JP6448442B2 - Aqueous curable composition, paint and adhesive containing the aqueous curable composition - Google Patents
Aqueous curable composition, paint and adhesive containing the aqueous curable composition Download PDFInfo
- Publication number
- JP6448442B2 JP6448442B2 JP2015071381A JP2015071381A JP6448442B2 JP 6448442 B2 JP6448442 B2 JP 6448442B2 JP 2015071381 A JP2015071381 A JP 2015071381A JP 2015071381 A JP2015071381 A JP 2015071381A JP 6448442 B2 JP6448442 B2 JP 6448442B2
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- JP
- Japan
- Prior art keywords
- epoxy resin
- curable composition
- mol
- aqueous
- aqueous curable
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 38
- 239000003973 paint Substances 0.000 title claims description 9
- 239000000853 adhesive Substances 0.000 title claims description 5
- 230000001070 adhesive effect Effects 0.000 title claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 118
- 229920000647 polyepoxide Polymers 0.000 claims description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 38
- 239000003085 diluting agent Substances 0.000 claims description 34
- -1 alkylene glycol diglycidyl ether Chemical compound 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 125000003700 epoxy group Chemical group 0.000 claims description 24
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 claims description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 4
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 4
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 description 24
- 239000010959 steel Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 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 17
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- BOJZPUPAXYETRK-UHFFFAOYSA-N 1,1-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(CN)C1=CC=CC=C1 BOJZPUPAXYETRK-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- IEVIXDLZSRLUHW-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diol Chemical class C=1C=CC=CC=1C(O)=C(O)C1=CC=CC=C1 IEVIXDLZSRLUHW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-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
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- NKNIZOPLGAJLRV-UHFFFAOYSA-N 2,2-diphenylpropane-1,1-diamine Chemical compound C=1C=CC=CC=1C(C(N)N)(C)C1=CC=CC=C1 NKNIZOPLGAJLRV-UHFFFAOYSA-N 0.000 description 1
- LLNSYBHDHRWWME-UHFFFAOYSA-N 2,3,5,6-tetrabutyl-4-[2-(2,3,5,6-tetrabutyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CCCCc1c(O)c(CCCC)c(CCCC)c(c1CCCC)C(C)(C)c1c(CCCC)c(CCCC)c(O)c(CCCC)c1CCCC LLNSYBHDHRWWME-UHFFFAOYSA-N 0.000 description 1
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- LYXAQAXLWMRPOZ-UHFFFAOYSA-N 2-[1-(2-aminophenyl)-9h-fluoren-2-yl]aniline Chemical compound NC1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=CC=C1N LYXAQAXLWMRPOZ-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OHPBKUJGDFXDRM-UHFFFAOYSA-N 3,4-diethyl-5-(2-phenylpropan-2-yl)benzene-1,2-diamine Chemical compound CCC1=C(N)C(N)=CC(C(C)(C)C=2C=CC=CC=2)=C1CC OHPBKUJGDFXDRM-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-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
- BDBMKUGEVIQCGQ-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dimethylaniline Chemical group C1=C(N)C(C)=C(C)C(C=2C=CC(N)=CC=2)=C1 BDBMKUGEVIQCGQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical compound NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane 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
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- UMILHIMHKXVDGH-UHFFFAOYSA-N Triethylene glycol diglycidyl ether Chemical compound C1OC1COCCOCCOCCOCC1CO1 UMILHIMHKXVDGH-UHFFFAOYSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
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- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 229960005237 etoglucid Drugs 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
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- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- 239000000600 sorbitol Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、水性塗料、水性接着剤、サイジング剤等に適用可能な乳化安定性、耐水性の優れたエポキシ樹脂水性分散体を含む水性硬化組成物に関する。 The present invention relates to an aqueous curable composition containing an aqueous dispersion of an epoxy resin excellent in emulsion stability and water resistance applicable to water-based paints, water-based adhesives, sizing agents and the like.
近年、大気汚染防止、作業環境改善等の理由で世界的にＶＯＣ総量規制強化の方向に進んでいる。塗料分野、特に屋外で大量の有機溶剤を使用する重防食塗料分野においてはハイソリッド化、無溶剤化、弱溶剤化が進んでいるが、中でも水性硬化性組成物は作業環境、取り扱い作業性等の面において有利であり各種の水性硬化性組成物の開発が活発に行なわれている。 In recent years, the VOC total amount regulation has been strengthened worldwide for reasons such as air pollution prevention and work environment improvement. In the paint field, especially in the field of heavy anti-corrosion paints that use a large amount of organic solvents outdoors, high-solids, solvent-free, and weak solvents are progressing. Among them, aqueous curable compositions are working environments, handling operability, etc. Therefore, various aqueous curable compositions have been actively developed.
上記の分野では一般にビスフェノールＡ型のエポキシ樹脂が使用されているがエポキシ樹脂は一般に疎水性でありこれを水性化する為には界面活性剤を添加して乳化分散させたエポキシ樹脂エマルションが一般的に用いられている。しかし通常の界面活性剤はエポキシ基と反応する官能基を持っていないため、使用した界面活性剤が硬化エポキシ樹脂中に単独で残り耐水性、機械的な安定性を悪化させるという問題点がある。これらの問題点を解決する手段として、特許文献１では、オキサゾリドン環含有エポキシ樹脂を使った組成物を開示しているが、十分な性能を有しているとは言い難く、特に塗膜の密着性と光沢性を満足するものではなく、更なる性能の向上が望まれている。 In the above fields, bisphenol A type epoxy resins are generally used. Epoxy resins are generally hydrophobic, and in order to make them water-based, epoxy resin emulsions added with a surfactant and emulsified and dispersed are generally used. It is used for. However, since normal surfactants do not have functional groups that react with epoxy groups, the surfactants used remain alone in the cured epoxy resin, which deteriorates water resistance and mechanical stability. . As means for solving these problems, Patent Document 1 discloses a composition using an oxazolidone ring-containing epoxy resin, but it is difficult to say that the composition has sufficient performance, and in particular, adhesion of a coating film. Therefore, further improvement in performance is desired.
本発明の課題は、密着性や光沢性に優れながら、可使時間が十分に長く、十分な硬度、耐水性、耐溶剤性等を有する塗膜を形成しうる水性硬化性組成物を提供することであり、その水性硬化性組成物を用いて得られる水性塗料及び水性接着剤を提供することである。 An object of the present invention is to provide an aqueous curable composition capable of forming a coating film having a sufficiently long pot life and sufficient hardness, water resistance, solvent resistance, etc. while having excellent adhesion and gloss. That is, to provide an aqueous paint and an aqueous adhesive obtained by using the aqueous curable composition.
本発明者らは上記問題点を解決すべく鋭意研究した結果、オキサゾリドン環含有エポキシ樹脂を乳化剤として使用したエポキシ樹脂水性分散体と、水性反応性希釈剤と、硬化剤を含む水性硬化性組成物がこれらの問題点を解決するのに最適な手段であることを見出し本発明を完成するに到った。 As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous epoxy resin dispersion using an epoxy resin containing an oxazolidone ring as an emulsifier, an aqueous reactive diluent, and an aqueous curable composition containing a curing agent. Has been found to be an optimal means for solving these problems, and the present invention has been completed.
すなわち、本発明は、エポキシ樹脂水性分散体（Ａ）と反応性希釈剤（Ｂ）と硬化剤（Ｃ）を含み、界面活性剤を含まない水性硬化性組成物であって、
該エポキシ樹脂水性分散体（Ａ）は、エポキシ当量５００〜１００００ｇ／ｅｑ．のオキサゾリドン環含有エポキシ樹脂（ｅ）とそれ以外のエポキシ樹脂（ｆ）と水（ｇ）とからなり、
該オキサゾリドン環含有エポキシ樹脂（ｅ）は、分子量１０００〜１００００のポリアルキレングリコール化合物（ａ）とポリイソシアネート化合物（ｂ）とを、（ａ）の水酸基１モルに対し、（ｂ）のイソシアネート基を１．５モル以上３．０モル以下の範囲で反応させて得られる末端イソシアネート基含有化合物（ｃ）と、分子内に２個以上のエポキシ基を持つエポキシ樹脂（ｄ）とを、（ｃ）のイソシアネート基１モルに対し、（ｄ）のエポキシ基を１．５モル以上５．０モル以下の範囲で反応させて得られ、
（ｅ）と（ｆ）と（ｇ）の割合は、質量比で（ｅ）：（ｆ）＝５：９５〜５０：５０の範囲であり、かつ｛（ｅ）＋（ｆ）｝：（ｇ）＝３０：７０〜７５：２５の範囲であり、
該反応性希釈剤（Ｂ）は、２５℃における水との溶解度が１０ｇ／水１００ｇ以上であるエポキシ樹脂であり、
該硬化剤（Ｃ）は、水溶性アミン系硬化剤であり、
（Ａ）と（Ｂ）と（Ｃ）の割合は、質量比で（Ａ）：（Ｂ）＝７０：３０〜９９：１の範囲であり、かつ（Ａ）と（Ｂ）の全エポキシ基１モルに対し、（Ｃ）の活性水素基が０．７モル以上１．１モル以下の範囲であることを特徴とする水性硬化性組成物である。
That is, the present invention is an epoxy resin aqueous dispersion (A) and seeing containing a reactive diluent (B) and the curing agent (C), an aqueous curable composition containing no surfactant,
The epoxy resin aqueous dispersion (A) has an epoxy equivalent of 500 to 10,000 g / eq. An oxazolidone ring-containing epoxy resin (e), another epoxy resin (f) and water (g),
The oxazolidone ring-containing epoxy resin (e) comprises a polyalkylene glycol compound (a) having a molecular weight of 1000 to 10,000 and a polyisocyanate compound (b) having an isocyanate group of (b) with respect to 1 mol of the hydroxyl group of (a). A terminal isocyanate group-containing compound (c) obtained by reacting in the range of 1.5 mol or more and 3.0 mol or less, and an epoxy resin (d) having two or more epoxy groups in the molecule, (c) It is obtained by reacting the epoxy group of (d) in the range of 1.5 mol or more and 5.0 mol or less with respect to 1 mol of the isocyanate group of
The ratio of (e), (f) and (g) is in the range of (e) :( f) = 5: 95-50: 50 by mass ratio and {(e) + (f)} :( g) = 30: 70 to 75:25,
The reactive diluent (B) is an epoxy resin having a solubility in water at 25 ° C. of 10 g / 100 g or more of water,
The curing agent (C) is a water-soluble amine curing agent,
The ratio of (A), (B), and (C) is in the range of (A) :( B) = 70: 30 to 99: 1 by mass ratio, and all the epoxy groups of (A) and (B) The aqueous curable composition is characterized in that the active hydrogen group (C) is in a range of 0.7 mol to 1.1 mol with respect to 1 mol.
