aromatic, aliphatic or alicyclic organic polyisocyanates can be used. Specific examples include aliphatic diisocyanates (for example, Tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate, etc.), alicyclic diisocyanates (for example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-cyclyl) Examples include cyclohexyl methane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane), aromatic diisocyanates (for example, tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate). 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1, 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like), araliphatic diisocyanates (for example, dialkyldiphenyl) Diisocyanate, tetraalkyl diphenylmethane diisocyanate, alpha, alpha, alpha, alpha-tetramethyl xylylene diisocyanate can be exemplified), tolylene diisocyanate - DOO and the like. These organic polysocyanates can be used alone or in a mixture of two or more.
[0017]
The active hydrogen-containing compound as component (b) contains two or more active hydrogens having reactivity with the NCO group. That is, it has a hydroxyl group, amino group or mercapto group, and is generally known polyether, polyester, polyether ester, polythioether, polyacetal, polybutadiene, polysiloxane, etc., preferably two or more at the molecular end It is a compound having a hydroxyl group. Specifically, as polyhydroxy compounds having two or more active hydrogen groups, ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, diglycerin, pentaerythritol, sorbitol and other polyhydric alcohols, their oxyalkylene derivatives or their polyhydric alcohols or oxy Estes obtained from alkylene derivatives and polycarboxylic acids, polycarboxylic anhydrides, or polycarboxylic esters Compounds, polycarbonate polyols, polycaprolactone polyols, polyester polyols, polythioether polyols, polyacetal polyols, polytetramethylene glycol, polybutadiene polyol, castor oil polyol, fluorine polyol, a polyol compound or a modified product such as silicon polyols.
[0018]
The component (c) carbonyl group-containing active hydrogen compound contains a ketonic carbonyl group and contains at least two active hydrogens having reactivity with an NCO group. A compound obtained by addition reaction of dialkanolamine with acetone acrylamide can be exemplified.
[0019]
The hydrazide compound of component (C) in the present invention has two or more hydrazide groups in one molecule. Specific examples thereof include oxalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, and azelaic acid dihydrazide. , Succinic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, and the like, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrantoin, carbohydrazide and the like. These may be used alone or in combination of two or more. Among these, adipic acid dihydrazide is more preferable from the viewpoint of versatility and good solubility in water. In addition, as the hydrazide compound of component (C), a —NHNH 2 group at the molecular end obtained by reacting a polyurethane prepolymer having a molecular terminal free isocyanate group with a compound having two or more hydrazide groups in one molecule. In this case, it is preferable to use adipic acid dihydrazide as a compound having two or more hydrazide groups in one molecule.
[0020]
Moreover, the one-component aqueous polyurethane resin composition according to another embodiment of the present invention has (B) two or more ketonic carbonyl groups and two or more hydrazide groups in one molecule as described above. An aqueous polyurethane resin is contained.
[0021]
Here, in the water-based polyurethane resin (B), the ketonic carbonyl group is contained in the polyurethane resin composition so as to have a carbonyl equivalent of 500 to 10,000 (g / mol). Preferably, it is contained so that it may become 1,000-5,000 g / mol). When this carbonyl equivalent is smaller than the above range, curing shrinkage becomes large, and it becomes economically disadvantageous. If the carbonyl equivalent is larger than the above range, the crosslinking effect tends to be insufficient.
[0022]
In the present invention, the water-based polyurethane resin as component (B) includes the organic polyisocyanate as component (a), the active hydrogen-containing compound as component (b), and the carbonyl group as component (c), respectively. A polyurethane prepolymer having an isocyanate group at the molecular terminal is obtained by reaction with the active hydrogen compound, and the molecular terminal free isocyanate group is obtained by reacting the hydrazide compound of component (C) exemplified above. A polyurethane prepolymer having —NHNH 2 group at the molecular end can be exemplified.
[0023]
【Example】
(Carbonyl group-containing active hydrogen compound X ... Synthesis of component (c))
As a component (c) carbonyl group-containing active hydrogen compound, a diethanolamine adduct of diacetone acrylamide was synthesized as follows.