上記反応性希釈剤（Ｂ）は、アルキレングリコールジグリシジルエーテルが好ましく、エチレングリコールジグリシジルエーテル及び／またはジエチレングリコールジグリシジルエーテルがより好ましい。 The reactive diluent (B) is preferably alkylene glycol diglycidyl ether, more preferably ethylene glycol diglycidyl ether and / or diethylene glycol diglycidyl ether .
上記ポリアルキレングリコール化合物（ａ）は、ポリエチレングリコールが好ましい。The polyalkylene glycol compound (a) is preferably polyethylene glycol.
上記ポリイソシアネート化合物（ｂ）は、ジイソシアネート化合物が好ましく、ジフェニルメタンジイソシアネート及び／またはトリレンジイソシアネートがより好ましい。 Upper Symbol polyisocyanate compound (b) is preferably a diisocyanate compound, diphenylmethane diisocyanate and / or tolylene diisocyanate are more preferred.
上記水溶性アミン系硬化剤がポリアミノアミド類、エポキシ樹脂アミンアダクト、脂肪族ポリアミン、変性ポリアミン、第３アミン、ヒドラジド、及びイミダゾールの群から選ばれる少なくとも１種が好ましい。 The water-soluble amine curing agent is preferably at least one selected from the group consisting of polyaminoamides, epoxy resin amine adducts, aliphatic polyamines, modified polyamines, tertiary amines, hydrazides, and imidazoles .
また、本発明は、上記水性硬化性組成物を含有することを特徴とする水性塗料であり、水性接着剤である。 Moreover, this invention is a water-based paint characterized by containing the said water-based curable composition, and is a water-based adhesive.
本発明によれば、密着性や光沢性に優れながら、可使時間が十分に長く、良好な硬度、外観、耐水性、耐溶剤性等を有する水性硬化性組成物を得ることができる。 According to the present invention, it is possible to obtain an aqueous curable composition having a sufficiently long pot life and excellent hardness, appearance, water resistance, solvent resistance and the like while being excellent in adhesion and gloss.
以下、本発明の実施の形態について、詳細に説明する。
本発明の水性硬化性組成物は、エポキシ樹脂水性分散体（Ａ）と水性反応性希釈剤（Ｂ）と硬化剤（Ｃ）を含み、水性反応性希釈剤（Ｂ）の２５℃における水との溶解度は、１０ｇ／水１００ｇ以上である。また、（Ｂ）は、（Ａ）と（Ｂ）の合計に対し、１質量％以上３０質量％以下の範囲である。さらに、（Ｃ）の活性水素基は、（Ａ）と（Ｂ）の全エポキシ基１モルに対し、０．７モル以上１．１モル以下の範囲である。
Hereinafter, embodiments of the present invention will be described in detail.
The aqueous curable composition of the present invention comprises an aqueous epoxy resin dispersion (A), an aqueous reactive diluent (B), and a curing agent (C), and water at 25 ° C. of the aqueous reactive diluent (B) The solubility of is 10 g / 100 g or more of water. Moreover, (B) is the range of 1 mass% or more and 30 mass% or less with respect to the sum total of (A) and (B). Further, the active hydrogen group of (C) is in the range of 0.7 mol or more and 1.1 mol or less with respect to 1 mol of all the epoxy groups of (A) and (B).
反応性希釈剤（Ｂ）が水性であることが重要であり、これにより塗膜の光沢性を低下させることなく、密着性を向上させることができる。２５℃における水との溶解度が１０ｇ／水１００ｇ未満の場合、塗膜にした時の密着性が悪化する恐れがある。２５℃における水との溶解度は２０ｇ／水１００ｇ以上が好ましく、５０ｇ／水１００ｇ以上がより好ましい。本発明での反応性希釈剤（Ｂ）の２５℃における水との溶解度とは、２５℃における水１００ｇに溶解する反応性希釈剤（Ｂ）の量（ｇ）を示す。反応性希釈剤（Ｂ）が完全水溶性の場合、無限混和が可能なため、上限値を特に定める必要はない。 It is important that the reactive diluent (B) is water-based, and thereby the adhesion can be improved without reducing the glossiness of the coating film. When the solubility with water at 25 ° C. is less than 10 g / 100 g of water, there is a possibility that the adhesion when formed into a coating film is deteriorated. The solubility with water at 25 ° C. is preferably 20 g / 100 g or more, more preferably 50 g / 100 g or more. The solubility of the reactive diluent (B) in the present invention with water at 25 ° C. indicates the amount (g) of the reactive diluent (B) dissolved in 100 g of water at 25 ° C. When the reactive diluent (B) is completely water-soluble, infinite miscibility is possible, so there is no need to set an upper limit value.
反応性希釈剤（Ｂ）は、２５℃における水との溶解度が１０ｇ／水１００ｇ以上であればどのようなエポキシ樹脂でも使用できるが、１分子中に平均で１．８個以上のエポキシ基を有するポリグリシジルエーテルが好ましい。具体的には、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル等のアルキレングリコールジグリシジルエーテルや、グリセリンポリグリシジルエーテル、ジグリセリンポリグリシジルエーテル、ポリグリセリンポリグリシジルエーテル等のグリセリン系ポリグリシジルエーテルやソルビトール系ポリグリシジルエーテル等が挙げられるがこれらに限定されるものではなく、これらの反応性希釈剤は単独で使用しても良いし、２種類以上併用しても良い。これらの中では、炭素数４〜８のポリエチレングリコールのジグリシジルエーテルが好ましい。 As the reactive diluent (B), any epoxy resin can be used as long as the solubility in water at 25 ° C. is 10 g / 100 g or more of water, but an average of 1.8 or more epoxy groups per molecule. Polyglycidyl ether having is preferable. Specifically, alkylene glycol diglycidyl ether such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether, and glycerin polyglycidyl. Examples include, but are not limited to, glycerin-based polyglycidyl ether and sorbitol-based polyglycidyl ether such as ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and these reactive diluents are used alone Alternatively, two or more types may be used in combination. Among these, diglycidyl ether of polyethylene glycol having 4 to 8 carbon atoms is preferable.
また、反応性希釈剤のエポキシ当量は、１００ｇ／ｅｑ．以上４００ｇ／ｅｑ．以下が好ましく、１１０ｇ／ｅｑ．以上３００ｇ／ｅｑ．以下がより好ましく、１２０ｇ／ｅｑ．以上２００ｇ／ｅｑ．以下がさらに好ましい。２５℃における粘度は、２００ｍＰａ・ｓ以下が好ましく、１５０ｍＰａ・ｓ以下がより好ましく、１００ｍＰａ・ｓ以下がさらに好ましい。なお、粘度は低い方が希釈効果が高くなるため低いほど好ましい。 The epoxy equivalent of the reactive diluent is 100 g / eq. 400 g / eq. The following is preferable, and 110 g / eq. 300 g / eq. The following is more preferable, and 120 g / eq. 200 g / eq. The following is more preferable. The viscosity at 25 ° C. is preferably 200 mPa · s or less, more preferably 150 mPa · s or less, and still more preferably 100 mPa · s or less. The lower the viscosity, the higher the dilution effect.
また、エポキシ樹脂水性分散体（Ａ）と水性反応性希釈剤（Ｂ）の配合割合も重要であり、これにより塗膜の密着性と光沢性を向上させることができる。（Ａ）と（Ｂ）の合計に対する（Ｂ）の割合は、１質量％以上３０質量％以下の範囲である。（Ａ）と（Ｂ）の合計に対し、（Ｂ）が少ないと塗膜にした時の密着性が向上しない恐れがあり、多すぎると塗膜にした時の光沢性が悪化する恐れがある。（Ａ）と（Ｂ）の合計に対する（Ｂ）の割合は、２質量％以上２５質量％以下の範囲が好ましく、５質量％以上２０質量％以下の範囲がより好ましい。 Further, the blending ratio of the epoxy resin aqueous dispersion (A) and the aqueous reactive diluent (B) is also important, whereby the adhesion and gloss of the coating film can be improved. The ratio of (B) to the sum of (A) and (B) is in the range of 1% by mass to 30% by mass. If the amount of (B) is less than the sum of (A) and (B), there is a fear that the adhesion when formed into a coating film may not be improved, and if too much, the glossiness when formed into a coating film may be deteriorated. . The ratio of (B) to the total of (A) and (B) is preferably in the range of 2% by mass to 25% by mass, and more preferably in the range of 5% by mass to 20% by mass.
エポキシ樹脂水性分散体（Ａ）は特に制限はないが、エポキシ当量５００〜１００００ｇ／ｅｑ．のオキサゾリドン環含有エポキシ樹脂（ｅ）とそれ以外のエポキシ樹脂（ｆ）と水（ｇ）とからなるエポキシ樹脂水性分散体（Ａ１）が好ましい。その割合が質量比で（ｅ）：（ｆ）＝５〜５０：５０〜９５であり、かつ｛（ｅ）＋（ｆ）｝：（ｇ）＝３０〜７５：２５〜７０であることが好ましい。 The epoxy resin aqueous dispersion (A) is not particularly limited, but an epoxy equivalent of 500 to 10,000 g / eq. An epoxy resin aqueous dispersion (A1) comprising the oxazolidone ring-containing epoxy resin (e), the other epoxy resin (f) and water (g) is preferred. The ratio is mass ratio (e) :( f) = 5-50: 50-95 and {(e) + (f)} :( g) = 30-75: 25-70. preferable.
エポキシ樹脂水性分散体（Ａ１）に占めるオキサゾリドン環含有エポキシ樹脂（ｅ）の割合が多いと耐水性、塗膜物性に悪影響を及ぼす恐れがあり、少ないと乳化安定性に劣る恐れがある。 If the proportion of the oxazolidone ring-containing epoxy resin (e) in the aqueous epoxy resin dispersion (A1) is large, the water resistance and the physical properties of the coating film may be adversely affected, and if it is small, the emulsion stability may be inferior.
エポキシ樹脂水性分散体（Ａ１）に用いるオキサゾリドン環含有エポキシ樹脂（ｅ）のエポキシ当量は、５００〜１００００ｇ／ｅｑ．が好ましく、５００〜５０００ｇ／ｅｑ．がより好ましい。エポキシ当量が小さいと乳化安定性に劣る恐れがあり、大きいと耐水性に劣る恐れがある。 The epoxy equivalent of the oxazolidone ring-containing epoxy resin (e) used for the epoxy resin aqueous dispersion (A1) is 500 to 10,000 g / eq. Is preferable, and 500 to 5000 g / eq. Is more preferable. If the epoxy equivalent is small, the emulsion stability may be inferior, and if it is large, the water resistance may be inferior.
また、エポキシ樹脂水性分散体（Ａ１）に占める水（ｇ）の割合が少ないと粘度が高すぎて作業性が悪くなる恐れがあり、多すぎると低粘度化により安定性が悪くなりまた塗膜にしたときの乾燥性が悪くなる恐れがある。 Also, if the proportion of water (g) in the epoxy resin aqueous dispersion (A1) is small, the viscosity is too high and the workability may be deteriorated. There is a risk that the dryness will worsen.
また、本発明に用いるエポキシ樹脂水性分散体（Ａ）は必要に応じて有機溶剤を使用することができる。その割合はオキサゾリドン環含有エポキシ樹脂（ｅ）とそれ以外のエポキシ樹脂（ｆ）の合計質量に対して、質量比で０〜２０の範囲が好ましい。多く使用すると有機溶剤削減という水性樹脂の特徴が損なわれる。また、有機溶剤は必要に応じ減圧蒸留により除去することができる。 Moreover, the epoxy resin aqueous dispersion (A) used for this invention can use an organic solvent as needed. The ratio is preferably in the range of 0 to 20 by mass ratio with respect to the total mass of the oxazolidone ring-containing epoxy resin (e) and the other epoxy resin (f). If it is used in a large amount, the characteristics of the water-based resin such as reduction of the organic solvent are impaired. The organic solvent can be removed by distillation under reduced pressure as necessary.
本発明に用いるエポキシ樹脂水性分散体（Ａ）を得るには、必要に応じて有機溶剤に溶解した後、撹拌しながら水を徐々に加えて乳化分散を行う。分散にはホモジナイザー等の高せん断力の撹拌機を使用してもよい。 In order to obtain the aqueous epoxy resin dispersion (A) used in the present invention, after dissolving in an organic solvent as necessary, water is gradually added while stirring to carry out emulsification dispersion. For dispersion, a high shearing stirrer such as a homogenizer may be used.
また、エポキシ樹脂水性分散体（Ａ１）は、必要に応じて、オキサゾリドン環含有エポキシ樹脂（ｅ）を各種エポキシ樹脂変性剤を使用することにより分子量（エポキシ当量）等を調整したエポキシ樹脂（ｈ）を用いても良い。その反応の際、それ以外のエポキシ樹脂（ｆ）を併用しても良い。使用できる量は、オキサゾリドン環含有エポキシ樹脂（ｅ）及び／またはそれ以外のエポキシ樹脂（ｆ）１００質量部に対し、７０質量部以下が好ましく、５０質量部以下がより好ましく、４０質量部以下がさらに好ましい。 Moreover, the epoxy resin aqueous dispersion (A1) is an epoxy resin (h) whose molecular weight (epoxy equivalent) and the like are adjusted by using various epoxy resin modifiers for the oxazolidone ring-containing epoxy resin (e) as necessary. May be used. In the reaction, other epoxy resin (f) may be used in combination. The amount that can be used is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and more preferably 40 parts by mass or less with respect to 100 parts by mass of the oxazolidone ring-containing epoxy resin (e) and / or other epoxy resin (f). Further preferred.
分子量（エポキシ当量）等を調整したエポキシ樹脂（ｈ）を用いる場合、エポキシ樹脂水性分散体（Ａ１）の水（ｇ）との配合割合は、質量比で、（ｈ）：（ｇ）＝３０〜７５：２５〜７０が好ましい。 When the epoxy resin (h) whose molecular weight (epoxy equivalent) is adjusted is used, the mixing ratio of the aqueous epoxy resin dispersion (A1) to water (g) is (h) :( g) = 30. ~ 75: 25-70 is preferred.
使用できるエポキシ樹脂変性剤としては、具体的には、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、テトラブチルビスフェノールＡ、ビスフェノールＺ、ビスフェノールＴＭＣ、ハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、ジブチルハイドロキノン、レゾルシン、メチルレゾルシン、ビフェノール、テトラメチルビフェノール、ジヒドロキシナフタレン、ジヒドロキシジフェニルエーテル、ジヒドロキシスチルベン類、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエンフェノール樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂、スチレン化フェノールノボラック樹脂、テルペンフェノール樹脂、重質油変性フェノール樹脂等の種々のフェノール類や、種々のフェノール類と、ヒドロキシベンズアルデヒド、クロトンアルデヒド、グリオキザール等の種々のアルデヒド類との縮合反応で得られる多価フェノール樹脂や、アニリン、フェニレンジアミン、トルイジン、キシリジン、ジエチルトルエンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルエタン、ジアミノジフェニルプロパン、ジアミノジフェニルケトン、ジアミノジフェニルスルフィド、ジアミノジフェニルスルホン、ビス（アミノフェニル）フルオレン、ジアミノジエチルジメチルジフェニルメタン、ジアミノジフェニルエーテル、ジアミノベンズアニリド、ジアミノビフェニル、ジメチルジアミノビフェニル、ビフェニルテトラアミン、ビスアミノフェニルアントラセン、ビスアミノフェノキシベンゼン、ビスアミノフェノキシフェニルエーテル、ビスアミノフェノキシビフェニル、ビスアミノフェノキシフェニルスルホン、ビスアミノフェノキシフェニルプロパン、ジアミノナフタレン等のアミン化合物が挙げられるがこれらに限定されるものではなく、これらエポキシ樹脂変性剤は単独で使用しても良いし、２種類以上を併用しても良い。 Specific examples of epoxy resin modifiers that can be used include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, bisphenol Z, bisphenol TMC, hydroquinone, methyl hydroquinone, dimethyl hydroquinone, dibutyl hydroquinone, resorcin, methyl resorcin, Biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxystilbenes, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolac resin, styrenated phenol novolac resin, terpene Phenolic resin, heavy oil modified phenol Various phenols such as fats, polyphenols obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, aniline, phenylenediamine, toluidine, xylidine, Diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone, diaminodiphenyl sulfide, diaminodiphenyl sulfone, bis (aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyl Diaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisamino Examples of amine compounds such as enoxybenzene, bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenylsulfone, bisaminophenoxyphenylpropane, and diaminonaphthalene are not limited to these, and these epoxy resin modifiers are You may use individually and may use 2 or more types together.
エポキシ樹脂水性分散体（Ａ１）に用いるエポキシ当量５００〜１００００ｇ／ｅｑ．のオキサゾリドン環含有エポキシ樹脂（ｅ）は、末端イソシアネート基含有化合物（ｃ）と、分子内に２個以上のエポキシ基を持つエポキシ樹脂（ｄ）とを、末端イソシアネート基含有化合物（ｃ）のイソシアネート基１モルに対し、エポキシ樹脂（ｄ）のエポキシ基を１．５モル以上５．０モル以下の範囲で反応させて得られる。そして、末端イソシアネート基含有化合物（ｃ）は、分子量１０００〜１００００のポリアルキレングリコール化合物（ａ）とポリイソシアネート化合物（ｂ）とを、ポリアルキレングリコール化合物（ａ）の水酸基１モルに対し、ポリイソシアネート化合物（ｂ）のイソシアネート基を１．５モル以上３．０モル以下の範囲で反応させて得られる。 Epoxy equivalent 500-10000 g / eq. Used for epoxy resin aqueous dispersion (A1). The oxazolidone ring-containing epoxy resin (e) comprises a terminal isocyanate group-containing compound (c) and an epoxy resin (d) having two or more epoxy groups in the molecule, and the isocyanate of the terminal isocyanate group-containing compound (c). It is obtained by reacting the epoxy group of the epoxy resin (d) in the range of 1.5 mol or more and 5.0 mol or less with respect to 1 mol of the group. The terminal isocyanate group-containing compound (c) is a polyisocyanate having a molecular weight of 1,000 to 10,000 and a polyisocyanate compound (a) and a polyisocyanate compound (b) with respect to 1 mol of the hydroxyl group of the polyalkylene glycol compound (a). It is obtained by reacting the isocyanate group of the compound (b) in the range of 1.5 mol or more and 3.0 mol or less.