[0024]
By adding 94.5 parts by weight of diethanolamine to 169 parts by weight of diacetone acrylamide and heating at 100 ° C. for 3 hours, a diethanolamine adduct of diacetone acrylamide as component (c) is obtained, which is converted to a carbonyl group. It was set as the containing active hydrogen compound X. The bromine number of this carbonyl group-containing active hydrogen compound X was 6.1. The bromine number was measured according to JIS-K-3331.
[0025]
(Synthesis Example 1 ... (A) Component Synthesis)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 107.2 parts by weight of isophorone diisocyanate, and 114 parts by weight of methyl ethyl ketone were added, and 70 to 75 ° C. The reaction was performed for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 5.10 (%). Next, the temperature of the system was set at 50 ° C., 18.1 parts by weight of dimethylolpropionic acid, 39.5 parts by weight of the previously synthesized carbonyl group-containing active hydrogen compound X, 7.3 parts by weight of triethylamine, and 94. 5 parts by weight was added and reacted at 70 to 75 ° C. for 180 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.20 (%). After diluting this prepolymer with water under stirring, 5.8 parts by weight of dipropylene triamine was added, the terminal NCO group was extended with amine, and disappearance of free isocyanate groups (%) was confirmed, and then methyl ethyl ketone was distilled off. As a result, an anionic polyurethane polymer aqueous solution I as component (A) having a ketonic carbonyl group in the molecular side chain of 35% pure was obtained (theoretical carbonyl equivalent was 3490 (g / mol)).
[0026]
(Synthesis Example 2 ... (B) Component Synthesis)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 107.2 parts by weight of isophorone diisocyanate, and 139 parts by weight of methyl ethyl ketone were added, and 70 to 75 ° C. The reaction was performed for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 6.90 (%). Next, the temperature of the system was 50 ° C., 18.1 parts by weight of dimethylolpropionic acid, 39.5 parts by weight of the previously synthesized carbonyl group-containing active hydrogen compound X, 7.3 parts by weight of triethylamine, and 93.3% of methyl ethyl ketone. 5 parts by weight was added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.20 (%). The prepolymer was stirred and diluted with dilute water in which 23.0 parts by weight of adipic acid dihydrazide was dissolved. After confirming the disappearance of free isocyanate groups (%), methyl ethyl ketone was distilled off to obtain a pure content of 35%. (B) component anionic polyurethane prepolymer aqueous solution II having a ketonic carbonyl group in its molecular side chain and a terminal hydrazide group was obtained (theoretical carbonyl equivalent was 3640 (g / mol)).
[0027]
(Synthesis Example 3 (synthesis of component (A))
200 parts by weight of carbonate of 1,6-hexanediol (Labe curve 102, manufactured by Mitex Co., Ltd., hydroxyl value = 112.0) and 26.7 parts by weight of sodium dimethylisophthalate sulfonate were added, and further sodium paratoluenesulfonate. 0.45 parts by weight was added and heated under reduced pressure at 160 ° C. for 8 hours. At this time, the hydroxyl value was 51.0. 127 parts by weight of this polyester polyol was sampled, and further, 240.0 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), previously synthesized carbonyl group-containing active hydrogen 35.1 parts by weight of Compound X, 83.3 parts by weight of isophorone diisocyanate, and 362 parts by weight of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 240 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.30 (%). After adding water to this and emulsifying, further diluting with water, 6.5 parts by weight of dipropylene triamine was added to extend the terminal NCO group, and after confirming disappearance of the free isocyanate group (%), methyl ethyl ketone was added. Was distilled off to obtain an anionic polyurethane polymer aqueous solution III of component (A) having a ketonic carbonyl group in the molecular side chain of 35% pure (theoretical carbonyl equivalent was 3430 (g / mol)).