オキサゾリドン環含有エポキシ樹脂（ｅ）の製造で用いられる末端イソシアネート基含有化合物（ｃ）と、分子内に２個以上のエポキシ基を持つエポキシ樹脂（ｄ）の使用割合は、末端イソシアネート基含有化合物（ｃ）のイソシアネート基１モルに対し、エポキシ樹脂（ｄ）のエポキシ基を１．５モル以上５．０モル以下が好ましい範囲である。エポキシ樹脂（ｄ）のエポキシ基が少ないと過剰な重合が進みゲル化が起こり易くなる恐れがあり、またイソシアネート基同士の重合によりイソシアヌレート環を生成し易くなる恐れがあるため、エポキシ基とイソシアネート基の反応率を高めるためにはエポキシ基が多少過剰にある方がよい。また多いと未反応のエポキシ樹脂が多くなり過ぎて乳化力が落ちる恐れがある。末端イソシアネート基含有化合物（ｃ）のイソシアネート基１モルに対し、エポキシ樹脂（ｄ）のエポキシ基を１．５〜４．０モルの範囲がより好ましく、１．７〜３．５モルの範囲がさらに好ましい。 The proportion of the terminal isocyanate group-containing compound (c) used in the production of the oxazolidone ring-containing epoxy resin (e) and the epoxy resin (d) having two or more epoxy groups in the molecule is as follows. The range of 1.5 mol or more and 5.0 mol or less of the epoxy group of the epoxy resin (d) is preferable with respect to 1 mol of the isocyanate group of c). If the epoxy resin (d) has a small number of epoxy groups, excessive polymerization may proceed and gelation may easily occur, and isocyanurate rings may be easily formed by polymerization of isocyanate groups. In order to increase the reaction rate of the group, it is better that the epoxy group is somewhat excessive. On the other hand, if the amount is too large, the amount of unreacted epoxy resin may increase and the emulsifying power may decrease. The epoxy group of the epoxy resin (d) is more preferably in the range of 1.5 to 4.0 mol, more preferably in the range of 1.7 to 3.5 mol with respect to 1 mol of the isocyanate group of the terminal isocyanate group-containing compound (c). Further preferred.
末端イソシアネート基含有化合物（ｃ）と分子内に２個以上のエポキシ基を持つエポキシ樹脂（ｄ）の反応は公知の方法により行うことができる。具体的な反応方法としては、末端イソシアネート含有化合物（ｃ）に分子内に２個以上のエポキシ基を持つエポキシ樹脂（ｄ）と触媒類を添加して１１０℃〜２００℃で１〜１０時間反応させることにより分子鎖内にオキサゾリドン環含有エポキシ樹脂（ｅ）を得ることができる。 The reaction of the terminal isocyanate group-containing compound (c) and the epoxy resin (d) having two or more epoxy groups in the molecule can be carried out by a known method. As a specific reaction method, an epoxy resin (d) having two or more epoxy groups in the molecule and a catalyst are added to the terminal isocyanate-containing compound (c), and the reaction is performed at 110 ° C. to 200 ° C. for 1 to 10 hours. By doing so, an oxazolidone ring-containing epoxy resin (e) can be obtained in the molecular chain.
この反応に用いられる触媒としては、トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン、ピリジン等の３級アミン、トリフェニルホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン等のホスフィン類、テトラメチルアンモニウムクロライド、ベンジルトリメチルアンモニウムクロライド、トリフェニルホスホニウムブロマイド、テトラメチルアンモニウムイオダイド等の４級アンモニウム塩、水酸化ナトリウム等のアルカリ金属酸化物等が挙げられるがこれらに限定されるものではなく、これらの触媒は単独で使用しても良いし、２種類以上併用しても良い。触媒量は末端イソシアネート基含有化合物（ｃ）に対して、０．０１〜１０質量％であり、好ましくは０．１〜１質量％である。 Catalysts used in this reaction include tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine and pyridine, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, tetramethylammonium chloride, benzyl Examples include, but are not limited to, quaternary ammonium salts such as trimethylammonium chloride, triphenylphosphonium bromide, and tetramethylammonium iodide, and alkali metal oxides such as sodium hydroxide. You may use, and may use 2 or more types together. The catalyst amount is 0.01 to 10% by mass, preferably 0.1 to 1% by mass, based on the terminal isocyanate group-containing compound (c).
また、分子内にエポキシ基を２つ以上持つエポキシ樹脂（ｄ）は特に限定されることはなく、公知のエポキシ樹脂を使用することができる。使用できるエポキシ樹脂（ｄ）としては、ビスフェノールＡ型エポキシ樹脂、例えばエポトート（登録商標）ＹＤ−１２７、エポトートＹＤ−１２８、エポトートＹＤ−８１２５、エポトートＹＤ−８２５ＧＳ、エポトートＹＤ−１３４、エポトートＹＤ−０１１、エポトートＹＤ−０１２、エポトートＹＤ−０１３、エポトートＹＤ−０１４、エポトートＹＤ−０１７、エポトートＹＤ−０１９、エポトートＹＤ−９０１、エポトートＹＤ−９０２、エポトートＹＤ−９０３、エポトートＹＤ−９０４、エポトートＹＤ−９０７、エポトートＹＤ−９０９（以上、商品名、新日鉄住金化学株式会社製）、ビスフェノールＦ型エポキシ樹脂、例えばエポトートＹＤＦ−１７０、エポトートＹＤＦ−１５００、エポトートＹＤＦ−８１７０、エポトートＹＤＦ−８７０ＧＳ、エポトートＹＤＦ−１７５Ｓ、エポトートＹＤＦ−２００１、エポトートＹＤＦ−２００４（以上、商品名、新日鉄住金化学株式会社製）、テトラメチルビスフェノールＦ型エポキシ樹脂、例えばＹＳＬＶ−８０ＸＹ、ＹＳＬＶ−７０ＸＹ（以上、商品名、新日鉄住金化学株式会社製）、ビフェノール型エポキシ樹脂、例えばＹＸ−４０００（商品名、三菱化学株式会社製）、ＺＸ−１２５１（商品名、新日鉄住金化学株式会社製）、ヒドロキノン型エポキシ樹脂、例えばエポトートＹＤＣ−１３１２、ＺＸ−１０２７（以上、商品名、新日鉄住金化学株式会社製）、ビスフェノールフルオレン型エポキシ樹脂、例えばＺＸ−１２０１（商品名、新日鉄住金化学株式会社製）、ナフタレンジオール型エポキシ樹脂、例えばＺＸ−１３５５（商品名、新日鉄住金化学株式会社製）、ビスフェノールＳ型エポキシ樹脂、例えばＴＸ−０７１０（商品名、新日鉄住金化学株式会社製）、エピクロン（登録商標）ＥＸＡ−１５１５（商品名、大日本インキ化学工業株式会社製）、ビスチオエーテル型エポキシ樹脂、例えばＹＳＬＶ−１２０ＴＥ（商品名、新日鉄住金化学株式会社製）、レゾルシノール型エポキシ樹脂、例えばエポトートＺＸ−１６８４（商品名、新日鉄住金化学株式会社製）、水添ビスフェノールＡ型エポキシ樹脂、例えばサントート（登録商標）ＳＴ−３０００、サントートＳＴ−４０００（以上、商品名、新日鉄住金化学株式会社製）、エピコート（登録商標）ＹＸ−８０００、エピコートＹＸ−８０３４（以上、商品名、三菱化学株式会社製）、フェノールノボラック型エポキシ樹脂、例えばエポトートＹＤＰＮ−６３８（以上、商品名、新日鉄住金化学株式会社製）、エピコート１５２、エピコート１５４（以上、商品名、三菱化学株式会社製）、エピクロンＮ−７４０、エピクロンＮ−７７０、エピクロンＮ−７７５（以上、商品名、ＤＩＣ株式会社製）、クレゾールノボラック型エポキシ樹脂、例えばエポトートＹＤＣＮ−７００シリーズ（商品名、新日鉄住金化学株式会社製）、エピクロンＮ−６６０、エピクロンＮ−６６５、エピクロンＮ−６７０、エピクロンＮ−６７３、エピクロンＮ−６９５（以上、商品名、ＤＩＣ株式会社製）、ＥＯＣＮ−１０２０、ＥＯＣＮ−１０２Ｓ、ＥＯＣＮ−１０４Ｓ（以上、商品名、日本化薬株式会社製）、アルキルノボラック型エポキシ樹脂、例えばエポトートＺＸ−１０７１Ｔ、ＺＸ−１２７０、ＺＸ−１３４２（以上、商品名、新日鉄住金化学株式会社製）、スチレン化フェノールノボラック型エポキシ樹脂、例えばエポトートＺＸ−１２４７、ＧＫ−５８５５、ＴＸ−１２１０（以上、商品名、新日鉄住金化学株式会社製）、ナフトールノボラック型エポキシ樹脂、例えばエポトートＺＸ−１１４２Ｌ（商品名、新日鉄住金化学株式会社製）、βナフトールアラルキル型エポキシ樹脂、例えばＥＳＮ−１５５、ＥＳＮ−１８５Ｖ、ＥＳＮ−１７５（以上、商品名、新日鉄住金化学株式会社製）、ジナフトールアラルキル型エポキシ樹脂、例えばＥＳＮ−３００シリーズのＥＳＮ−３５５、ＥＳＮ−３７５（以上、商品名、新日鉄住金化学株式会社製）、αナフトールアラルキル型エポキシ樹脂、例えばＥＳＮ−４００シリーズのＥＳＮ−４７５Ｖ、ＥＳＮ−４８５（以上、商品名、新日鉄住金化学株式会社製）、ビフェニルアラルキルフェノール型エポキシ樹脂、例えばＮＣ−３０００、ＮＣ−３０００Ｈ（以上、商品名、日本化薬株式会社製）等のポリグリシジルエーテル化合物、ネオペンチルグリコールジグリシジルエーテル、例えばＳＲ−ＮＰＧ（商品名、坂本薬品工業株式会社製）、ポリプロピレングリコールジグリシジルエーテル、例えばエポトートＰＧ−２０７、エポトートＰＧ−２０７ＧＳ（以上、商品名、新日鉄住金化学株式会社製）、トリメチロールプロパントリグルシジルエーテル、例えばエポトートＹＨ−３００、エポトートＺＸ−１６５８ＧＳ（以上、商品名、新日鉄住金化学株式会社製）、ＳＲ−ＴＭＰ（商品名、坂本薬品工業株式会社製）、１，６−ヘキサンジオールジグリシジルエーテル、例えばＳＲ−１６Ｈ、ＳＲ−１６ＨＬ（以上、商品名、坂本薬品工業株式会社製）等の脂肪族ポリグリシジルエーテル、ジアミノジフェニルメタンテトラグリシジルエーテル、例えばエポトートＹＨ−４３４、エポトートＹＨ−４３４ＧＳ（以上、商品名、新日鉄住金化学株式会社製）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−１，３−ベンゼンジ（メタンアミン）、例えばＴＥＴＲＡＤ−Ｘ（商品名、三菱ガス化学株式会社製）等のポリグリシジルアミン化合物、ダイマー酸型エポキシ樹脂、例えばＹＤ−１７１（商品名、新日鉄住金化学株式会社製）等のポリグリシジルエステル化合物、脂肪族環状エポキシ樹脂、例えばセロキサイド（登録商標）２０２１（商品名、ダイセル化学工業株式会社製）等の脂環式エポキシ化合物等が挙げられるがこれらに限定されるものではなく、これらのエポキシ樹脂は単独で使用しても良いし、２種類以上併用しても良い。 Moreover, the epoxy resin (d) having two or more epoxy groups in the molecule is not particularly limited, and a known epoxy resin can be used. Usable epoxy resins (d) include bisphenol A type epoxy resins such as Epototo (registered trademark) YD-127, Epototo YD-128, Epototo YD-8125, Epototo YD-825GS, Epototo YD-134, Epototo YD-011. Epototo YD-012, Epototo YD-013, Epototo YD-014, Epototo YD-017, Epototo YD-019, Epototo YD-901, Epototo YD-902, Epototo YD-903, Epototo YD-904, Epoto Y 7 , Epototo YD-909 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol F type epoxy resin, for example, Epotot YDF-170, Epototo YDF-1500, Epototo YDF-8170, E Tote YDF-870GS, Epototo YDF-175S, Epototo YDF-2001, Epototo YDF-2004 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), tetramethylbisphenol F type epoxy resin such as YSLV-80XY, YSLV-70XY ( Above, trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenol type epoxy resin, for example, YX-4000 (trade name, manufactured by Mitsubishi Chemical Co., Ltd.), ZX-1251 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroquinone type Epoxy resins such as Epototo YDC-1312, ZX-1027 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol fluorene type epoxy resins such as ZX-1201 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalenediol Type epoxy tree For example, ZX-1355 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol S type epoxy resin, for example TX-0710 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicron (registered trademark) EXA-1515 (trade name) , Dainippon Ink Chemical Co., Ltd.), bisthioether type epoxy resins such as YSLV-120TE (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), resorcinol type epoxy resins such as Epototo ZX-1684 (trade name, Nippon Steel & Sumikin Chemical) Co., Ltd.), hydrogenated bisphenol A type epoxy resin such as Santo Tote (registered trademark) ST-3000, Santo Tote ST-4000 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicote (registered trademark) YX-8000, Epicoat YX-8034 (above, trade name, Mitsubishi Chemical Corporation) Manufactured by Co., Ltd.), phenol novolac type epoxy resin, such as Epototo YDPN-638 (above, trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (above, trade name, manufactured by Mitsubishi Chemical Corporation), Epicron N- 740, Epicron N-770, Epicron N-775 (trade name, manufactured by DIC Corporation), Cresol novolac type epoxy resin such as Epototo YDCN-700 series (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicron N- 660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-695 (above, trade name, manufactured by DIC Corporation), EOCN-1020, EOCN-102S, EOCN-104S (above, trade name, Nippon Kayaku Co., Ltd.), alkyl novolac type Poxy resins such as Epototo ZX-1071T, ZX-1270, ZX-1342 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), styrenated phenol novolac type epoxy resins such as Epototo ZX-1247, GK-5855, TX- 1210 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthol novolac type epoxy resin, for example, Epototo ZX-1142L (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), β-naphthol aralkyl type epoxy resin, for example, ESN-155, ESN-185V, ESN-175 (above, trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), dinaphthol aralkyl type epoxy resin, for example, ESN-300 series ESN-355, ESN-375 (above, trade name, NS Manufactured by Co., Ltd.) Aralkyl type epoxy resins such as ESN-400 series ESN-475V, ESN-485 (above, trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl aralkyl phenol type epoxy resins such as NC-3000, NC-3000H (above, Polyglycidyl ether compounds such as trade name, manufactured by Nippon Kayaku Co., Ltd.), neopentyl glycol diglycidyl ether, such as SR-NPG (trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), polypropylene glycol diglycidyl ether, such as Epototo PG- 207, epototo PG-207GS (above, trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), trimethylolpropane triglycidyl ether such as epototo YH-300, epototo ZX-1658GS (above, trade name, NS SR-TMP (trade name, manufactured by Sakamoto Pharmaceutical Co., Ltd.), 1,6-hexanediol diglycidyl ether, such as SR-16H, SR-16HL (trade name, manufactured by Sakamoto Pharmaceutical Co., Ltd.) ) Aliphatic polyglycidyl ether, diaminodiphenylmethane tetraglycidyl ether such as epototo YH-434, epototo YH-434GS (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), N, N, N ′, N′-tetra Polyglycidylamine compounds such as glycidyl-1,3-benzenedi (methanamine) such as TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), dimer acid type epoxy resins such as YD-171 (trade name, Nippon Steel & Sumikin Chemical) Polyglycidyl ester compounds, aliphatic cyclic epoxy resins, etc. Examples include, but are not limited to, alicyclic epoxy compounds such as Celoxide (registered trademark) 2021 (trade name, manufactured by Daicel Chemical Industries, Ltd.), and these epoxy resins may be used alone. It is good and two or more types may be used together.
末端イソシアネート基含有化合物（ｃ）の製造で用いられるポリアルキレングリコール化合物（ａ）とポリイソシアネート化合物（ｂ）の使用割合は、ポリアルキレングリコール化合物（ａ）の水酸基１モルに対し、ポリイソシアネート化合物（ｂ）のイソシアネート基は１．５モル以上３．０モル以下が好ましい範囲である。ポリイソシアネート化合物（ｂ）のイソシアネート基が少ないと重合が進み分子量が大きくなり過ぎる恐れがあり、多いと反応に関与しないイソシアネートが多くなる恐れがある。ポリアルキレングリコール化合物（ａ）の水酸基１モルに対し、１．７モル以上２．５モル以下の範囲がより好ましく、１．８モル以上２．２モル以下の範囲がさらに好ましい。 The polyalkylene glycol compound (a) and the polyisocyanate compound (b) used in the production of the terminal isocyanate group-containing compound (c) are used in a proportion of 1 mol of the hydroxyl group of the polyalkylene glycol compound (a). The isocyanate group of b) is preferably in the range of 1.5 mol to 3.0 mol. When there are few isocyanate groups of a polyisocyanate compound (b), there exists a possibility that superposition | polymerization may advance and molecular weight may become large too much, and when there are many, there exists a possibility that the isocyanate which does not participate in reaction may increase. The range of 1.7 mol or more and 2.5 mol or less is more preferable with respect to 1 mol of the hydroxyl group of the polyalkylene glycol compound (a), and the range of 1.8 mol or more and 2.2 mol or less is more preferable.
ポリアルキレングリコール化合物（ａ）の分子量（数平均）は、１０００〜１００００であり、好ましくは２０００〜１００００であり、より好ましくは２０００〜８０００である。分子量が小さいと乳化性が悪くなる恐れがあり、大きいと耐水性が損なわれる恐れがある。ポリアルキレングリコール化合物（ａ）としては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリペンタメチレングリコール、ポリヘキサメチレングリコール等が挙げられるがこれらに限定されるものではなく、これらのポリアルキレングリコール化合物は単独で使用しても良いし、２種類以上併用しても良い。これらの中では、ポリエチレングリコールが好ましい。 The molecular weight (number average) of the polyalkylene glycol compound (a) is 1000 to 10000, preferably 2000 to 10000, more preferably 2000 to 8000. If the molecular weight is small, the emulsifiability may be deteriorated, and if it is large, the water resistance may be impaired. Examples of the polyalkylene glycol compound (a) include, but are not limited to, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, and the like. These polyalkylene glycol compounds May be used alone or in combination of two or more. Of these, polyethylene glycol is preferred.
ポリイソシアネート化合物（ｂ）としては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、１，５−ナフタレ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、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、トリジンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネ−ト等が挙げられるがこれらに限定されるものではなく、これらのポリイソシアネート化合物は単独で使用しても良いし、２種類以上併用しても良い。これらの中では、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート等の芳香族ジイソシアネートが好ましい。 Examples of the polyisocyanate compound (b) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-cyclohexane. Examples include, but are not limited to, diisocyanates, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, tolidine diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and these polyisocyanates. The compounds may be used alone or in combination of two or more. Among these, aromatic diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are preferable.
ポリアルキレングリコール化合物（ａ）とポリイソシアネート化合物（ｂ）の反応は公知の方法で行うことができる。具体的な方法としては、ポリアルキレングリコール化合物（ａ）を溶融加熱してガスパージ、減圧により系内の水分を除去した後に、ポリイソシアネート化合物（ｂ）とを、触媒存在下または無触媒で５０℃〜１５０℃にて０．５〜１０時間反応させることにより末端イソシアネート化合物を製造することができる。この反応に用いられる触媒としては、トリエチルアミン、ジメチルベンジルアミン、ピリジン等の３級アミン、ジブチルスズジラウレート等の有機金属化合物等が挙げられるがこれらに限定されるものではなく、これらの触媒は単独で使用しても良いし、２種類以上併用しても良い。触媒量は用いるポリイソシアネート化合物（ｂ）に対して０．００１〜０．５質量％である。 The reaction of the polyalkylene glycol compound (a) and the polyisocyanate compound (b) can be performed by a known method. As a specific method, after the polyalkylene glycol compound (a) is melted and heated, gas purge, and moisture in the system is removed by decompression, the polyisocyanate compound (b) is added at 50 ° C. in the presence of a catalyst or without a catalyst. A terminal isocyanate compound can be manufactured by making it react at -150 degreeC for 0.5 to 10 hours. Examples of the catalyst used in this reaction include tertiary amines such as triethylamine, dimethylbenzylamine and pyridine, and organometallic compounds such as dibutyltin dilaurate, but these catalysts are not limited to these, and these catalysts are used alone. Alternatively, two or more types may be used in combination. A catalyst amount is 0.001-0.5 mass% with respect to the polyisocyanate compound (b) to be used.