[0028]
(Synthesis Example 4 ... (A) Component Synthesis)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 13.4 parts by weight of trimethylolpropane, 153.2 parts by weight of isophorone diisocyanate, and 140 parts by weight of methyl ethyl ketone Was added and reacted at 70-75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 7.10 (%). Next, the temperature of the system was 50 ° C., 20.1 parts by weight of dimethylolpropionic acid, 44.2 parts by weight of the previously synthesized carbonyl group-containing active hydrogen compound X, 7.3 parts by weight of triethylamine, and 125. 4 parts by weight was added and reacted at 70 to 75 ° C. for 180 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.50 (%). After diluting this prepolymer with water under stirring, 7.7 parts by weight of dipropylene triamine was added to extend the terminal NCO group, and after confirming disappearance of free isocyanate groups (%), methyl ethyl ketone was distilled off. As a result, an anionic polyurethane polymer aqueous solution IV of component (A) having a ketonic carbonyl group in the molecular side chain of 35% pure was obtained (theoretical carbonyl equivalent is 3590 (g / mol)).
(Synthesis Example 5 ... (A) Component Synthesis)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 39.5 parts by weight of the previously synthesized carbonyl group-containing active hydrogen compound X, and isophorone diisocyanate 75. 9 parts by weight and 206 parts by weight of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.20 (%). Next, the temperature of the system was cooled to 50 ° C., 8.1 parts by weight of acetic acid was added, and after sufficient stirring, this prepolymer was diluted with water under stirring, and 5.0 parts by weight of dipropylene triamine was further added. After adding the amine to extend the terminal NCO group and confirming the disappearance of the free isocyanate group (%), the methyl ethyl ketone is distilled off to have a ketonic carbonyl group in the molecular side chain of 35% pure (A) The component cationic polyurethane polymer aqueous solution V was obtained (theoretical carbonyl equivalent was 3060 (g / mol)).
(Synthesis Example 6 ... (C) Component Synthesis)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 83.3 parts by weight of isophorone diisocyanate, and 114 parts by weight of methyl ethyl ketone were added, and 70 to 75 ° C. The reaction was performed for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.90 (%). Next, the temperature of the system was adjusted to 50 ° C., 20.1 parts by weight of dimethylolpropionic acid, 1.5 parts by weight of triethylamine, and 85.2 parts by weight of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.60 (%). The prepolymer was cooled to 35 ° C., diluted water in which 26.8 parts by weight of adipic acid dihydrazide was dissolved was added, and disappearance of free isocyanate groups (%) was confirmed. A component (C) anionic polyurethane prepolymer aqueous solution VI having a hydrazide group at the molecular end of 35% was obtained.
(Comparative Synthesis Example 1)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 83.3 parts by weight of isophorone diisocyanate, and 114 parts by weight of methyl ethyl ketone were added, and 70 to 75 ° C. The reaction was performed for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.90 (%). Next, the temperature of the system was adjusted to 50 ° C., 20.1 parts by weight of dimethylolpropionic acid, 1.5 parts by weight of triethylamine, and 85.2 parts by weight of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.60 (%). The prepolymer was cooled to 60 ° C., 19.6 parts by weight of diacetone alcohol was added, and the mixture was reacted at 75 ° C. for 3 hours. The free isocyanate group content at this time was 0.2%. This prepolymer was cooled to 35 ° C., diluted water was added, and disappearance of free isocyanate groups (%) was confirmed. Then, methyl ethyl ketone was distilled off, so that only a ketonic carbonyl group was present at the molecular terminal having a pure content of 35%. A urethane polymer aqueous solution i having the following was obtained:
(Comparative Synthesis Example 2)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 13.4 parts by weight of trimethylolpropane, 114.9 parts by weight of isophorone diisocyanate, and 140 parts by weight of methyl ethyl ketone Was added and reacted at 70-75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.20 (%). Next, the temperature of the system was set to 50 ° C., 20.1 parts by weight of dimethylolpropionic acid, 7.3 parts by weight of triethylamine, and 125.4 parts by weight of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 180 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.30 (%). After this prepolymer was cooled to 60 ° C., 17.7 parts by weight of diacetone alcohol was added and reacted at 75 ° C. for 3 hours. The free isocyanate group content (in terms of solid content) at this time was 0.20 (%). This was diluted with water under stirring, and after confirming the disappearance of free isocyanate groups (%), methyl ethyl ketone was distilled off to obtain a polyurethane polymer aqueous solution ii having a ketonic carbonyl group at the molecular end with a pure content of 35%. Got.