本発明の水性硬化性組成物に用いるエポキシ樹脂水性分散体（Ａ）と水性反応性希釈剤（Ｂ）に対する、硬化剤（Ｃ）の配合割合も重要である。（Ｃ）の活性水素基は、（Ａ）と（Ｂ）の全エポキシ基１モルに対し、０．７モル以上１．１モル以下の範囲である。これにより塗料の硬化性の最適化や作業性の向上、及び塗膜物性の最適化を行うことができる。（Ｃ）の活性水素基は、（Ａ）と（Ｂ）の全エポキシ基１モルに対し、０．８モル以上１．１モル以下の範囲が好ましく、０．９モル以上１．０５モル以下の範囲がより好ましい。 The blending ratio of the curing agent (C) to the aqueous epoxy resin dispersion (A) and the aqueous reactive diluent (B) used in the aqueous curable composition of the present invention is also important. The active hydrogen group of (C) is in the range of 0.7 mol or more and 1.1 mol or less with respect to 1 mol of all the epoxy groups of (A) and (B). Thereby, the sclerosis | hardenability of a coating material, the improvement of workability | operativity, and the coating-film physical property can be optimized. The active hydrogen group of (C) is preferably in the range of 0.8 mol to 1.1 mol, preferably 0.9 mol to 1.05 mol, per mol of all the epoxy groups of (A) and (B). The range of is more preferable.
本発明でいう活性水素基とは、エポキシ基と反応性の活性水素を有する官能基（加水分解等により活性水素を生ずる潜在性活性水素を有する官能基や、同等な硬化作用を示す官能基を含む。）のことであり、具体的には、酸無水物基やカルボキシル基やアミノ基やフェノール性水酸基等が挙げられる。なお、活性水素基に関して、１モルのカルボキシル基やフェノール性水酸基は１モルと、アミノ基（ＮＨ２）は２モルと計算される。また、活性水素基が明確ではない場合は、測定によって活性水素当量を求めることができる。例えば、エポキシ当量が既知の、フェニルグリシジルエーテル等のモノエポキシ樹脂と活性水素当量が未知の硬化剤を反応させて、消費したモノエポキシ樹脂の量を測定することによって、使用した硬化剤の活性水素当量を求めることができる。 The active hydrogen group in the present invention means a functional group having an active hydrogen reactive with an epoxy group (a functional group having a latent active hydrogen that generates active hydrogen by hydrolysis or the like, or a functional group having an equivalent curing action). Specifically, an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and the like can be given. In addition, regarding an active hydrogen group, 1 mol of carboxyl groups and phenolic hydroxyl groups are calculated as 1 mol, and an amino group (NH 2 ) is calculated as 2 mol. If the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, by reacting a monoepoxy resin such as phenyl glycidyl ether with a known epoxy equivalent with a curing agent with an unknown active hydrogen equivalent, and measuring the amount of monoepoxy resin consumed, the active hydrogen of the used curing agent Equivalent weight can be determined.
硬化剤（Ｃ）としては、各種フェノール樹脂類、酸無水物類、アミン類、ヒドラジド類、酸性ポリエステル類等の通常使用されるエポキシ樹脂用硬化剤を使用することができる。これらの硬化剤は単独で使用しても良いし、２種類以上併用しても良い。これらのうち、アミン系硬化剤が特に好ましい。 As a hardening | curing agent (C), normally used hardening | curing agents for epoxy resins, such as various phenol resins, acid anhydrides, amines, hydrazides, acidic polyesters, can be used. These curing agents may be used alone or in combination of two or more. Of these, amine curing agents are particularly preferred.
使用できるアミン系硬化剤としては、ポリアミノアミド類、エポキシ樹脂アミンアダクト、脂肪族ポリアミン、変性ポリアミン、第３アミン、ヒドラジド、イミダゾール等通常のエポキシ樹脂に使用される硬化剤が使用可能であるが、特にポリアミノアミド類、エポキシ樹脂アミンアダクト等が好ましい。 Examples of amine curing agents that can be used include polyaminoamides, epoxy resin amine adducts, aliphatic polyamines, modified polyamines, tertiary amines, hydrazides, imidazoles, and other curing agents used in ordinary epoxy resins. Particularly preferred are polyaminoamides, epoxy resin amine adducts and the like.
本発明の水性硬化性組成物は必要に応じて、石油樹脂、クマロンインデン樹脂、キシレン樹脂、ケトン樹脂等の非反応性希釈剤より選ばれた１種または２種以上の樹脂を所望の目的範囲で含有することができる。また、各種用途に応じてタルク、炭酸カルシウム、シリカ、カーボン等の充填材や、ベンガラ、酸化チタン、硫化亜鉛、酸化鉄等の顔料及び増粘剤、消泡剤、可塑剤等の添加剤を適量配合することができる。 The water-based curable composition of the present invention can be obtained by using one or more resins selected from non-reactive diluents such as petroleum resins, coumarone indene resins, xylene resins, and ketone resins as desired. It can be contained in a range. In addition, fillers such as talc, calcium carbonate, silica, carbon, etc., pigments such as bengara, titanium oxide, zinc sulfide, iron oxide, thickeners, antifoaming agents, plasticizers, etc. are added according to various applications. An appropriate amount can be blended.
本発明の水性硬化性組成物は、水性の反応性希釈剤を含むため、反応性希釈剤を含まない水性硬化性組成物または非水性の反応性希釈剤を含む水性硬化性組成物を使用した場合のように硬化塗膜の光沢が失われることなく、外観が良好な、耐食性、耐水性に優れた硬化塗膜が得られる。また乳化安定性にも優れ、作業性にも優れたものである。
[実施例及び比較例]
Since the aqueous curable composition of the present invention contains an aqueous reactive diluent, an aqueous curable composition containing no reactive diluent or an aqueous curable composition containing a non-aqueous reactive diluent was used. A cured coating film with good appearance, excellent corrosion resistance and water resistance can be obtained without losing the gloss of the cured coating film as in the case. Moreover, it is excellent in emulsion stability and workability.
[Examples and Comparative Examples]
以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。特に断りがない限り「部」は質量部を表し、「％」は質量％を表す。測定方法はそれぞれ以下の方法により測定した。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these. Unless otherwise specified, “parts” represents parts by mass, and “%” represents mass%. The measurement method was measured by the following methods.
エポキシ当量：ＪＩＳ Ｋ７２３６規格に準じた。 Epoxy equivalent: Conforms to JIS K7236 standard.
粘度：ＪＩＳ Ｋ７２３３規格、単一円筒回転粘度計法に準じた。 Viscosity: Conforms to JIS K7233 standard, single cylinder rotational viscometer method.
平均粒径：レーザー回折・散乱法で測定した。具体的には、マイクロトラックＭＴ−３３００ＥＸII測定機（日機装株式会社製）を使用した。 Average particle diameter: measured by laser diffraction / scattering method. Specifically, a Microtrac MT-3300EXII measuring machine (manufactured by Nikkiso Co., Ltd.) was used.
水との溶解度：２５℃の恒温水槽中で、イオン交換水１００ｇに試料（反応性希釈剤）を０．１ｇずつを添加、混合して、未溶解分や分離の有無を目視で判断した。溶解度は未溶解分や分離の発生が起こる直前の量（ｇ）とした。なお、添加量が５０ｇを越えた場合はその時点で操作を終了した。 Solubility with water: In a constant temperature bath of 25 ° C., 0.1 g of a sample (reactive diluent) was added to and mixed with 100 g of ion-exchanged water, and the presence or absence of separation was visually determined. The solubility was the amount (g) immediately before the occurrence of undissolved matter and separation. When the addition amount exceeded 50 g, the operation was terminated at that time.
密着性及び耐水性：ＪＩＳ Ｋ５６００−５−６規格に準じた。塗膜に１００個の２ｍｍ×２ｍｍの碁盤目を基板に至る深さでカッターナイフで切り込みを入れてからセロハンテープを貼って瞬間的に引き剥がし、基板上に残っている碁盤目数を目視で判定した。
耐水性（１）は、２３℃のイオン交換水に１日浸漬した後の塗膜を対象とした。
耐水性（２）は、２３℃のイオン交換水に１日浸漬し、温度２３℃、湿度５５ＲＨ％の恒温恒湿装置に２日保管した後の塗膜を対象とした。判定はＪＩＳ規格の分類に従った。
Adhesion and water resistance: Conforms to JIS K5600-5-6 standard. Cut 100 2 mm x 2 mm grids on the coating film with a cutter knife at a depth to reach the substrate, then apply cellophane tape and peel it off instantaneously, and visually check the number of grids remaining on the substrate. Judged.
The water resistance (1) was for a coating film immersed in ion exchange water at 23 ° C. for 1 day.
The water resistance (2) was applied to the coating film after being immersed in ion exchange water at 23 ° C. for 1 day and stored for 2 days in a constant temperature and humidity apparatus at a temperature of 23 ° C. and a humidity of 55 RH%. The judgment was in accordance with the classification of JIS standard.