(Comparative Synthesis Example 3)
300 parts by weight of carbonate of 1,6-hexanediol (Labe curve 106, manufactured by Mitex Co., Ltd., hydroxyl value = 56.1), 83.3 parts by weight of isophorone diisocyanate, and 114 parts by weight of methyl ethyl ketone were added, and 70 to 75 ° C. The reaction was performed for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.90 (%). Next, the temperature of the system was adjusted to 50 ° C., 20.1 parts by weight of dimethylolpropionic acid, 1.5 parts by weight of triethylamine, and 85.2 parts by weight of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.60 (%). The prepolymer is cooled to 35 ° C., diluted water is added, and an aqueous solution in which 6.7 parts by weight of dipropylenetriamine is dissolved is added. After confirming disappearance of free isocyanate groups (%), methyl ethyl ketone is distilled off. In particular, a urethane polymer aqueous solution iii having a pure content of 35% was obtained.
[0029]
<Preparation of room temperature curable aqueous resin composition>
(Examples 1-8)
The urethane polymer or urethane prepolymer obtained in Synthesis Examples 1 to 6 was blended in the ratio shown in Table 1 to prepare a room temperature curable aqueous resin composition.
[0030]
[Table 1]
(Comparative Examples 1-3)
The urethane polymer or urethane prepolymer obtained in Comparative Synthesis Examples 1 to 3 was blended in the ratio shown in Table 2 to prepare a room temperature curable aqueous resin composition.
[0032]
[Table 2]
A coating film was formed using the aqueous resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3 prepared above, and the water resistance, acetone insoluble matter, strength and elongation were measured by the method shown below. evaluated. The evaluation results are shown in Table 1 and Table 2, respectively.
[0034]
As a result, the coating films of Examples 1 to 8 were excellent in water resistance, but all the coating films of Comparative Examples 1 to 3 were whitened. Moreover, about the acetone insoluble matter, although the coating film of Examples 1-8 showed all the high numerical values, the coating film of the comparative example 1 and the comparative example 3 became a low numerical value. Furthermore, also about the intensity | strength and elongation of the coating film, although the coating film of Examples 1-8 showed the high numerical value, the coating film of the comparative example 1 and the comparative example 2 became a low numerical value. If these results are put together, it can be determined that the aqueous resin compositions of Examples 1 to 8 can be replaced with polyurethane resins containing organic solvents. In contrast, Comparative Examples 1 to 3 are found to be inferior to organic solvent-based polyurethane resins in any of water resistance, solvent resistance, and durability.
[0035]
<Water resistance>
A normal temperature curable aqueous resin composition of each example and each comparative example was applied to a glass plate using a 6MIL doctor blade, and dried at room temperature for 3 days to form a coating film. This coating film was immersed in warm water of 40 ° C. for 1 day, and the change in the appearance of the coating film was visually evaluated. The evaluation criteria are as follows.
[0036]
A: No abnormality O: Slightly whitening Δ: Whitening x: Swelling or dissolution.
[0037]
<Acetone insoluble matter>
The coating film was formed by apply | coating the room temperature curable aqueous resin composition of each Example and each comparative example to the aluminum plate using # 40 bar coater, and drying at room temperature for 3 days. The weight residual ratio (%) of the coating film when the coating film was boiled with acetone for 3 hours was determined.
[0038]
<Strength and elongation of coating film>
A film was prepared using the room temperature curable aqueous resin composition of each Example and each Comparative Example so that the film thickness of the coating film was about 70 μm when dried. This was cured according to the elongation test method of JIS-A-6910, and the one punched out by No. 2 dumbbell was used as a test piece, and the strength and elongation were measured at 20 ° C.