光沢性：ＪＩＳ Ｋ５６００−４−７規格に準じた。具体的には、可変角度光沢計（有限会社 東京電色製、ＴＣ−１０８ＤＰ／Ａ）と測色色差計（有限会社 東京電色製、ＴＣ−１５００ＭＣ−８８）を使用して、入射角度６０°で測定した。 Glossiness: Conforms to JIS K5600-4-7 standard. Specifically, using a variable angle gloss meter (manufactured by Tokyo Denshoku, TC-108DP / A) and a colorimetric color difference meter (manufactured by Tokyo Denshoku, TC-1500MC-88), an incident angle of 60 Measured at °.
合成例１
撹拌機、温度計、冷却管及び窒素ガス導入装置を備えたガラス製４ツ口の反応装置に、分子量３２００のポリエチレングリコールを４８０部仕込み、窒素ガスを導入１２０℃まで加熱溶融し、脱水を行った。その後７０℃まで冷却しコロネート（登録商標）Ｔ−８０（製品名、三井化学株式会社製、２，４−トリレンジイソシアネート（８０％）と２，６−トリレンジイソシアネート（２０％）の混合物、ＮＣＯ濃度４８％）を５５．７部仕込み、８０℃で５時間保持した。次にエポトートＹＤ−１２８（新日鉄住金化学株式会社製、ビスフェノールＡ型液状エポキシ樹脂、エポキシ当量１８７ｇ／ｅｑ．）を１８０部仕込み１２０℃まで昇温した後、触媒としてテトラメチルアンモニウムブロマイドを０．８部添加し、１５０℃で５時間反応させＩＲ測定によるイソシアネートの消失を確認し、オキサゾリドン環含有エポキシ樹脂ｅ１を得た。得られたオキサゾリドン環含有エポキシ樹脂ｅ１のエポキシ当量は１１２０ｇ／ｅｑ．であった。
Synthesis example 1
480 parts of polyethylene glycol having a molecular weight of 3200 is charged into a glass four-necked reactor equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introducing device, and nitrogen gas is introduced and heated to 120 ° C. for dehydration. It was. Thereafter, it was cooled to 70 ° C. and Coronate (registered trademark) T-80 (product name, manufactured by Mitsui Chemicals, Inc., a mixture of 2,4-tolylene diisocyanate (80%) and 2,6-tolylene diisocyanate (20%), 55.7 parts of NCO concentration 48%) was charged and held at 80 ° C. for 5 hours. Next, 180 parts of Epototo YD-128 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type liquid epoxy resin, epoxy equivalent 187 g / eq.) Was charged to 120 ° C., and then tetramethylammonium bromide as a catalyst was added to 0.8. Part was added and reacted at 150 ° C. for 5 hours to confirm the disappearance of isocyanate by IR measurement to obtain an oxazolidone ring-containing epoxy resin e1. The epoxy equivalent of the obtained oxazolidone ring-containing epoxy resin e1 was 1120 g / eq. Met.
得られたオキサゾリドン環含有エポキシ樹脂ｅ１を５５部、エポトートＹＤ−１２８を４９５部混合し、撹拌しながら、イオン交換水４５０部を徐々に加えて、エポキシ樹脂水性分散体Ａ１を得た。得られたエポキシ樹脂水性分散体Ａ１（樹脂分５５％、固形分エポキシ当量２０４ｇ／ｅｑ．、平均粒径０．６μｍ）は、２０℃で９０日保管した後の目視判断では分離無く、乳化安定性は良好だった。 55 parts of the obtained oxazolidone ring-containing epoxy resin e1 and 495 parts of epototo YD-128 were mixed, and 450 parts of ion-exchanged water was gradually added while stirring to obtain an aqueous epoxy resin dispersion A1. The obtained epoxy resin aqueous dispersion A1 (resin content: 55%, solid content epoxy equivalent: 204 g / eq., Average particle size: 0.6 μm) was emulsion-stable without visual separation after storage at 20 ° C. for 90 days. The sex was good.
合成例２
合成例１で得られたオキサゾリドン環含有エポキシ樹脂ｅ１を５５部、エポトートＹＤ−０１１（新日鉄住金化学株式会社製、ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量４７０ｇ／ｅｑ．）を４９５部、有機溶剤としてエチレングリコールモノブチルエーテルを１００部混合し、撹拌しながら、イオン交換水３５０部を徐々に加えて、エポキシ樹脂水性分散体Ａ２を得た。得られたエポキシ樹脂水性分散体Ａ２（樹脂分５５％、固形分エポキシ当量５０４ｇ／ｅｑ．、均粒径０．６μｍ）は、２０℃で９０日保管した後の目視判断では分離無く、乳化安定性は良好だった。
Synthesis example 2
55 parts of the oxazolidone ring-containing epoxy resin e1 obtained in Synthesis Example 1 and 495 parts of Epototo YD-011 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type solid epoxy resin, epoxy equivalent 470 g / eq.) As an organic solvent 100 parts of ethylene glycol monobutyl ether was mixed and 350 parts of ion-exchanged water was gradually added while stirring to obtain an aqueous epoxy resin dispersion A2. The obtained epoxy resin aqueous dispersion A2 (resin content: 55%, solid content epoxy equivalent: 504 g / eq., Average particle size: 0.6 μm) is emulsion-stable without visual separation after storage at 20 ° C. for 90 days. The sex was good.
合成例３
撹拌機、温度計、冷却管及び窒素ガス導入装置を備えたガラス製４ツ口の反応装置に、分子量３２００のポリエチレングリコールを２５６部と分子量８０００のポリエチレングリコールを５６０部仕込み、窒素ガスを導入１２０℃まで加熱溶融し、脱水を行った。その後７０℃まで冷却しコロネートＴ−８０を５５．７部仕込み８０℃で５時間保持した。次にエポトートＰＧ−２０７（新日鉄住金化学株式会社製、ポリプロピレングリコールジグリシジルエーテル、エポキシ当量３２０ｇ／ｅｑ．）を２１８部仕込み、１２０℃まで昇温した後、触媒としてテトラメチルアンモニウムブロマイドを１．２部添加し、１５０℃で５時間反応させＩＲ測定によるイソシアネート消失を確認し、オキサゾリドン環含有エポキシ樹脂ｅ２を得た。得られたオキサゾリドン環含有エポキシ樹脂ｅ２のエポキシ当量は３２１０ｇ／ｅｑ．であった。
Synthesis example 3
A glass four-necked reactor equipped with a stirrer, thermometer, condenser and nitrogen gas introduction device is charged with 256 parts of polyethylene glycol having a molecular weight of 3200 and 560 parts of polyethylene glycol having a molecular weight of 8000, and nitrogen gas is introduced. The mixture was melted by heating to ° C. and dehydrated. Thereafter, the mixture was cooled to 70 ° C., 55.7 parts of Coronate T-80 was charged, and held at 80 ° C. for 5 hours. Next, 218 parts of Epototo PG-207 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., polypropylene glycol diglycidyl ether, epoxy equivalent 320 g / eq.) Was charged and the temperature was raised to 120 ° C. Then, tetramethylammonium bromide as a catalyst was added in 1.2. Part was added and reacted at 150 ° C. for 5 hours to confirm the disappearance of isocyanate by IR measurement to obtain an oxazolidone ring-containing epoxy resin e2. Epoxy equivalent of the obtained oxazolidone ring-containing epoxy resin e2 was 3210 g / eq. Met.
得られたオキサゾリドン環含有エポキシ樹脂ｅ２を５５部、エポトートＹＤ−１２８を３８５部、ビスフェノールＡを１１０部仕込、触媒としてトリフェニルホスフィンを０．１部添加して、１５０℃で５時間反応させエポキシ当量４９５ｇ／ｅｑ．の樹脂を得た。そこに、エチレングリコールモノブチルエーテルを１００部混合し、撹拌しながら、イオン交換水３５０部を徐々に加えて、エポキシ樹脂水性分散体Ａ３（樹脂分５５％、固形分エポキシ当量４９５ｇ／ｅｑ．、平均粒径０．６μｍ）を得た。得られたエポキシ樹脂水性分散体Ａ３は、２０℃で９０日保管した後の目視判断では分離無く、乳化安定性は良好だった。 55 parts of the obtained oxazolidone ring-containing epoxy resin e2, 385 parts of epototo YD-128, 110 parts of bisphenol A, 0.1 part of triphenylphosphine as a catalyst were added and reacted at 150 ° C. for 5 hours to give an epoxy. Equivalent 495 g / eq. Of resin was obtained. Thereto, 100 parts of ethylene glycol monobutyl ether was mixed, and 350 parts of ion-exchanged water was gradually added while stirring to obtain an epoxy resin aqueous dispersion A3 (resin content 55%, solid content epoxy equivalent 495 g / eq., Average). A particle size of 0.6 μm) was obtained. The obtained epoxy resin aqueous dispersion A3 was not separated by visual judgment after storage at 20 ° C. for 90 days, and the emulsion stability was good.
実施例及び比較例で使用した略号の説明は以下のとおりである。 The abbreviations used in Examples and Comparative Examples are as follows.