[0039]
【The invention's effect】
The one-component water-based polyurethane resin composition of the present invention and the aqueous resin composition containing the composition are industrially produced from a carbonyl group-containing active hydrogen compound for introducing a ketonic carbonyl group into a side chain of an aqueous urethane resin. Industrial production became possible by establishing a technology that could be easily manufactured.
[0040]
As a result, an aqueous urethane resin having a ketonic carbonyl group introduced into the molecular side chain can be obtained, so that the number of crosslinking points with a crosslinking agent such as adipic acid dihydrazide can be arbitrarily controlled, and a film having a high crosslinking density can be obtained. It becomes possible. As a result, it is possible to obtain a film excellent in water resistance and solvent resistance with a urethane resin alone, and it is possible to obtain film elasticity and toughness like a solvent-based urethane resin. Film elasticity, toughness, water resistance, solvent resistance and the like can be obtained.
Claims (9)
（Ｃ）１分子中に２個以上のヒドラジド基を有するヒドラジド化合物と
を含有してなることを特徴とする一液性水系ポリウレタン樹脂組成物。(A) an aqueous polyurethane resin having two or more ketonic carbonyl groups in one molecule;
(C) A one-part aqueous polyurethane resin composition comprising a hydrazide compound having two or more hydrazide groups in one molecule.
を含有してなることを特徴とする一液性水系ポリウレタン樹脂組成物。(B) A one-component aqueous polyurethane resin composition comprising an aqueous polyurethane resin having two or more ketonic carbonyl groups and two or more hydrazide groups in one molecule.
（ａ）有機ポリイソシアネートと、
（ｂ）ＮＣＯ基との反応性を有する活性水素を２個以上含有する活性水素含有化合物と、
（ｃ）ケトン性カルボニル基を含有し、かつ、ＮＣＯ基との反応性を有する２個以上の活性水素を含有するカルボニル基含有活性水素化合物と
の反応により得られるポリウレタン水分散体であり、
（ｃ）成分中に含まれるケトン性カルボニル基１モルに対して、（Ｃ）成分中に含まれるヒドラジド基が０．１〜３モルとなるように（Ｃ）成分を添加して得られることを特徴とする請求項１記載の一液性水系ポリウレタン樹脂組成物。The water-based polyurethane resin as the component (A) is
(A) an organic polyisocyanate;
(B) an active hydrogen-containing compound containing two or more active hydrogens having reactivity with an NCO group;
(C) a polyurethane water dispersion obtained by a reaction with a carbonyl group-containing active hydrogen compound containing two or more active hydrogens containing a ketonic carbonyl group and having reactivity with an NCO group,
(C) It is obtained by adding the component (C) so that the hydrazide group contained in the component (C) is 0.1 to 3 mol with respect to 1 mol of the ketonic carbonyl group contained in the component (c). The one-component water-based polyurethane resin composition according to claim 1.
（ａ）有機ポリイソシアネートと、
（ｂ）ＮＣＯ基との反応性を有する活性水素を２個以上含有する活性水素含有化合物と、
（ｃ）ケトン性カルボニル基を含有し、かつ、ＮＣＯ基との反応性を有する２個以上の活性水素を含有するカルボニル基含有活性水素化合物と
の反応により得られる分子末端にイソシアネート基を有するポリウレタンプレポリマーの分子末端遊離イソシアネート基に対して、
（Ｃ）１分子中に２個以上のヒドラジド基を有するヒドラジド化合物
を反応させることにより得られる、分子末端に−ＮＨＮＨ２基を有するポリウレタンプレポリマーであることを特徴とする請求項２記載の一液性水系ポリウレタン樹脂組成物。The aqueous polyurethane resin as component (B)
(A) an organic polyisocyanate;
(B) an active hydrogen-containing compound containing two or more active hydrogens having reactivity with an NCO group;
(C) Polyurethane having an isocyanate group at the molecular end obtained by reaction with a carbonyl group-containing active hydrogen compound containing two or more active hydrogens containing a ketonic carbonyl group and having reactivity with an NCO group For the molecular end free isocyanate group of the prepolymer,
(C) A polyurethane prepolymer having a —NHNH 2 group at a molecular end obtained by reacting a hydrazide compound having two or more hydrazide groups in one molecule. Liquid aqueous polyurethane resin composition.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005255833A (en) * | 2004-03-11 | 2005-09-22 | Dai Ichi Kogyo Seiyaku Co Ltd | One-component aqueous resin composition and aqueous coating agent composition using the same |
| JP2006028343A (en) * | 2004-07-16 | 2006-02-02 | Chuo Rika Kogyo Corp | Polyurethane-based resin composition |
| JP2008214617A (en) * | 2007-02-09 | 2008-09-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Reactive one-pack type polyurethane-based aqueous primer composition |
| JP2009108173A (en) * | 2007-10-29 | 2009-05-21 | Kansai Paint Co Ltd | Water-base urethane resin composition |
| JP2011231353A (en) * | 2010-04-26 | 2011-11-17 | Kansai Paint Co Ltd | Metal surface treatment agent |
| WO2013146986A1 (en) * | 2012-03-29 | 2013-10-03 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion |
| EP2716675A1 (en) * | 2011-05-31 | 2014-04-09 | UBE Industries, Ltd. | Aqueous polyurethane resin dispersion and coating composition comprising same |
| US20160159959A1 (en) * | 2013-08-26 | 2016-06-09 | Valspar Sourcing, Inc. | Self-Crosslinkable Polymer and Aqueous Dispersion Comprising Particles of the Same |
| EP3039049A4 (en) * | 2013-08-26 | 2017-04-26 | Valspar Sourcing, Inc. | Self-crosslinkable polymer and aqueous dispersion comprising particles of the same |
| JP2017145287A (en) * | 2016-02-16 | 2017-08-24 | 第一工業製薬株式会社 | Polyurethane aqueous dispersion and method for producing polyurethane aqueous dispersion |
| JP2020012091A (en) * | 2018-07-10 | 2020-01-23 | ダイセル・オルネクス株式会社 | Curable resin composition and cured product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005255833A (en) * | 2004-03-11 | 2005-09-22 | Dai Ichi Kogyo Seiyaku Co Ltd | One-component aqueous resin composition and aqueous coating agent composition using the same |
| JP2006028343A (en) * | 2004-07-16 | 2006-02-02 | Chuo Rika Kogyo Corp | Polyurethane-based resin composition |
| JP2008214617A (en) * | 2007-02-09 | 2008-09-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Reactive one-pack type polyurethane-based aqueous primer composition |
| JP2009108173A (en) * | 2007-10-29 | 2009-05-21 | Kansai Paint Co Ltd | Water-base urethane resin composition |
| JP2011231353A (en) * | 2010-04-26 | 2011-11-17 | Kansai Paint Co Ltd | Metal surface treatment agent |
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| JPWO2013146986A1 (en) * | 2012-03-29 | 2015-12-14 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion |
| US20160159959A1 (en) * | 2013-08-26 | 2016-06-09 | Valspar Sourcing, Inc. | Self-Crosslinkable Polymer and Aqueous Dispersion Comprising Particles of the Same |
| EP3039049A4 (en) * | 2013-08-26 | 2017-04-26 | Valspar Sourcing, Inc. | Self-crosslinkable polymer and aqueous dispersion comprising particles of the same |
| US10081696B2 (en) * | 2013-08-26 | 2018-09-25 | The Sherwin-Williams Company | Self-crosslinkable polymer and aqueous dispersion comprising particles of the same |
| JP2017145287A (en) * | 2016-02-16 | 2017-08-24 | 第一工業製薬株式会社 | Polyurethane aqueous dispersion and method for producing polyurethane aqueous dispersion |
| JP2020012091A (en) * | 2018-07-10 | 2020-01-23 | ダイセル・オルネクス株式会社 | Curable resin composition and cured product thereof |
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