（エポキシ樹脂水性分散体）
エポキシ樹脂水性分散体Ａ１：合成例１で得られたエポキシ樹脂水性分散体
エポキシ樹脂水性分散体Ａ２：合成例２で得られたエポキシ樹脂水性分散体
エポキシ樹脂水性分散体Ａ３：合成例３で得られたエポキシ樹脂水性分散体
(Epoxy resin aqueous dispersion)
Epoxy resin aqueous dispersion A1: Epoxy resin aqueous dispersion obtained in Synthesis Example 1 Epoxy resin aqueous dispersion A2: Epoxy resin aqueous dispersion obtained in Synthesis Example 2 Epoxy resin aqueous dispersion A3: Obtained in Synthesis Example 3 Epoxy resin aqueous dispersion
（反応性希釈剤）
反応性希釈剤Ｂ１：エチレングリコールジグリシジルエーテル（ＳＲ−ＥＧＭ、坂本薬品工業株式会社製、エポキシ当量１３０ｇ／ｅｑ．、粘度２０ｍＰａ・ｓ、水との溶解度５０ｇ／水１００ｇ以上）
反応性希釈剤Ｂ２：ジエチレングリコールジグリシジルエーテル（ＳＲ−２ＥＧ、坂本薬品工業株式会社製、エポキシ当量１５０ｇ／ｅｑ．、粘度２５ｍＰａ・ｓ、水との溶解度５０ｇ／水１００ｇ以上）
反応性希釈剤Ｂ３：１，６−ヘキサンジオールジグリシジルエーテル（ＳＲ−１６Ｈ、坂本薬品工業株式会社製、エポキシ当量１６０ｇ／ｅｑ．、粘度２５ｍＰａ・ｓ、水との溶解度０．２ｇ／水１００ｇ）
反応性希釈剤Ｂ４：Ｃ１５〜１６混合アルコールモノグリシジルエーテル（エポゴーセー（登録商標）ＡＮ、四日市合成株式会社製、エポキシ当量３００ｇ／ｅｑ．、粘度８ｍＰａ・ｓ、水との溶解度０．１ｇ／水１００ｇ未満）
(Reactive diluent)
Reactive diluent B1: Ethylene glycol diglycidyl ether (SR-EGM, Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent 130 g / eq., Viscosity 20 mPa · s, solubility in water 50 g / water 100 g or more)
Reactive diluents B2: diethylene Les glycol diglycidyl ether (. SR-2EG, Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent 150 g / eq, viscosity 25 mPa · s, solubility 50 g / 100g water or with water)
Reactive diluent B3: 1,6-hexanediol diglycidyl ether (SR-16H, Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent 160 g / eq., Viscosity 25 mPa · s, solubility in water 0.2 g / 100 g water)
Reactive diluent B4: C15-16 mixed alcohol monoglycidyl ether (Epogosei (registered trademark) AN, Yokkaichi Gosei Co., Ltd., epoxy equivalent 300 g / eq., Viscosity 8 mPa · s, water solubility 0.1 g / water 100 g Less than)
（硬化剤）
硬化剤Ｃ１：水溶性変性ポリアミドアミン（ＴＸＨ−６７４−Ｂ、株式会社 Ｔ＆Ｋ ＴＯＫＡ製、活性水素当量２００ｇ／ｅｑ．、樹脂分７０％）
硬化剤Ｃ２：水溶性変性脂肪族ポリアミン（ＦＸＩ−９１９、株式会社 Ｔ＆Ｋ ＴＯＫＡ製、活性水素当量２００ｇ／ｅｑ．、樹脂分８０％）
(Curing agent)
Curing agent C1: Water-soluble modified polyamidoamine (TXH-674-B, manufactured by T & K TOKA, active hydrogen equivalent 200 g / eq., Resin content 70%)
Curing agent C2: Water-soluble modified aliphatic polyamine (FXI-919, manufactured by T & K TOKA, active hydrogen equivalent 200 g / eq., Resin content 80%)
実施例１〜６、比較例１〜３
表１に示す配合量（部）で配合して、樹脂分５０％の水性硬化性組成物（塗料）を得た。なお、表中の「（Ａ）／（Ｂ）比」はエポキシ樹脂水性分散体／反応性希釈剤の質量比を、「（Ｃ）／（Ａ）モル比」はエポキシ樹脂水性分散体及び反応性希釈剤の全エポキシ基の1モルに対する硬化剤の活性水素基のモル比を、「−」は不使用をそれぞれ表す。
Examples 1-6, Comparative Examples 1-3
Blended in the blending amount (parts) shown in Table 1, an aqueous curable composition (paint) having a resin content of 50% was obtained. In the table, “(A) / (B) ratio” is the mass ratio of the epoxy resin aqueous dispersion / reactive diluent, and “(C) / (A) molar ratio” is the epoxy resin aqueous dispersion and reaction. The molar ratio of the active hydrogen group of the curing agent to 1 mol of all the epoxy groups of the reactive diluent, and “-” represents nonuse.
得られた水性硬化性組成物を、メチルエチルケトンで拭き洗浄を行ったスレート板（ＦＢ（ＰＳ−Ｎ）、株式会社 ノザワ製）に、湿潤膜厚が１５０μｍになるようにバーコーターで塗装し、温度２３℃、湿度５５ＲＨ％の恒温恒湿装置内で４日間乾燥させた。得られた塗膜で、密着性、耐水性を評価した。評価結果を表１に示す。 The obtained aqueous curable composition was applied to a slate plate (FB (PS-N), manufactured by Nozawa Co., Ltd.) that had been wiped and washed with methyl ethyl ketone, with a bar coater so that the wet film thickness was 150 μm. It was dried for 4 days in a constant temperature and humidity apparatus at 23 ° C. and humidity 55 RH%. The obtained coating film was evaluated for adhesion and water resistance. The evaluation results are shown in Table 1.
実施例７〜１２、比較例４〜６
表２に示す配合量（部）で配合して、樹脂分４５％の水性硬化性組成物（塗料）を得た。なお、表中の「（Ａ）／（Ｂ）比」はエポキシ樹脂水性分散体／反応性希釈剤の質量比を、「（Ｃ）／（Ａ）モル比」はエポキシ樹脂水性分散体及び反応性希釈剤の全エポキシ基の1モルに対する硬化剤の活性水素基のモル比を、「−」は不使用をそれぞれ表す。
Examples 7-12, Comparative Examples 4-6
Blended in the blending amounts (parts) shown in Table 2, an aqueous curable composition (paint) having a resin content of 45% was obtained. In the table, “(A) / (B) ratio” is the mass ratio of the epoxy resin aqueous dispersion / reactive diluent, and “(C) / (A) molar ratio” is the epoxy resin aqueous dispersion and reaction. The molar ratio of the active hydrogen group of the curing agent to 1 mol of all the epoxy groups of the reactive diluent, and “-” represents nonuse.
得られた水性硬化性組成物を、メチルエチルケトンで拭き洗浄を行ったスレート板（ＦＢ（ＰＳ−Ｎ）、株式会社 ノザワ製）に、湿潤膜厚が２ｍｍになるようにバーコーターで塗装し、温度２３℃、湿度５５ＲＨ％の恒温恒湿装置内で７日間乾燥させた。得られた塗膜で、光沢性を評価した。評価結果を表２に示す。 The obtained aqueous curable composition was applied to a slate plate (FB (PS-N), manufactured by Nozawa Co., Ltd.), which was wiped and washed with methyl ethyl ketone, with a bar coater so that the wet film thickness was 2 mm. It was dried for 7 days in a constant temperature and humidity apparatus at 23 ° C. and humidity 55 RH%. The gloss was evaluated with the obtained coating film. The evaluation results are shown in Table 2.
Claims (10)
該エポキシ樹脂水性分散体（Ａ）は、エポキシ当量５００〜１００００ｇ／ｅｑ．のオキサゾリドン環含有エポキシ樹脂（ｅ）とそれ以外のエポキシ樹脂（ｆ）と水（ｇ）とからなり、
該オキサゾリドン環含有エポキシ樹脂（ｅ）は、分子量１０００〜１００００のポリアルキレングリコール化合物（ａ）とポリイソシアネート化合物（ｂ）とを、（ａ）の水酸基１モルに対し、（ｂ）のイソシアネート基を１．５モル以上３．０モル以下の範囲で反応させて得られる末端イソシアネート基含有化合物（ｃ）と、分子内に２個以上のエポキシ基を持つエポキシ樹脂（ｄ）とを、（ｃ）のイソシアネート基１モルに対し、（ｄ）のエポキシ基を１．５モル以上５．０モル以下の範囲で反応させて得られ、
（ｅ）と（ｆ）と（ｇ）の割合は、質量比で（ｅ）：（ｆ）＝５：９５〜５０：５０の範囲であり、かつ｛（ｅ）＋（ｆ）｝：（ｇ）＝３０：７０〜７５：２５の範囲であり、
該反応性希釈剤（Ｂ）は、２５℃における水との溶解度が１０ｇ／水１００ｇ以上であるエポキシ樹脂であり、
該硬化剤（Ｃ）は、水溶性アミン系硬化剤であり、
（Ａ）と（Ｂ）と（Ｃ）の割合は、質量比で（Ａ）：（Ｂ）＝７０：３０〜９９：１の範囲であり、かつ（Ａ）と（Ｂ）の全エポキシ基１モルに対し、（Ｃ）の活性水素基が０．７モル以上１．１モル以下の範囲であることを特徴とする水性硬化性組成物 Aqueous epoxy resin dispersion (A) and seeing containing a reactive diluent (B) and the curing agent (C), an aqueous curable composition containing no surfactant,
The epoxy resin aqueous dispersion (A) has an epoxy equivalent of 500 to 10,000 g / eq. An oxazolidone ring-containing epoxy resin (e), another epoxy resin (f) and water (g),
The oxazolidone ring-containing epoxy resin (e) comprises a polyalkylene glycol compound (a) having a molecular weight of 1000 to 10,000 and a polyisocyanate compound (b) having an isocyanate group of (b) with respect to 1 mol of the hydroxyl group of (a). A terminal isocyanate group-containing compound (c) obtained by reacting in the range of 1.5 mol or more and 3.0 mol or less, and an epoxy resin (d) having two or more epoxy groups in the molecule, (c) It is obtained by reacting the epoxy group of (d) in the range of 1.5 mol or more and 5.0 mol or less with respect to 1 mol of the isocyanate group of
The ratio of (e), (f) and (g) is in the range of (e) :( f) = 5: 95-50: 50 by mass ratio and {(e) + (f)} :( g) = 30: 70 to 75:25,
The reactive diluent (B) is an epoxy resin having a solubility in water at 25 ° C. of 10 g / 100 g or more of water,
The curing agent (C) is a water-soluble amine curing agent,
The ratio of (A), (B), and (C) is in the range of (A) :( B) = 70: 30 to 99: 1 by mass ratio, and all the epoxy groups of (A) and (B) The aqueous curable composition characterized in that the active hydrogen group of (C) is in the range of 0.7 mol to 1.1 mol with respect to 1 mol.
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